When designing a high energy density battery, one of the critical features is a high voltage, high capacity cathode material. In the development of Mg batteries, oxide cathodes that can reversibly intercalate Mg, while at the same time being compatible with an electrolyte that can deposit Mg reversibly are rare. Herein, we report the compatibility of Mg anodes with α-V 2 O 5 by employing magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolytes at very low water levels. Electrolytes that contain a high water level do not reversibly deposit Mg, but interestingly these electrolytes appear to enable much higher capacities for an α-V 2 O 5 cathode. Solid state NMR indicates that the major source of the higher capacity in high water content electrolytes originates from reversible proton insertion. In contrast, we found that lowering the water level of the magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte is critical to achieve reversible Mg deposition and direct evidence for reversible Mg intercalation is shown. Findings we report here elucidate the role of proton intercalation in water-containing electrolytes and clarify numerous conflicting reports of Mg insertion into α-V 2 O 5 .
(19)F NMR spectroscopy has been used to study the local environments of anions in supercapacitor electrodes and to quantify changes in the populations of adsorbed species during charging. In the absence of an applied potential, anionic species adsorbed within carbon micropores (in-pore) are distinguished from those in large mesopores and spaces between particles (ex-pore) by a characteristic nucleus-independent chemical shift (NICS). Adsorption experiments and two-dimensional exchange experiments confirm that anions are in dynamic equilibrium between the in- and ex-pore environments with an exchange rate in the order of tens of Hz. (19)F in situ NMR spectra recorded at different charge states reveal changes in the intensity and NICS of the in-pore resonances, which are interpreted in term of changes in the population and local environments of the adsorbed anions that arise due to the charge-storage process. A comparison of the results obtained for a range of electrolytes reveals that several factors influence the charging mechanism. For a tetraethylammonium tetrafluoroborate electrolyte, positive polarisation of the electrode is found to proceed by anion adsorption at a low concentration, whereas increased ion exchange plays a more important role for a high concentration electrolyte. In contrast, negative polarization of the electrode proceeds by cation adsorption for both concentrations. For a tetrabutylammonium tetrafluoroborate electrolyte, anion expulsion is observed in the negative charging regime; this is attributed to the reduced mobility and/or access of the larger cations inside the pores, which forces the expulsion of anions in order to build up ionic charge. Significant anion expulsion is also observed in the negative charging regime for alkali metal bis(trifluoromethane)sulfonimide electrolytes, suggesting that more subtle factors also affect the charging mechanism.
Wearable electronics, electronic
skins, and human–machine
interfaces demand flexible sensors with not only high sensitivity
but also a wide linear working range. The latter remains a great challenge
and has become a big hurdle for some of the key advancements imperative
to these fields. Here, we present a flexible capacitive pressure sensor
with ultrabroad linear working range and high sensitivity. The dielectric
layer of the sensor is composed of multiple layers of double-sided
microstructured ionic gel films. The multilayered structure and the
gaps between adjacent films with random topography and size enhance
the compressibility of the sensor and distribute the stress evenly
to each layer, enabling a linear working range from 0.013 to 2063
kPa. Also, the densely distributed protrusive microstructures in the
electric double layer contribute to a sensitivity of 9.17 kPa–1 for the entire linear working range. For the first
time, a highly sensitive pressure sensor that can measure loading
conditions across 6 orders of magnitude is demonstrated. With the
consistent and stable performance from a low- to high-measurement
range, the proposed pressure sensor can be used in many applications
without the need for recalibration to suit different loading scenarios.
Electronic supplementary information (ESI) available: pore size distributions, EDX data, MOF(Fe) element mapping, C1s and O1s XPS spectra, RHE calibration, Electrochemical impedance spectra, MOF(Fe) CV curves, RDE voltammograms and corresponding K-L curves, MnO 2 ORR activities comparison, HORR and ORR catalytic activities comparison, and methanol crossover tests.
AbstractAn ε-MnO 2 /metal-organic-framework(Fe) (i.e., ε-MnO 2 /MOF(Fe)) composite was synthesised by integrating ε-MnO 2 and a MOF(Fe) support. The composite was characterised using X-ray diffraction, N 2 adsorption-desorption, field emission scanning electron microscopy, transmission electron microscopy, element mapping, Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The ORR activity of the composite was evaluated by cyclic and linear sweep voltammetries in an alkaline electrolyte. The results revealed that in the ε-MnO 2 /MOF(Fe) composite, ε-MnO 2 are in the form of nanorods, each with one end protruding and the other firmly anchored on the MOF(Fe) matrix with a high porosity and a high specific surface area. This unique structure of the composite is advantageous for oxygen diffusion and contact with the ε-MnO 2 during reactions, resulting in much better ORR activity and stability than those of the ε-MnO 2 in an alkaline electrolyte. The ε-MnO 2 /MOF(Fe)-catalysed ORR favours an apparent 4-electron transfer pathway in which oxygen was firstly reduced to hydroperoxide, which was further chemically decomposed into primarily OH -and O 2 .
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