We carried out a complete study (magnetic, electronic, dielectric, dynamic, and elastic properties) of the nickel hydroxide [Ni(OH)2] from first-principles calculations based on density functional theory. No theoretical investigations of these physical properties have been previously reported in literature. Our work supports that Ni(OH)2 is an A-type antiferromagnetic material. In addition, it is negative uniaxial and semiconducting with a direct band gap at the $\Gamma${} point around 3 eV. By contrast to its electronic dielectric tensor, its static tensor is strongly anisotropic in the plane orthogonal to its optical axis. This anisotropy is mainly governed by a highly polar phonon centered around 510 cm$-${}1 and assigned as a rotational Eu mode. Both Raman and infrared spectra have been computed to clarify the longstanding debate on the assignment of the Ni(OH)2 phonon modes reported in literature. All these theoretical results are fruitfully compared to the experimental ones obtained on large Ni(OH)2 ``pseudosingle'' crystals when available.
11 January 2022 in ACS Applied Materials & Interfaces
Proton exchange membrane fuel cells have been recognized as a promising zero-emission power source for portable, mobile and stationary applications. The information of water content distribution in the different components of the cell during operation, particularly the proton conducting membrane, is a critical issue for the validation of mass transfer models, the definition of optimized operating conditions and the development of efficient systems with innovative designs for efficient water management. In order to fully understand the way a fuel cell performs, water transport and distribution have to be investigated in situ and operando. In this review, we critically examine the state-of-the-art of operando diagnostics sensitive to the membrane water content, particularly those techniques able (in principle) to give insights into water transport occurring along both the in- and through-plane directions. Particular attention is devoted to experimental results obtained across the membrane thickness i.e. to the determination of water concentration profiles originating from the water activity and electrical gradients occurring through the working fuel cell. Different operando techniques have been developed for this purpose, from the early 1990s up to the last few years: internal resistance measurements, magnetic resonance and neutron imaging, neutron and X-ray scattering, confocal μ-Raman spectroscopy. These techniques can be roughly separated as either direct (i.e. the water amount can be directly derived from the detected signal, avoiding sometimes arbitrary assumptions during data processing) but intrusive (i.e. they require significant modification of the fuel cell, compared to the current design and materials) or indirect but with a significantly lower intrusiveness. It appears that operando measurements of the membrane water distribution allow a unique picture of how the internal part of the fuel cell works, thus certainly contributing to the development of more effective cell designs and materials in the near future. Nevertheless, improvement in the fundamental understanding of the actual fuel cell requires further efforts to increase spatial and, more particularly, temporal resolution of current operando techniques. Also, the comparison of limitations arising from the basic principles of the different operando approaches suggests that ultimate progress will arise from the combination of complementary techniques for simultaneous measurements.