Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

Iodine from brown algae in human nutrition,with an emphasis on bioaccessibility,bioavailability, chemistry,and effects of processing: A systematic review

Brown algae are becoming increasingly popular as a food source and dietary supplement in Europe and other Western countries. As they are highly rich in iodine, they represent a potential new dietary iodine source. Iodine deficiency has been re-emerging in Europe, and it is important to ensure adequate intake through one's diet. However, macroalgae, and especially brown algae, may contain very high amounts of iodine, and both iodine deficiency and excessive iodine may increase the risk of negative health effects. The iodine content of algae or foods containing algae is currently not regulated in the European Union. The aim of this paper is to review the literature to determine the chemical species of iodine in brown algae, the loss of iodine during processing, and the bioavailability and bioaccessibility of iodine. A systematic search of the literature was performed in April 2021, via the databases Web of Science and PubMed. The review includes studies of iodine in brown macroalgae in relation to bioavailability, bioaccessibility, processing and speciation. A meta-analysis was conducted in relation to the following topics: (i) the correlation between total iodine and iodide (I^–) content in brown algae; (ii) the correlation between the loss of iodine during processing and the I^– content; and (iii) the correlation between bioavailability and the I^– content. The bioavailability of iodine from brown algae was generally high, with in vivo bioavailability ranging from 31% to 90%. The in vitro bioavailability of iodine (2%–28%) was systematically lower than in vivo bioavailability (31%–90%), indicating an inadequate in vitro methodology. Processing may reduce the iodine content of brown algae, and a higher I^– content was positively correlated with increased iodine loss during processing. Although processing strategies may reduce the iodine content of brown algae significantly, the iodine content may still be high after processing. These findings may be used in food safety evaluations of brown algae as well as in the development of macroalgae-containing foods with iodine contents suitable for human consumption. Further research on processing techniques to reduce the iodine content in brown macroalgae are warranted.     

Influence of Se and Te substitutions at Tl-site of Tl(Ba,Sr)CaCu2O7 superconductor on the AC susceptibility and electrical properties

The Sr and Ba bearing Tl-1212 phase, Tl(Ba,Sr)CaCu₂O₇ is an interesting superconductor. The Sr only bearing TlSr₂CaCu₂O₇ is not easily prepared in the superconducting form. The Ba only bearing TlBa₂CaCu₂O₇ on the other hand does not show improvement in the transition temperature with elemental substitution. In this work the influence of multivalent Se (non-metal) and Te (metalloid) substitutions at the Tl-site of Tl_1-xM_x(Ba,Sr)CaCu₂O₇ (M = Se or Te) superconductors for x = 0–0.6 was studied. The samples were prepared via the conventional solid-state reaction method. XRD patterns showed a single Tl-1212 phase for x = 0 and 0.1 Se substituted samples. The critical current density at the peak temperature, T_p of the imaginary (χ”) part of the AC susceptibility (χ = χ’ +χ”), J_c-inter(T_p) for all samples was between 15 and 21 A cm⁻². The highest superconducting transition temperature was shown by the x = 0.3 Se-substituted sample (T_c-onset = 104 K, T_c-zero = 89 K, T_cχ’ = 104 K and T_p = 80 K). Te suppressed the superconductivity of Tl-1212 phase. The order of highest transition temperatures are as follows: Tl_1-xTe_x(Ba,Sr)CaCu₂O₇<Tl(Ba,Sr)CaCu₂O₇<Tl_1-xSe_x(Ba,Sr)CaCu₂O₇. This work showed that Se was better than Te in improving the transition temperature and flux pinning of the Tl-1212 phase. The roles of ionic radius of Se and Te on the superconductivity of Tl(Ba,Sr)CaCu₂O₇ are discussed in this paper.     

Anisotropic thermal expansion and ionic conductivity of a crystal-oriented,Mg2+-conducting NASICON-type solid electrolyte

Multivalent ion-conducting ceramics are required for the manufacture of high-safety, high-capacity rechargeable batteries. However, the low ionic conductivity of solid electrolytes and discrepancies in the thermal expansion between the battery components limit their widespread application. Furthermore, anisotropic thermal expansion in crystals during battery manufacturing and the charge-discharge cycles causes the formation of microcracks, which degrade the battery performance. The physical properties of ceramic materials with anisotropic crystal structures can be modified by varying the crystallographic orientation of their grains. In this study, a co-precipitation approach was used to synthesize an Mg²⁺-conducting (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ solid electrolyte, and the grain orientation in the bulk sample was controlled using strong magnetic fields during the slip casting process. The results showed that inducing an orientation along the c-axis enhanced the apparent ionic conductivity of the bulk sample. It was also observed that (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ crystal has a negative volumetric thermal expansion despite a positive linear thermal expansion along its c-axis. By adjusting the c-axis orientation of the grains, (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ electrolytes with negative or positive linear thermal expansion coefficient have been produced. The findings of this study suggest that solid-electrolytes with negative, positive, or zero linear thermal expansion can be produced to create more compatible and higher-performance solid-state devices.     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.     

Review on zirconate-cerate-based electrolytes for proton-conducting solid oxide fuel cell

The performance of low-to-intermediate temperature (400–800?°C) solid oxide fuel cells (SOFCs) depends on the properties of electrolyte used. SOFC performance can be enhanced by replacing electrolyte materials from conventional oxide ion (O^2-) conductors with proton (H⁺) conductors because H⁺ conductors have higher ionic conductivity and theoretical electrical efficiency than O^2- conductors within the target temperature range. Electrolytes based on cerate and/or zirconate have been proposed as potential H⁺ conductors. Cerate-based electrolytes have the highest H⁺ conductivity, but they are chemically and thermally unstable during redox cycles, whereas zirconate-based electrolytes exhibit the opposite properties. Thus, tailoring the properties of cerate and/or zirconate electrolytes by doping with rare-earth metals has become a main concern for many researchers to further improve the ionic conductivity and stability of electrolytes. This article provides an overview on the properties of four types of cerate and/or zirconate electrolytes including cerate-based, zirconate-based, single-doped cerate–zirconate and hybrid-doped cerate–zirconate. The properties of the proton electrolytes such as ionic conductivity, chemical stability and sinterability are also systematically discussed. This review further provides a summary of the performance of SOFCs operated with cerate and/or zirconate proton conductors and the actual potential of these materials as alternative electrolytes for proton-conducting SOFC application.     

Fabrication and characterization of In doped Li13.9Sr0.1Zn(GeO4+δ)4 electrolytes for proton-conducting solid oxide fuel cells

Li_13.9Sr_0.1Zn(GeO_4+δ)₄ (LSZG) materials can exhibit proton conduction by Li⁺/H⁺ ion exchange in hydrogen atmosphere. It can be used in solid oxide fuel cells (SOFCs) as an electrolyte. In this study, In³⁺ doped LSZG powders are synthesized by sol-gel method. X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer, and electrochemical impedance spectroscopy are used to investigate the effects of In doping on LSZG. All Li_13.9-xIn_xSr_0.1Zn(GeO_4+δ)₄ (LISZG, 0 ≤ x ≤ 0.3) ceramics exhibit the same phase with LSZG. The dopant of In promotes the sintering activity and Li⁺/H⁺ ion exchange rate of LSZG. The optimum doping of In is x = 0.2. At 600 °C, Li_13.7In_0.2Sr_0.1Zn(GeO_4+δ)₄ (0.2LISZG) shows a proton conductivity of 0.094 S/cm under 0.9 V direct current bias voltage. In addition, the single cell based on 0.2LISZG electrolyte is prepared, and it has been demonstrated that the practical utilization of 0.2LISZG in IT-SOFCs is feasible.     

Ionic conductivities and high resolution microscopic evaluation of grain and grain boundaries of cerium-based codoped solid electrolytes

Doped CeGdO and codoped CeGdOSmO compositions were synthesized, giving rise to nanoparticulate powders. Ionic conductivities at bulk and grain boundaries of the sintered samples were determined, exhibiting increased conductivity in the samaria-codoped samples. Scanning electron microscopy (SEM) showed a significant reduction in the grain size of samaria-codoped electrolytes. This reduced grain size of the codoped samples caused a reduction in Schottky barrier height, increasing oxygen vacancy concentration in the space-charge layer of the grain boundary and culminating in greater ionic conductivity in the boundary region. For the gadolinium doped samples, high resolution transmission electron microscopy images at grains showed the presence of large cluster of defects (nanodomains), hindering the movement of charge carriers and reducing ionic conductivity. However, the samaria-codoped system displayed better homogeneity at atomic level, resulting in reduced oxygen vacancy ordering and, consequently, smaller nanodomains and higher bulk (grain) conductivity. The reduced grain sizes and smaller nanodomains caused by codoping favor the ionic conductivity of ceria-based ceramics, doped with gadolinia and codoped with samaria.     

The effect of ionic cross-links on the deformation behavior of homoblends made of poly(styrene-co-styrenesulfonic acid) and poly(styrene-co-4-vinylpyridine)

Deformation behavior of stoichiometric blends made from poly(styrene-co-styrenesulfonic acid) (SPS) and poly(styrene-co-4-vinylpyridine) (SVP) was investigated by TEM observation of strained thin films. An FTIR investigation revealed that ionic cross-links were formed between the component polymers upon blending due to intermolecular ion-ion interactions, which arose from proton transfer from sulfonic acid groups to pyridine groups. TEM observations indicate that the deformation mode of the blends changed from crazing only to crazing plus shear deformation, with the shear contribution becoming larger, as the ion content in the blends increased. Such changes in deformation mode can be understood as arising from an increase in the ‘effective’ strand density due to the formation of ionic cross-links upon blending. It was also found that the ionic cross-links via pyridinium cation/sulfonate anion ion pairs were more effective in inducing the transition of deformation mode than ionic cross-links via -SO₃⁻/Na⁺ or -SO₃⁻/Ca²⁺ ion pairs.     

Ionic transport in amorphous anodic titania stabilised by incorporation of silicon species

Incorporation of silicon species from an alloy substrate into anodic titania is shown to stabilise the structure of the film, facilitating investigation of the ionic transport processes in amorphous titania grown at high efficiency. Thus, an amorphous anodic film developed on a sputtering-deposited Ti-6 at.%Si alloy formed to 100 V in phosphoric acid electrolyte in contrast to a partially crystalline film developed on relatively pure titanium at <20 V. Silicon species, which are immobile and act as marker species in the growing film, are present in the inner 58% of the film thickness. Evidently, the film material forms simultaneously at the film/electrolyte and alloy/film interfaces by co-operative transport of cations and anions, as is usual in amorphous anodic oxides. The phosphate anions incorporated from the electrolyte migrate inward at 0.34 times the rate of O²⁻ ions and hence are present in the outer 62% of the film thickness.