Role of perfluorosulfonic ionomer as protective agent against strong adsorption of (bi)sulfate anions. Relevance in the determination of the area of Pt/C electrocatalysts

This work aims to shed light on the wide dispersion of the values of the area of Pt/C electrodes reported when evaluated by means of the thin-film electrode approach. The effect of the Perfluorosulfonic Ionomer (PFSI) content of the electrodes and the nature of the electrolyte are discussed. The results disclose that the area of the Pt electrodes evaluated by electrochemical techniques is related to the actual PFSI content on the electrode and to the nature of the electrolyte. Using HClO₄ as electrolyte, electrode area values are independent of the PFSI content. On the contrary, if experiments are recorded in H₂SO₄, the electrode area value increases with the increasing PFSI content, irrespectively of the Pt loading. Such effect is ascribed to the interaction of the sulfonic groups from the PFSI with the surface of the Pt nanoparticles, avoiding the strong adsorption of the bisulfate anions.     

Development of an experimentally validated semi-empirical fully-coupled performance model of a PEM electrolysis cell with a 3-D structured porous transport layer

A semi-empirical non-isothermal model incorporating coupled momentum, heat and mass transport phenomena for predicting the performance of a proton exchange membrane (PEM) water electrolysis cell operating without flow channels is presented. Model input parameters such as electro-kinetics properties and mean pore size of the porous transport layer (PTL) were determined by rotating disc electrode and capillary flow porometry, respectively. This is the first report of a semi-empirical fully coupled model which allows one to quantify and investigate the effect of the gas phase and bubble coverage on PEM cell performance up to very high current densities of about 5 A/cm². The mass transport effects are discussed in terms of the operating conditions, design parameters and the microstructure of the PTL. The results show that, the operating temperature and pressure, and the inlet water flowrate and thickness of the PTL are the critical parameters for mitigating mass transport limitation at high current densities. The model presented here can serve as a tool for further development and scale-up effort in the area of PEM water electrolysis, and provide insight during the design stage.     

Oxidation of magnetron sputtered La-Si thin films for solide oxide fuel cell electronlytes

La-Si thin films were deposited on stainless steel substrates by magnetron sputtering from pure La and Si targets. The Si/(Si + La) atomic ratio in the films was varied from 43.2 to 59.3% by adjusting the discharge current on the La target. The films had a homogeneous chemical composition down to the substrate and sharp interfaces. Annealing the films in air at 1173 K promotes the formation of apatite-structure La_9.33Si₆O₂₆ and the diffusion of different species from the film to the substrate and vice-versa, resulting in broadening the interfaces. X-Ray diffraction showed that all the as-deposited films had an amorphous structure. The formation of the LaSi₂ phase at intermediate temperatures was observed for the films deposited with higher Si contents while the films deposited with lower Si contents remained amorphous up to the start of the apatite structure crystallization process. The lanthanum silicate apatite-like phase (La_9.33Si₆O₂₆) was obtained only after annealing at 1173 K, excepted for the film with the lower Si content which is already partially crystallized after annealing at 1073 K. Quite pure La_9.33Si₆O₂₆ was obtained only after annealing the film with the highest Si content (Si/(Si + La) = 59.3%) although the theoretical Si/(Si + La) atomic ratio for apatite structure lanthanum silicate is 39%. For the other films, La₂O₃ was always detected when the lanthanum silicate phase was formed. Both phenomena clearly resulted from the strong diffusion of silicon excess towards the stainless steel substrate.     

Enhanced sinterability of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ by addition of nickel oxide

The effect of nickel oxide addition on the sintering behavior and electrical properties of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) as an electrolyte for solid oxide fuel cells was systematically studied. Results suggest that the addition of a small amount (∼1 wt%) of NiO to BZCYYb greatly promoted densification, achieving ∼96% of the theoretical density after sintering at 1350 °C in air for 3 h (reducing the sintering temperature by ∼200 °C). Further, a sample sintered at 1450 °C for 3 h showed high open circuit voltages (OCVs) when used as the electrolyte membrane to separate the two electrodes under typical SOFC operating conditions, indicating that the electrical conductivity of the electrical conductivity of the BZCYYb was not adversely affected by the addition of ∼1 wt% NiO.     

Fused ring and linking groups effect on overcharge protection for lithium-ion batteries

The derivatives of 1,3-benzodioxan (DBBD1) and 1,4-benzodioxan (DBBD2) bearing two tert-butyl groups have been synthesized as new redox shuttle additives for overcharge protection of lithium-ion batteries. Both compounds exhibit a reversible redox wave over 4 V vs Li/Li⁺ with better solubility in a commercial electrolyte (1.2 M LiPF₆ dissolved in ethylene carbonate/ethyl methyl carbonate (EC/EMC 3/7) than the di-tert-butyl-substituted 1,4-dimethoxybenzene (DDB). The electrochemical stability of DBBD1 and DBBD2 was tested under charge/discharge cycles with 100% overcharge at each cycle in MCMB/LiFePO₄ and Li₄Ti₅O₁₂/LiFePO₄ cells. DBBD2 shows significantly better performance than DBBD1 for both cell chemistries. The structural difference and reaction energies for decomposition have been studied by density functional calculations.     

Investigation and application of lithium difluoro(oxalate)borate (LiDFOB) as additive to improve the thermal stability of electrolyte for lithium-ion batteries

Lithium difluoro (oxalate) borate (LiDFOB) is used as thermal stabilizing and solid electrolyte interface (SEI) formation additive for lithium-ion battery. The enhancements of electrolyte thermal stability and the SEIs on graphite anode and LiFePO₄ cathode with LiDFOB addition are investigated via a combination of electrochemical methods, nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), as well as density functional theory (DFT). It is found that cells with electrolyte containing 5% LiDFOB have better capacity retention than cells without LiDFOB. This improved performance is ascribed to the assistance of LiDFOB in forming better SEIs on anode and cathode and also the enhancement of the thermal stability of the electrolyte. LiDFOB-decomposition products are identified experimentally on the surface of the anode and cathode and supported by theoretical calculations.     

Surface characterisation of DC plasma electrolytic oxidation treated 6082 aluminium alloy: Effect of current density and electrolyte concentration

Plasma electrolytic oxidation (PEO) is a specialised but well-developed process which has found applications in aerospace, oil/gas, textile, chemical, electrical and biomedical sectors. A novel range of coatings having technologically attractive physical and chemical properties (e.g. wear- and corrosion-resistance) can be produced by suitable control of the electrolyte as well as electrical parameters of the PEO process. Oxide ceramic films, 3 to 40 μm thick, were produced on 6082 aluminium alloy by DC PEO using 5 to 20 A/dm² current density in KOH electrolyte with varied concentration (0.5 to 2.0 g/l). Phase analysis (composition and crystallite size) was carried out using X-ray diffraction and TEM techniques. Residual stresses associated with the crystalline coating phase (α-Al₂O₃) were evaluated using the X-ray diffraction Sin²ψ method. Nanoindentation studies were conducted to evaluate the hardness and elastic modulus. SEM, SPM and TEM techniques were utilised to study surface as well as cross-sectional morphology and nano features of the PEO coatings. Correlations between internal stress and coating thickness, surface morphology and phase composition are discussed. It was found that, depending on the current density and electrolyte concentration used, internal direct and shear stresses in DC PEO alumina coatings ranged from − 302 ± 19 MPa to − 714 ± 22 MPa and − 25 ± 12 MPa to − 345 ± 27 MPa, respectively. Regimes of PEO treatment favourable for the production of thicker coatings with minimal stress level, dense morphology and relatively high content of α-Al₂O₃ phase are identified.     

Gamma ray degradation of electrolytes containing alkylcarbonate solvents and a lithium salt

Lithium-ion batteries for space applications, such as satellites, are subjected to cosmic radiations, in particular, γ-irradiation. In this study, the effects of this radiation on electrolytes and their components used in the lithium-ion batteries are investigated. The conductivity and viscosity of the samples have been measured before and after the irradiation. The modifications are evaluated by spectral analyses such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H and ¹³C NMR), solid phase microextraction-gas chromatography (SPME-GC) and gas chromatography-mass spectroscopy (GC-MS). The experimental results show that only the samples containing vinylene carbonate and/or the lithium salt LiPF₆ are degraded by γ-radiation.     

Improving the direct methanol fuel cell performance with poly(vinyl alcohol)/titanium dioxide nanocomposites as a novel electrolyte additive

The present investigation deals with the fabrication of new poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites (NCs) with different titanium dioxide (TiO₂) loading by using ultrasound irradiation. For the improvement of nanoparticles (NPs) dispersion and increasing possible interactions between NPs and PVA, the surface of TiO₂ NPs was modified by γ-aminopropyltriethoxy silane. The as-prepared NCs were characterized by spectroscopic, thermogravimetric analysis and electron microscopy methods. The results demonstrate that NPs dispersed homogeneously within the PVA matrix on nanoscale, which could be assigned to the hydrogen and covalent bonds formed between PVA and NPs. The results indicated that heat stability of NCs was improved in the presence of modified TiO₂ NPs. The mechanisms of surface modification and a possible mechanism of ultrasonic induced interaction between polymer and NPs have been analyzed.     

Effect of succinic anhydride as an electrolyte additive on electrochemical characteristics of silicon thin-film electrode

The effect of an electrolyte additive, succinic anhydride (SA), on the electrochemical performances of a silicon thin-film electrode, which is prepared by radio-frequency magnetron sputtering, is investigated. The introduction of SA into a liquid electrolyte consisting of ethylene carbonate/diethyl carbonate/1 M LiPF₆ significantly enhances the capacity retention and coulombic efficiency of the electrode. This improvement in the electrochemical performance of the electrode is attributed to modification of the solid/electrolyte interphase (SEI) layer by the introduction of SA. The differences in the characteristic properties of SEI layers, with or without SA, are explained by analysis with scanning electron microscopy, electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy.