Search

A highly complex crystal structure of stoichiometric Mg5(en)6(BH4)10 was solved from single crystal synchrotron X-ray diffraction and confirmed by neutron powder diffraction (NPD) on isotopically substituted Mg(en)1.2(11BD4)2. We highlight the role of the amorphous Mg(BH4)2 in the reactivity of the Mg(BH4)2-en system and characterized a previously overlooked phase, Mg(en)2(BH4)2. [ABSTRACT FROM AUTHOR]

In operando powder diffraction remains one of the most powerful tools for non‐destructive investigation of battery electrode materials. While in operando X‐ray, especially synchrotron radiation, powder diffraction is by now a routine experimental technique, in operando neutron powder diffraction is still less established. We present a new electrochemical cell for in operando neutron powder diffraction, which is, first and foremost, easy to use, but can also cycle electrode materials under electrochemical conditions close to those achieved using standard laboratory cells. The cell has been designed in multiple sizes, and high‐quality electrochemical and neutron powder diffraction data is presented for sample sizes as low as 48 mg total active material. The cell handles lithium‐ion and sodium‐ion materials equally well, with no difference in how the cell is prepared and assembled. The cell is intended to be used as sample environment at powder diffractometers at the neutron facilities MLZ, ORNL and ACNS. [ABSTRACT FROM AUTHOR]

A lab-made, multilayered Li-ion battery pouch cell is investigated using in-operando neutron powder diffraction (NPD) and spatially resolved powder X-ray diffraction (SR-PXRD) with the aim of investigating how to compare the information obtained from the two complementary techniques on a cell type with a complicated geometry for diffraction. The work focusses on the anode and cathode lithiation as obtained from the LiC6/LiC12 weight ratio and the NMC111 c/a-ratio, respectively. Neutron powder diffractograms of a sufficient quality for Rietveld refinement are measured using a rotation stage to minimize geometrical effects. Using SR-PXRD, the cell is shown to be non-uniform in its anode and cathode lithiation, with the edges of the cell being less lithiated/delithiated than the center in the fully charged state. The non-uniformity is more pronounced for high charging current than low charging current. The averaged SR-PXRD data is found to match the bulk NPD data well. This is encouraging as it seems to allow comparisons between studies using either of these complementary techniques. This work will also serve as a benchmark for our future studies on pouch cells with novel non-commercial cathode and/or anode materials. [ABSTRACT FROM AUTHOR]

Alkali and alkaline-earth metal borohydrides are intensely studied in view of their high hydrogen content and more recently, due to the observed decent ionic conductivities which would make them interesting candidates for solid state batteries. Neutron scattering techniques offer a unique tool to study both the structure and the dynamics of borohydride materials. This review summarizes recent work in this field, illuminating the rich and interconnectivity between hydrogen dynamic and crystallographic phases. [ABSTRACT FROM AUTHOR]

The dehydrogenation reaction pathway of a 0.91 (0.62LiBH 4 -0.38NaBH 4 )-0.09Ni mixture in the temperature range of 25–650 °C in flowing Ar and the cycling stability in H 2 are presented. No H 2 is released immediately after melting at 225 °C. The major dehydrogenation occurs above 350 °C. Adding nano-sized Ni reduces the dehydrogenation peak temperatures by 20–25 °C, leading to three decomposition steps where Ni 4 B 3 and Li 1.2 Ni 2.5 B 2 are found in the major dehydrogenation products for the 1 st and the 3 rd step; whilst the Ni-free mixture decomposes through a two-step decomposition pathway. A total of 8.1 wt% of hydrogen release from the 0.91 (0.62LiBH 4 -0.38NaBH 4 )-0.09Ni mixture is achieved at 650 °C in Ar. This mixture has a poor hydrogen cycling stability as its reversible hydrogen content decreases from 5.1 wt% to 1.1 wt% and 0.6 wt% during three complete desorption-absorption-cycles. However, the addition of nano-sized Ni facilitates the reformation of LiBH 4 . [ABSTRACT FROM AUTHOR]

In this work, praseodymium(iii) borohydride, Pr(BH4)3, and an isotopically enriched analogue, Pr(11BD4)3, are prepared by a new route via a solvate complex, Pr(11BD4)3S(CH3)2. Nd(BH4)3 was synthesized using the same method and the structures, polymorphic transformations, and thermal stabilities of these compounds are investigated in detail. α-Pr(BH4)3 and α-Nd(BH4)3 are isostructural with cubic unit cells (Pa3̅) stable at room temperature (RT) and a unit cell volume per formula unit (V/Z) of 180.1 and 175.8 Å3, respectively. Heating α-Pr(BH4)3 to T∼ 190 °C, p(Ar) = 1 bar, introduces a transition to a rhombohedral polymorph, r-Pr(BH4)3 (R3̅c) with a smaller unit cell volume and a denser structure, V/Z = 156.06 Å3. A similar transition was not observed for Nd(BH4)3. However, heat treatment of α-Pr(BH4)3, at T ∼ 190 °C, p(H2) = 40 bar and α-Nd(BH4)3, at T ∼ 270 °C, p(H2) = 98 bar facilitates reversible formation of another three cubic polymorph, denoted as β, β′ and β′′-RE(BH4)3 (Fm3̅c). Moreover, the transition β- to β′- to β′′- is considered a rare example of stepwise negative thermal expansion. For Pr(BH4)3, ∼2/3 of the sample takes this route of transformation whereas in argon only ∼5 wt%, and the remaining transforms directly from α- to r-Pr(BH4)3. The β-polymorphs are porous with V/Z = 172.4 and 172.7 Å3 for β′′-RE(BH4)3, RE = Pr or Nd, respectively, and are stabilized by the elevated hydrogen pressures. The polymorphic transitions occur due to rotation of RE(BH4)6 octahedra without breaking or forming chemical bonds. Structural DFT optimization reveals the decreasing stability of α-Pr(BH4)3 ＞ β-Pr(BH4)3 ＞ r-Pr(BH4)3. [ABSTRACT FROM AUTHOR]

In this work, praseodymium(iii) borohydride, Pr(BH4)3, and an isotopically enriched analogue, Pr(11BD4)3, are prepared by a new route via a solvate complex, Pr(11BD4)3S(CH3)2. Nd(BH4)3 was synthesized using the same method and the structures, polymorphic transformations, and thermal stabilities of these compounds are investigated in detail. α-Pr(BH4)3 and α-Nd(BH4)3 are isostructural with cubic unit cells (Pa3̅) stable at room temperature (RT) and a unit cell volume per formula unit (V/Z) of 180.1 and 175.8 Å3, respectively. Heating α-Pr(BH4)3 to T∼ 190 °C, p(Ar) = 1 bar, introduces a transition to a rhombohedral polymorph, r-Pr(BH4)3 (R3̅c) with a smaller unit cell volume and a denser structure, V/Z = 156.06 Å3. A similar transition was not observed for Nd(BH4)3. However, heat treatment of α-Pr(BH4)3, at T ∼ 190 °C, p(H2) = 40 bar and α-Nd(BH4)3, at T ∼ 270 °C, p(H2) = 98 bar facilitates reversible formation of another three cubic polymorph, denoted as β, β′ and β′′-RE(BH4)3 (Fm3̅c). Moreover, the transition β- to β′- to β′′- is considered a rare example of stepwise negative thermal expansion. For Pr(BH4)3, ∼2/3 of the sample takes this route of transformation whereas in argon only ∼5 wt%, and the remaining transforms directly from α- to r-Pr(BH4)3. The β-polymorphs are porous with V/Z = 172.4 and 172.7 Å3 for β′′-RE(BH4)3, RE = Pr or Nd, respectively, and are stabilized by the elevated hydrogen pressures. The polymorphic transitions occur due to rotation of RE(BH4)6 octahedra without breaking or forming chemical bonds. Structural DFT optimization reveals the decreasing stability of α-Pr(BH4)3 ＞ β-Pr(BH4)3 ＞ r-Pr(BH4)3. [ABSTRACT FROM AUTHOR]

The need for rapid data collection and studies of small sample volumes in the range of cubic millimetres are the main driving forces for the concept of a new high‐throughput monochromatic diffraction instrument at the Heinz Maier‐Leibnitz Zentrum (MLZ), Germany. A large region of reciprocal space will be accessed by a detector with sufficient dynamic range and microsecond time resolution, while allowing for a variety of complementary sample environments. The medium‐resolution neutron powder diffraction option for `energy research with neutrons' (ErwiN) at the high‐flux FRM II neutron source at the MLZ is foreseen to meet future demand. ErwiN will address studies of energy‐related systems and materials with respect to their structure and uniformity by means of bulk and spatially resolved neutron powder diffraction. A set of experimental options will be implemented, enabling time‐resolved studies, rapid parametric measurements as a function of external parameters and studies of small samples using an adapted radial collimator. The proposed powder diffraction option ErwiN will bridge the gap in functionality between the high‐resolution powder diffractometer SPODI and the time‐of‐flight diffractometers POWTEX and SAPHiR at the MLZ. [ABSTRACT FROM AUTHOR]

Rare earth (RE) borohydrides have received considerable attention during the past ten years as possible hydrogen storage materials due to their relatively high gravimetric hydrogen density. This review illustrates the rich chemistry, structural diversity and thermal properties of borohydrides containing RE elements. In addition, it highlights the decomposition and rehydrogenation properties of composites containing RE-borohydrides, light-weight metal borohydrides such as LiBH4 and additives such as LiH. [ABSTRACT FROM AUTHOR]

Rare earth (RE) metal borohydrides have recently been receiving attention as possible hydrogen storage materials and solid-state Li-ion conductors. In this paper, the decomposition and reabsorption of Er(BH4)3 in composite mixtures with LiBH4 and/or LiH were investigated. The composite of 3LiBH4 + Er(BH4)3 + 3LiH has a theoretical hydrogen storage capacity of 9 wt %, nevertheless, only 6 wt % hydrogen are accessible due to the formation of thermally stable LiH. Hydrogen sorption measurements in a Sieverts-type apparatus revealed that during three desorption-absorption cycles of 3LiBH4 + Er(BH4)3 + 3LiH, the composite desorbed 4.2, 3.7 and 3.5 wt % H for the first, second and third cycle, respectively, and thus showed good rehydrogenation behavior. In situ synchrotron radiation powder X-ray diffraction (SR-PXD) after ball milling of Er(BH4)3 + 6LiH resulted in the formation of LiBH4, revealing that metathesis reactions occurred during milling in these systems. Impedance spectroscopy of absorbed Er(BH4)3 + 6LiH showed an exceptional high hysteresis of 40-60 K for the transition between the high and low temperature phases of LiBH4, indicating that the high temperature phase of LiBH4 is stabilized in the composite. [ABSTRACT FROM AUTHOR]

Two new bimetallic sodium or potassium lanthanum borohydrides, NaLa(BH4)4 and K3La(BH4)6, are formed using La(BH4)3 free of metal halide by-products. NaLa(BH4)4 crystallizes in an orthorhombic crystal system with unit cell parameters, a = 6.7987(19), b = 17.311(5), c = 7.2653(19) Å and space group symmetry Pbcn. This compound has a new structure type built from brucite-like layers of octahedra (hcp packing of anions) with half of the octahedral sites empty leading to octahedral chains similar to rutile (straight chains) or α-PbO2 (zig-zag chains). K3La(BH4)6 crystallizes in the monoclinic crystal system with unit cell parameters a = 7.938(2), b = 8.352(2), c = 11.571(3) Å, β = 90.19(6)° and space group P21/n with a double-perovskite type structure. Thermogravimetric analysis shows a mass loss of 5.86 and 2.83 wt% for NaLa(BH4)4 and K3La(BH4)6, respectively, in the temperature range of room temperature to 400 °C. Mass spectrometry shows that hydrogen release starts at 212 and 275 °C for NaLa(BH4)4 and K3La(BH4)6, respectively and confirms that no diborane is released. Sieverts’ measurements reveal that 2.03 and 0.49 wt% of hydrogen can be released from the NaLa(BH4)4 and K3La(BH4)6, respectively, during the second hydrogen desorption cycle at the selected physical condition for hydrogen absorption. [ABSTRACT FROM AUTHOR]

Rare earth (RE) metal borohydrides are receiving immense consideration as possible hydrogen storage materials and solid-state Li-ion conductors. In this study, halide free Er(BH4)3 and Pr(BH4)3 have been successfully synthesized for the first time by the combination of mechanochemical milling and/or wet chemistry. Rietveld refinement of Er(BH4)3 confirmed the formation of two different Er(BH4)3 polymorphs: α-Er(BH4)3 with space group Pa3̅, a = 10.76796(5) Å, and β-Er(BH4)3 in Pm3̅m with a = 5.4664(1) Å. A variety of Pr(BH4)3 phases were found after extraction with diethyl ether: α-Pr(BH4)3 in Pa3̅ with a = 11.2465(1) Å, β-Pr(BH4)3 in Pm3̅m with a = 5.716(2) Å and LiPr(BH4)3Cl in I4̅3m, a = 11.5468(3) Å. Almost phase pure α-Pr(BH4)3 in Pa3̅ with a = 11.2473(2) Å was also synthesized. The thermal decomposition of Er(BH4)3 and Pr(BH4)3 proceeded without the formation of crystalline products. Rehydrogenation, as such, was not successful. However, addition of LiH promoted the rehydrogenation of RE hydride phases and LiBH4 from the decomposed RE(BH4)3 samples. [ABSTRACT FROM AUTHOR]

Light metal complex borohydrides have high hydrogen storage capacities but suffer from drawbacks of slow hydrogen sorption kinetics, poor reversibility and high thermodynamic stability. The NaF + 9NaH + 5MgB 2 composite has a theoretical hydrogen capacity of 7.7 wt% H assuming the formation of 10NaBH 3.9 F 0.1 + 5MgH 2 . Hydrogenation and dehydrogenation properties as well as the effect of different ball milling times have been investigated. The in situ hydrogenation is faster in the composite ball milled for 87 h than the 5 h milled composite. A boron-rich phase with space group Pa -3, a = 7.4124(5) Å was formed during hydrogenation at 325 °C and 50 bar hydrogen for both short and long milling times. In the long milled composite the boron-rich phase disappeared after 3 h of hydrogenation, whereas it became a major phase in the short milled composite after 1.5 h of hydrogenation. NaBH 4 was formed at 206 °C. NaMgH 1-x F x was formed at 290 °C instead of the assumed MgH 2 . The same phases formed at 268 °C and 325 °C, respectively, and only in minor amounts in the short milled composite. Ex situ hydrogenation in a Sieverts' type apparatus at the same temperature and hydrogen pressure conditions followed a different reaction pathway with formation of MgH 2 in addition to NaBH 4 and NaMgH 3-x F x (0 ≤ x ≤ 1). The measured hydrogen uptake was 6.0 and 6.3 wt% for the long and short milled composites, respectively. [ABSTRACT FROM AUTHOR]

Hydrogen as an energy carrier is very versatile in energy storage applications. Developments in novel, sustainable technologies towards a CO2-free society are needed and the exploration of all-solid-state batteries (ASSBs) as well as solid-state hydrogen storage applications based on metal hydrides can provide solutions for such technologies. However, there are still many technical challenges for both hydrogen storage material and ASSBs related to designing low-cost materials with low-environmental impact. The current materials considered for all-solid-state batteries should have high conductivities for Na+, Mg2+ and Ca2+, while Al3+-based compounds are often marginalised due to the lack of suitable electrode and electrolyte materials. In hydrogen storage materials, the sluggish kinetic behaviour of solid-state hydride materials is one of the key constraints that limit their practical uses. Therefore, it is necessary to overcome the kinetic issues of hydride materials before discussing and considering them on the system level. This review summarizes the achievements of the Marie Skłodowska-Curie Actions (MSCA) innovative training network (ITN) ECOSTORE, the aim of which was the investigation of different aspects of (complex) metal hydride materials. Advances in battery and hydrogen storage materials for the efficient and compact storage of renewable energy production are discussed. [ABSTRACT FROM AUTHOR]

This paper is a collection of selected contributions of the 1st International Workshop on Mechanochemistry of Metal Hydrides that was held in Oslo in May 2018. In this paper, the recent developments in the use of mechanochemistry to synthesize and modify metal hydrides are reviewed. A special emphasis is made on new techniques beside the traditional way of ball milling. High energy milling, ball milling under hydrogen reactive gas, cryomilling and severe plastic deformation techniques such as High-Pressure Torsion (HPT), Surface Mechanical Attrition Treatment (SMAT) and cold rolling are discussed. The new characterization method of in-situ X-ray diffraction during milling is described. [ABSTRACT FROM AUTHOR]

Rare earth borohydrides RE (BH 4) 3 are studied in the context of energy storage, luminescence and magnetic applications. We have investigated the structural behavior of praseodymium borohydride Pr (11BH 4) 3 containing 11B isotope because of the previously reported negative thermal expansion. Differential scanning calorimetry (DSC), in-situ variable temperature synchrotron radiation powder X-ray diffraction (SR-PXD) and infrared studies reveal that Pr (11BH 4) 3 undergoes to a volume contraction during the phase transition from alpha α-Pr (11BH 4) 3 to rhombohedral r-Pr (11BH 4) 3 phase upon heating to 493 K. Surprisingly, the phase transition persists upon cooling at room temperature. Vibrational analysis also shows that the stretching frequency of BH 4 − anion does not change upon heating which indicates that the B–H bond length remains constant during the structural phase transition from α-Pr (11BH 4) 3 to r-Pr (11BH 4) 3 phase. Additionally, the energy barrier of reorientation motion of the BH 4 − anion in the α-phase was estimated to be ca 23 kJ/mol by quasi-elastic neutron scattering (QENS) and Raman spectroscopy. [Display omitted] • SR-XRD confirms volume contraction at the α-Pr (11BH 4) 3 to r-Pr (11BH 4) 3 phase transition. • Vibrational spectra confirm that B–H bond length do not change at this phase transition. • QENS experiments give the activation energy for BH4 reorientation. [ABSTRACT FROM AUTHOR]

Understanding an interrelation between the structure, chemical composition and hydrogenation properties of intermetallic hydrides is crucial for the improvement of their hydrogen storage performance. Ability to form the hydrides and to tune the thermodynamics and kinetics of their interaction with hydrogen is related to their chemical composition. Some features of the metal–hydrogen interactions remain however poorly studied, including chemistry of Sc-containing hydrides. ZrNiAl-type ScNiSn-based intermetallic hydride has been probed in the present work using a broad range of experimental techniques including Synchrotron and Neutron Powder Diffraction, 119Sn Möessbauer Spectroscopy, hydrogenation at pressures reaching several kbar H 2 and hydrogen Thermal Desorption Spectroscopy studies. Computational DFT calculations have been furthermore performed. This allowed to establish the mechanism of the phase-structural transformation and electronic structure changes causing a unique contraction of the metal lattice of intermetallic alloy and the formation of the...H-Ni-H-Ni... chains in the structure with H atoms carrying a partial negative charge. Such hydrogen absorption accompanied by a formation of a covalent Ni-H bonding and causing an unusual behavior contracts to the conventionally observed bonding mechanism of hydrogen in metals as based on the metallic bonding frequently accompanied by a jumping diffusion movement of the inserted H atoms – in contrast to the directional Metal-Hydrogen bonding observed in the present work. At high applied pressures ScNiSnH 0.83 orthorhombic TiNiSi type hydride is formed with H atoms filling Sc 3 Ni tetrahedra. Finally, this study shows that scandium closely resembles the behavior of the heavy rare earth metal holmium. [Display omitted] [ABSTRACT FROM AUTHOR]

18650-type cells with 2.5 Ah capacity are cycled at both 25 °C and 0 °C separately, and at 25 °C two charging protocols (constant current, and constant current-constant voltage charge) are used. Differential voltage analysis (dV/dQ) and alternating current (AC) impedance are mainly used to investigate battery degradation mechanisms quantitatively. The dV/dQ suggests that active cathode loss and loss of lithium inventory (LLI) are the dominating degradation factors. Significant microcracks are observed in the fatigued cathode particles from the scanning electron microscopy (SEM) images. Crystal structure parameters of selected fatigued batteries at fully charged state are determined by in situ high-resolution neutron powder diffraction. Obvious increases of ohmic resistance and solid electrolyte interphase (SEI) resistance occur when the battery capacity fade falls beneath 20%. Continuous charge transfer resistance and Warburg impedance coefficient (W.eff) increase are observed in the course of cycling. Correlation analysis is performed to bridge the gap between material loss as well as LLI and impedance increase. The increase of the charge transfer resistance is related to both active cathode loss and LLI, and a functional relationship is revealed between LLI and W.eff regardless of the used cycling protocols. • 18650-type Cells are cycled at 0 °C and 25 °C using two charging protocols. • Main degradation factors are loss of lithium inventory (LLI) and active cathode loss. • Neutron powder diffraction and post-mortem analysis are done for deep understanding. • Correlations between material loss and impedance parameters are revealed. • Warburg impedance coefficient could be correlated to LLI in the course of cycling. [ABSTRACT FROM AUTHOR]

Aliovalent substitution is a common strategy to improve the ionic conductivity of solid electrolytes for solid-state batteries. The substitution of SbS 4 3- by WS 4 2- in Na 2.9 Sb 0.9 W 0.1 S 4 leads to a very high ionic conductivity of 41 mS cm -1 at room temperature. While pristine Na 3 SbS 4 crystallizes in a tetragonal structure, the substituted Na 2.9 Sb 0.9 W 0.1 S 4 crystallizes in a cubic phase at room temperature based on its X-ray diffractogram. Here, we show by performing pair distribution function analyses and static single-pulse 121 Sb NMR experiments that the short-range order of Na 2.9 Sb 0.9 W 0.1 S 4 remains tetragonal despite the change in the Bragg diffraction pattern. Temperature-dependent Raman spectroscopy revealed that changed lattice dynamics due to the increased disorder in the Na + substructure leads to dynamic sampling causing the discrepancy in local and average structure. While showing no differences in the local structure, compared to pristine Na 3 SbS 4 , quasi-elastic neutron scattering and solid-state 23 Na nuclear magnetic resonance measurements revealed drastically improved Na + diffusivity and decreased activation energies for Na 2.9 Sb 0.9 W 0.1 S 4 . The obtained diffusion coefficients are in very good agreement with theoretical values and long-range transport measured by impedance spectroscopy. This work demonstrates the importance of studying the local structure of ionic conductors to fully understand their transport mechanisms, a prerequisite for the development of faster ionic conductors.

In this work, praseodymium(iii) borohydride, Pr(BH4)3, and an isotopically enriched analogue, Pr(11BD4)3, are prepared by a new route via a solvate complex, Pr(11BD4)3S(CH3)2. Nd(BH4)3 was synthesized using the same method and the structures, polymorphic transformations, and thermal stabilities of these compounds are investigated in detail. α-Pr(BH4)3 and α-Nd(BH4)3 are isostructural with cubic unit cells (Pa3[combining macron]) stable at room temperature (RT) and a unit cell volume per formula unit (V/Z) of 180.1 and 175.8 Å3, respectively. Heating α-Pr(BH4)3 to T ∼ 190 °C, p(Ar) = 1 bar, introduces a transition to a rhombohedral polymorph, r-Pr(BH4)3 (R3[combining macron]c) with a smaller unit cell volume and a denser structure, V/Z = 156.06 Å3. A similar transition was not observed for Nd(BH4)3. However, heat treatment of α-Pr(BH4)3, at T ∼ 190 °C, p(H2) = 40 bar and α-Nd(BH4)3, at T ∼ 270 °C, p(H2) = 98 bar facilitates reversible formation of another three cubic polymorph, denoted as β, β' and β''-RE(BH4)3 (Fm3[combining macron]c). Moreover, the transition β- to β'- to β''- is considered a rare example of stepwise negative thermal expansion. For Pr(BH4)3, ∼2/3 of the sample takes this route of transformation whereas in argon only ∼5 wt%, and the remaining transforms directly from α- to r-Pr(BH4)3. The β-polymorphs are porous with V/Z = 172.4 and 172.7 Å3 for β''-RE(BH4)3, RE = Pr or Nd, respectively, and are stabilized by the elevated hydrogen pressures. The polymorphic transitions occur due to rotation of RE(BH4)6 octahedra without breaking or forming chemical bonds. Structural DFT optimization reveals the decreasing stability of α-Pr(BH4)3 > β-Pr(BH4)3 > r-Pr(BH4)3.