Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.
Understanding the mechanism(s) of polysulfide formation and knowledge about the interactions of sulfur and polysulfides with a host matrix and electrolyte are essential for the development of long-cycle-life lithium-sulfur (Li-S) batteries. To achieve this goal, new analytical tools need to be developed. Herein, sulfur K-edge X-ray absorption near-edge structure (XANES) and (6,7) Li magic-angle spinning (MAS) NMR studies on a Li-S battery and its sulfur components are reported. The characterization of different stoichiometric mixtures of sulfur and lithium compounds (polysulfides), synthesized through a chemical route with all-sulfur-based components in the Li-S battery (sulfur and electrolyte), enables the understanding of changes in the batteries measured in postmortem mode and in operando mode. A detailed XANES analysis is performed on different battery components (cathode composite and separator). The relative amounts of each sulfur compound in the cathode and separator are determined precisely, according to the linear combination fit of the XANES spectra, by using reference compounds. Complementary information about the lithium species within the cathode are obtained by using (7) Li MAS NMR spectroscopy. The setup for the in operando XANES measurements can be viewed as a valuable analytical tool that can aid the understanding of the sulfur environment in Li-S batteries.
Magnesium−sulfur batteries are considered as attractive energystorage devices due to the abundance of electrochemically active materials and high theoretical energy density. Here we report the mechanism of a Mg−S battery operation, which was studied in the presence of simple and commercially available salts dissolved in a mixture of glymes. The electrolyte offers high sulfur conversion into MgS in the first discharge with low polarization. The electrochemical conversion of sulfur with magnesium proceeds through two well-defined plateaus, which correspond to the equilibrium between sulfur and polysulfides (high-voltage plateau) and polysulfides and MgS (low-voltage plateau). As shown by XANES, RIXS (resonant inelastic X-ray scattering), and NMR studies, the end discharge phase involves MgS with Mg atoms in a tetrahedral environment resembling the wurtzite structure, while chemically synthesized MgS crystallizes in the rock-salt structure with octahedral coordination of magnesium.
To increase the power density of battery materials, without significantly affecting their main advantage of a high energy density, novel material architectures need to be developed. Using the example of LiFePO 4 , we demonstrate a simple, sol-gel-based route that leads to large (up to 20 µm) primary LiFePO 4 particles, each of which contains hierarchically organized pores in the meso and macro range. As the pores are formed due to vigorous gas evolution (mainly CO and CO 2 ) during degradation of a citrate precursor, they are perfectly interconnected within each particle. Elementary carbon, the other citrate-degradation product, is deposited on the walls of emerging pores. The superposition of a continuous 1-2 nm thick carbon film (electron conductor) on pores (ion conductor when filled with electrolyte) represents a unique architecture in which the electrons and ions are simultaneously supplied to the site of insertion in the particle interior. The material can operate at current rates up to 50 C while preserving a high tap density of ca. 1.9 g cm -3 .
Moybdenum-based subnanometre diameter nanowires are easy to synthesize and disperse,
and they exhibit a variety of functional properties in which they are superior to other
one-dimensional materials. However, further progress in the understanding of
physical properties and the development of new and specific applications have so far
been impeded by the fact that their structure was not accurately known. Here
we report on a combination of systematic x-ray diffraction and extended x-ray
absorption fine structure experiments, and first-principles theoretical structure
calculations, which are used to determine the atomic skeletal structure of individual
Mo6S9−xIx (MoSIx) nanowires, their packing arrangement within bundles and their electronic band structure.
From this work we conclude that the variations in functional properties appear to arise
from different stoichiometry, not skeletal structure. A supplementary data file is available
from http://stacks.iop.org/0957-4484/16/1578
3 molar ratios of ≥3 in an oxidation atmosphere have been synthesized in the pure state. X-ray absorption near-edge structure (XANES) spectroscopy has been used to determine the average valence state of chromium in the samples. The presence of unusual chromium valence states, 4+ and 5+, which was proposed via X-ray diffractometry studies, is strongly supported.
Combining the abundance
and inexpensiveness of their constituent
elements with their atomic dispersion, atomically dispersed Fe–N–C
catalysts represent the most promising alternative to precious-metal-based
materials in proton exchange membrane (PEM) fuel cells. Due to the
high temperatures involved in their synthesis and the sensitivity
of Fe ions toward carbothermal reduction, current synthetic methods
are intrinsically limited in type and amount of the desired, catalytically
active Fe–N4 sites, and high active site densities
have been out of reach (dilemma of Fe–N–C catalysts).
We herein identify a paradigm change in the synthesis of Fe–N–C
catalysts arising from the developments of other M–N–C
single-atom catalysts. Supported by DFT calculations we propose fundamental
principles for the synthesis of M–N–C materials. We
further exploit the proposed principles in a novel synthetic strategy
to surpass the dilemma of Fe–N–C catalysts. The selective
formation of tetrapyrrolic Zn–N4 sites in a tailor-made
Zn–N–C material is utilized as an active-site imprint
for the preparation of a corresponding Fe–N–C catalyst.
By successive low- and high-temperature ion exchange reactions, we
obtain a phase-pure Fe–N–C catalyst, with a high loading
of atomically dispersed Fe (>3 wt %). Moreover, the catalyst is
entirely
composed of tetrapyrrolic Fe–N4 sites. The density
of tetrapyrrolic Fe–N4 sites is more than six times
as high as for previously reported tetrapyrrolic single-site Fe–N–C
fuel cell catalysts.
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