High-entropy
oxides based on transition metals, such as Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O (TM-HEO),
have recently drawn special attention as potential anodes in lithium-ion
batteries due to high specific capacity and cycling reversibility.
However, the lithiation/delithiation mechanism of such systems is
still controversial and not clearly addressed. Here, we report on
an operando XAS investigation into TM-HEO-based anodes for lithium-ion
cells during the first lithiation/delithiation cycle. This material
showed a high specific capacity exceeding 600 mAh g–1 at 0.1 C and Coulombic efficiency very close to unity. The combination
of functional and advanced spectroscopic studies revealed complex
charging mechanisms, developing through the reduction of transition-metal
(TM) cations, which triggers the conversion reaction below 1.0 V.
The conversion is irreversible and incomplete, leading to the final
collapse of the HEO rock-salt structure. Other redox processes are
therefore discussed and called to account for the observed cycling
behavior of the TM-HEO-based anode. Despite the irreversible phenomena,
the HEO cubic structure remains intact for ∼60% of lithiation
capacity, so proving the beneficial role of the configuration entropy
in enhancing the stability of the HEO rock-salt structure during the
redox phenomena.
The most common MXene composition Ti 3 C 2 T x (T = F, O) shows outstanding stability as anode for sodium ion batteries (100% of capacity retention after 530 cycles with charge efficiency >99.7%). However, the reversibility of the intercalation/deintercalation process is strongly affected by the synthesis parameters determining, in turn, significant differences in the material structure. This study proposes a new approach to identify the crystal features influencing the performances, using a structural model built with a multitechnique approach that allows exploring the short-range order of the lamella. The model is then used to determine the long-range order by inserting defective elements into the structure. With this strategy it is possible to fit the MXene diffraction patterns, obtain the structural parameters including the stoichiometric composition of the terminations (neutron data), and quantify the structural disorder which can be used to discriminate the phases with the best electrochemical properties.
The
mechanisms of CO oxidation on the Mg
0.2
Co
0.2
Ni
0.2
Cu
0.2
Zn
0.2
O high-entropy oxide
were studied by means of operando soft X-ray absorption spectroscopy.
We found that Cu is the active metal and that Cu(II) can be rapidly
reduced to Cu(I) by CO when the temperature is higher than 130 °C.
Co and Ni do not have any role in this respect. The Cu(II) oxidation
state can be easily but slowly recovered by treatment of the sample
with O
2
at ca. 250 °C. However, it should be noted
that CuO is readily and irreversibly reduced to Cu(I) when it is treated
with CO at
T
> 100 °C. Thus, the main conclusion
of this work is that the high configurational entropy of Mg
0.2
Co
0.2
Ni
0.2
Cu
0.2
Zn
0.2
O
stabilizes the rock-salt structure and permits the oxidation/reduction
of Cu to be reversible, thus permitting the catalytic cycle to take
place.
Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented. The main advantages of these electrochemical devices are associated with their compactness and with the precision of the three-dimensional printing systems which allows details to be obtained that would otherwise be difficult. Thanks to these systems it was possible to combine synchrotron-based methods with complementary techniques in order to study the mechanism of the photoelectrocatalytic process.
Light-driven water splitting is one of the most promising approaches for using solar energy in light of more sustainable development. In this paper, a highly efficient p-type copper(II) oxide photocathode is studied. The material, prepared by thermal treatment of CuI nanoparticles, is initially partially reduced upon working conditions and soon reaches a stable form. Upon visible-light illumination, the material yields a photocurrent of 1.3 mA cm(-2) at a potential of 0.2 V vs a reversible hydrogen electrode at mild pH under illumination by AM 1.5 G and retains 30% of its photoactivity after 6 h. This represents an unprecedented result for a nonprotected Cu oxide photocathode at neutral pH. The photocurrent efficiency as a function of the applied potential was determined using scanning electrochemical microscopy. The material was characterized in terms of photoelectrochemical features; X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, fixed-energy X-ray absorption voltammetry, and extended X-ray absorption fine structure analyses were carried out on pristine and used samples, which were used to explain the photoelectrochemical behavior. The optical features of the oxide are evidenced by direct reflectance spectroscopy and fluorescence spectroscopy, and Mott-Schottky analysis at different pH values explains the exceptional activity at neutral pH.
α-FeOOH (goethite) and γ-FeOOH (lepidocrocite) were found to be the main corrosion products of the steel cathode in the sodium chlorate process; the identification of the phases formed under reducing potentials, along with the study of the electrodes during the reoxidation, is fundamental to understanding their role in this process. In this work, FeOOHbased electrodes were investigated through in situ and in operando X-ray absorption spectroscopy (XAS), combined to electrochemical measurements (e.g., voltammetry and chronoamperometry). At sufficiently negative potentials (below −0.4 V vs RHE ca.) and under hydrogen evolution conditions an unknown iron(II)-containing phase is formed. A comprehensive analysis of the whole XAS spectrum allowed proposing a structure bearing a relation with that of green rust (space group P3̅ 1m). This phase occurs independently of the nature of the starting electrode (α-or γ-FeOOH). During electrochemical reoxidation, however, the original phase is restored, meaning that the reduced phase brings some memory of the structure of the starting material. Spontaneous reoxidation in air suppresses the memory effect, producing a mixture of α and γ phases.
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