Institut de Chimie et des Matériaux Paris-Est

Globally, the accelerating use of renewable energy sources, enabled by increased efficiencies and reduced costs, and driven by the need to mitigate the effects of climate change, has significantly increased research in the areas of renewable energy production, storage, distribution and end-use. Central to this discussion is the use of hydrogen, as a clean, efficient energy vector for energy storage. This review, by experts of Task 32, “Hydrogen-based Energy Storage” of the International Energy Agency, Hydrogen TCP, reports on the development over the last 6 years of hydrogen storage materials, methods and techniques, including electrochemical and thermal storage systems. An overview is given on the background to the various methods, the current state of development and the future prospects. The following areas are covered; porous materials, liquid hydrogen carriers, complex hydrides, intermetallic hydrides, electrochemical storage of energy, thermal energy storage, hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage.

16th International Symposium on Metal - Hydrogen Systems, Guangzhou / China, 28 Oct - 2 Nov 2018 (oral); MH2018: Abstract ID 300

International audience

) provide a promising solution for the requirement to store large amounts of hydrogen in a future hydrogen-based energy system. This requires the design of alloys which allow for a very high H/M ratio. Transition metal hydrides typically have a maximum H/M ratio of 2 and higher ratios can only be obtained in alloys based on rare-earth elements. In this study we demonstrate, for the first time to the best of our knowledge, that a high entropy alloy of TiVZrNbHf can absorb much higher amounts of hydrogen than its constituents and reach an H/M ratio of 2.5. We propose that the large hydrogen-storage capacity is due to the lattice strain in the alloy that makes it favourable to absorb hydrogen in both tetrahedral and octahedral interstitial sites. This observation suggests that high entropy alloys have future potential for use as hydrogen storage materials.

The vanadium-based terephthalate analogs of MIL-68 have been obtained with gallium and indium (network composition: M(OH)(O(2)C-C(6)H(4)-CO(2)), M = Ga or In) by using a solvothermal synthesis technique using N,N-dimethylformamide as a solvent (10 and 48 h, for Ga and In, respectively, at 100 degrees C). They have been characterized by X-ray diffraction analysis; vibrational spectroscopy; and solid-state (1)H and (1)H-(1)H radio-frequency-driven dipolar recoupling (RFDR), (1)H-(1)H double quantum correlation (DQ), and (13)C{(1)H} cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The three-dimensional network with a Kagomé-like lattice is built up from the connection of infinite trans-connected chains of octahedral units MO(4)(OH)(2) (M = Ga or In), linked to each other through the terephthalate ligands in order to generate triangular and hexagonal one-dimensional channels. The presence of DMF molecules with strong interactions within the channels as well as their departure upon calcination (150 degrees C under a primary vacuum) of the materials has been confirmed by subjecting MIL-68 (Ga) to solid-state (1)H MAS NMR. The (1)H-(1)H RFDR and (1)H-(1)H DQ spectra revealed important information on the spatial arrangement of the guest species with respect to the hybrid organic-inorganic network. (13)C{(1)H} CPMAS NMR of activated samples provided crystallographically independent sites in agreement with X-ray diffraction structure determination. Brunauer-Emmett-Teller surface areas are 1117(24) and 746(31) m(2) g(-1) for MIL-98 (Ga) and MIL-68 (In), respectively. Hydrogen adsorption isotherms have been measured at 77 K, and the storage capacities are found to be 2.46 and 1.98 wt % under a saturated pressure of 4 MPa for MIL-68 (Ga) and MIL-68 (In), respectively. For comparison, the hydrogen uptake for the aluminum trimesate MIL-110, which has an open framework with 16 A channels, is 3 wt % under 4 MPa.

We investigate the dispersion mechanisms of nanocomposites made of well-defined polymer (polystyrene, PS) grafted-nanoparticles (silica) mixed with free chains of the same polymer using a combination of scattering (SAXS/USAXS) and imaging (TEM) techniques. We show that the relevant parameter of the dispersion, the grafted/free chains mass ratio R tuned with specific synthesis process, enables to manage the arrangement of the grafted nanoparticles inside the matrix either as large and compact aggregates (R < 0.24) or as individual nanoparticles dispersion (R > 0.24). From the analysis of the interparticles structure factor, we can extract the thickness of the spherical corona of grafted brushes and correlate it with the dispersion: aggregation of the particles is associated with a significant collapse of the grafted chains, in agreement with the theoretical models describing the free energy as a combination of a mixing entropy term between the free and the grafted chains and an elastic term of deformation of the grafted brushes. At fixed grafting density, the individual dispersion of particles below the theoretical limit of R = 1 can be observed, due to interdiffusion between the grafted and the free chains but also to processing kinetics effects, surface curvature and chains poly dispersity. Mechanical analysis of nanocomposites show the appearance of a longer relaxation time at low frequencies, more pronounced in the aggregated case even without direct connectivity between the aggregates. Correlation between the local structure and the rheological behavior suggests that the macroscopic elastic modulus of the nanocomposite could be described mainly by a short-range contribution, at the scale of the interactions between grafted particles, without significant effect of larger scale organizations.

An equiatomic, single-phase TiZrNbHfTa high-entropy alloy was subjected to high-pressure torsion, leading to a grain size below 100 nm. Introducing a nanocrystalline microstructure to the material should help to accelerate a possible phase decomposition of the material by having a high amount of fast diffusion pathways and possible nucleation sites in the form of grain boundaries. In order to test the materials thermodynamic stability the nanocrystalline high-entropy alloy. was subjected to various heat treatments for temperatures between 300 °C and 1100 °C. Isochronal heat treatments (1 h) resulted in a hardness increase from 420 HV1 for the as-processed state to 530 HV1 for an annealing temperature of 500 °C, while for temperatures of 700 °C and higher a softening compared to the as-processed state occurred. In order to clarify this unexpected annealing response, analysis of selected microstructural states was performed utilizing electron microscopy, x-ray diffraction as well as mechanical testing to gain further information on microstructure-property relationships. Complementary, thermodynamic simulations were performed via the Calphad approach and compared to the experimental results. A phase decomposition of the originally equimolar single-phase high-entropy alloy into a NbTa-rich body-centered cubic phase and ZrHf-rich phases, which occurred in two different crystal structures depending on the annealing temperature, was the main reason for the property changes. The obtained results not only give valuable new insights into the phase stability of the TiZrNbHfTa alloy, but also demonstrate the impact of the newly forming phases in regards to mechanical properties and its implication for a possible practical application of this alloy.

The hydrogen adsorption capacity and heat of adsorption at 77 K have been evaluated for several porous metal terephthalate MOFs (MIL-53(Fe), MIL-125(Ti) and UiO-66(Zr)), as well as in their -NH(2) and -(CF(3))(2) functionalized isoreticular structures. The capacity of hydrogen is basically related to the textural properties of the solids and not to their composition. The heats of adsorption at low coverage are on the whole close to those usually reported for MOFs (6-7 kJ mol(-1)), except for the UiO-66(Zr) and MIL-53(Fe)-(CF(3))(2) analogues, whereas the presence of Lewis acid sites and/or a confinement effect enhances significantly the strength of interaction with hydrogen.

High-entropy alloys (HEAs) and related concept of complex concentrated alloys (CCAs) expand the diversity of the materials world and inspire new ideas and approaches for the design of materials with an attractive combination of properties. Here, we present a critical review of the field with the intent of summarizing the principles underlying their birth and growth. We highlight the major accomplishments and progresses over the last 14 years, especially in the discovery of new microstructures and mechanical properties. Finally, we outline the main challenges and provide guidance for future works.

A new bcc Ti-rich high-entropy alloy (HEA) of composition Ti35Zr27.5Hf27.5Nb5Ta5 was designed using the ‘d-electron alloy design’ approach. The tensile behavior displays a marked transformation-induced plasticity effect resulting in a high normalized work-hardening rate of 0.103 without loss of ductility when compared to the reference composition Ti20Zr20Hf20Nb20Ta20. In this paper, a detailed microstructural analysis was performed to understand the deformation process, revealing architectural-type microstructures and a high volume fraction (65%) of internally twinned stress-induced martensite α″ after mechanical testing. This study opens the way to mechanical properties optimization and enhancement of titanium-based HEAs by combining multiple alloying designs.IMPACT STATEMENTFor the first time, proof is given that transformation-induced plasticity was triggered in a bcc refractory high-entropy alloy, leading to a twofold increase in the normalized work-hardening rate.

International audience

Raman microspectrometry has been used to investigate the local structural changes induced by the electrochemical lithium intercalation reaction in crystalline sputtered V2O5 thin films in a liquid electrolyte. Contrary to usual composite electrodes made of a mixture of active material and conductive and binding agents, the use of a pure V2O5 thin film allows a homogeneous Li insertion in the material and a high quality of Raman signatures to be obtained. The Raman spectra of LixV2O5 compounds for 0 < x < 1 are examined as a function of the lithium content and discussed in relation with the X-ray diffraction data pertinent to these h00-oriented thin films and literature data. An assignment of all Raman bands is proposed, and the Raman fingerprint of the ϵ-type phase, whose interlayer distance continuously increases with x, is clearly evidenced all along the Li insertion process: lithium ions rapidly produce an orthorhombic ϵ phase characterized by a vanadyl stretching mode at 984 cm−1 for 0 < x < 0.5, and further Li accommodation induces a splitting into two stretching modes, the first one shifting from 984 to 975 cm−1, the second from x = 0.7 located at a fixed wavenumber of 957 cm−1. Both modes are consistent with the local structure of the ϵ lithium-rich phase called ϵ′ and reflect the existence of two different lithium sites. This work illustrates that the structural changes, in terms of long-range order and local structure, are strongly dependent on the microstructure and morphology of the material.

The battery market is undergoing quick expansion owing to the urgent demand for mobile devices, electric vehicles and energy storage systems, convoying the current energy transition. Beyond Li-ion batteries are of high importance to follow these multiple-speed changes and adapt to the specificity of each application. This review-study will address some of the relevant post-Li ion issues and battery technologies, including Na-ion batteries, Mg batteries, Ca-ion batteries, Zn-ion batteries, Al-ion batteries and anionic (F- and Cl-) shuttle batteries. MH-based batteries are also presented with emphasize on NiMH batteries, and novel MH-accommodated Li-ion batteries. Finally, to facilitate further research and development some future research trends and directions are discussed based on comparison of the different battery systems with respect to Li-ion battery assumptions. Remarkably, aqueous systems are most likely to be given reconsideration for intensive, cost-effective and safer production of batteries; for instance to be utilized in (quasi)-stationary energy storage applications.

TiFe-based alloys are key materials for large-scale applications based on solid-state hydrogen storage. A comprehensive overview is here provided on chemical substitutions in TiFe for tuning at will their reversible hydrogen storage properties.

This data article presents the compilation of mechanical properties for 122 refractory high entropy alloys (RHEAs) and refractory complex concentrated alloys (RCCAs) reported in the period from 2010 to the end of January 2018. The data sheet gives alloy composition, type of microstructures and the metallurgical states in which the properties are measured. Data such as the computed alloy mass density, the type of mechanical loadings to which they are subjected and the corresponding macroscopic mechanical properties, such as the yield stress, are made available as a function of the testing temperature. For practical use, the data are tabulated and some are also graphically presented, allowing at a glance to access relevant information for this attractive category of RHEAs and RCCAs.

A high-entropy alloy (HEA) of HfNbTiVZr was synthesized using an arc furnace followed by ball milling. The hydrogen absorption mechanism was studied by in situ X-ray diffraction at different temperatures and by in situ and ex situ neutron diffraction experiments. The body centered cubic (BCC) metal phase undergoes a phase transformation to a body centered tetragonal (BCT) hydride phase with hydrogen occupying both tetrahedral and octahedral interstitial sites in the structure. Hydrogen cycling of the alloy at 500 °C is stable. The large lattice strain in the HEA seems favorable for absorption in both octahedral and tetrahedral sites. HEAs therefore have potential as hydrogen storage materials because of favorable absorption in all interstitial sites within the structure.

Arrays of ordered hollow urchin-like ZnO single-crystal nanowires with controlled core dimensions and wire morphology are obtained by a new method that combines electrochemical deposition with colloidal templating rendered electrically conductive. This method opens new opportunities for processing novel metal oxide or hydroxide materials based on a similar growth mechanism. Such ordered structures exhibit superior optical reflectance compared to nanowire arrays.

The concept of a hybrid nanostructured collector made of thin vertically aligned carbon nanotubes (CNTs) decorated with Si nanoparticles provides high power density anodes in lithium-ion batteries. An impressive rate capability is achieved due to the efficient electronic conduction of CNTs combined with well defined electroactive Si nanoparticles: capacities of 3000 mAh g−1 at 1.3C and 800 mAh g−1 at 15C are achieved.

Gold nanoparticles (AuNPs) have stimulated a wide range of interest these past years due to their remarkable optical, electronic, and catalytic properties. Generally, the use of these nanoparticles requires their functionalization or combination with functional molecules, the nature of which depends on the target application. Among the numerous possibilities offered by chemistry, some recent papers report the coupling of AuNPs with molecularly imprinted polymers (MIPs) for the design of plasmonic-based AuNPs@MIP sensors. In such systems, a target analyte can be captured from a complex medium with a high specificity and selectivity owing to the exceptional chemical properties of the MIP matrix while the recognition event can be translated into a measurable physical signal (optical, electric, piezoelectric), the enhancement of which can be mediated by AuNPs. Despite such unique and intriguing advantages of AuNPs@MIP nanocomposites, there are still only limited numbers of studies regarding this field at the interface between plasmonics and functional polymers. This review focuses on the chemistry, processing, and applications of these nanohybrid materials, especially in the field of highly sensitive sensors. A prospect for the exploration of novel multicomposites combining AuNPs@MIPs with other kinds of nanoparticles (such as carbon nanotubes, graphene, and TiO2) is provided along with original strategies to optimize the functionality and sensitivity of these nanocomposites-based sensors.

A systematic study of the role of KCl on the electrodeposition of ZnO nanowire arrays from the reduction of oxygen in ZnCl2 solutions was performed. Besides its role as a supporting electrolyte, other major effects were found. An increase of KCl concentration ([KCl]) considerably decreased the rate of O2 reduction. The consequent decrease in OH- production rate resulted in an augmentation of the ZnO deposition efficiency, from a value around 3% for [KCl] = 5 × 10-2 M to more than 40% for [KCl] = 3.4 M. The increase of the deposition efficiency mainly resulted in an enhancement of the longitudinal growth rate. However, high [KCl] (>1 M) also favored the lateral growth of the ZnO nanowires, resulting in diameters as big as 300 nm (in comparison to the diameter of 80 nm obtained for [KCl] < 1 M). The observed effects were discussed in terms of Cl- ion adsorption on the cathode surface. The possible preferential adsorption of the anion on the (0001) ZnO surface was emphasized. Transmission electron microscopy revealed that the ZnO nanowires were single crystals, irrespective of [KCl] in the electrolyte. Thus, playing with the chloride content in the solution is an interesting way to obtain ZnO single-crystal nanowire arrays with tailored dimensions under controlled deposition rates. The influence of the nanowire dimensions on the optical properties was also discussed, showing the interest of this study in the frame of nanostructured solar cells.