Lithium Borohydride Nanorods: Self-Assembling Growth and Remarkable Hydrogen Cycling Properties.

Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.

Hydrogen Storage in Partially Exfoliated Magnesium Diboride Multilayers.

Metal boride nanostructures have shown significant promise for hydrogen storage applications. However, the synthesis of nanoscale metal boride particles is challenging because of their high surface energy, strong inter- and intraplanar bonding, and difficult-to-control surface termination. Here, it is demonstrated that mechanochemical exfoliation of magnesium diboride in zirconia produces 3-4 nm ultrathin MgB2 nanosheets (multilayers) in high yield. High-pressure hydrogenation of these multilayers at 70 MPa and 330 °C followed by dehydrogenation at 390 °C reveals a hydrogen capacity of 5.1 wt%, which is ≈50 times larger than the capacity of bulk MgB2 under the same conditions. This enhancement is attributed to the creation of defective sites by ball-milling and incomplete Mg surface coverage in MgB2 multilayers, which disrupts the stable boron-boron ring structure. The density functional theory calculations indicate that the balance of Mg on the MgB2 nanosheet surface changes as the material hydrogenates, as it is energetically favorable to trade a small number of Mg vacancies in Mg(BH4 )2 for greater Mg coverage on the MgB2 surface. The exfoliation and creation of ultrathin layers is a promising new direction for 2D metal boride/borohydride research with the potential to achieve high-capacity reversible hydrogen storage at more moderate pressures and temperatures.

An Ultra-Stable Electrode-Solid Electrolyte Composite for High-Performance All-Solid-State Li-Ion Batteries.

The low ionic and electronic conductivity between current solid electrolytes and high-capacity anodes limits the long-term cycling performance of all-solid-state lithium-ion batteries (ASSLIBs). Herein, this work reports the fabrication of an ultra-stable electrode-solid electrolyte composite for high-performance ASSLIBs enabled by the homogeneous coverage of ultrathin Mg(BH4 )2 layers on the surface of each MgH2 nanoparticle that are uniformly distributed on graphene. The initial discharge process of Mg(BH4 )2 layers results in uniform coverage of MgH2 nanoparticle with both LiBH4 as the solid electrolyte and Li2 B6 with even higher Li ion conductivity than LiBH4 . Consequently, the Li ion conductivity of graphene-supported MgH2 nanoparticles covered with ultrathin Mg(BH4 )2 layers is two orders of magnitude higher than that without Mg(BH4 )2 layers. Moreover, the thus-formed inactive Li2 B6 with strong adsorption capability toward LiBH4 , acts as a stabilizing framework, which, coupled with the structural support role of graphene, alleviates the volume change of MgH2 nanoparticles and facilitates the intimate contact between LiBH4 and individual MgH2 nanoparticles, leading to the formation of uniform stable interfaces with high ionic and electronic conductivity on each MgH2 nanoparticles. Hence, an ultrahigh specific capacity of 800 mAh g-1 is achieved for MgH2 at 2 A g-1 after 350 cycles.

Coupling Titanium and Chromium Catalysis in a Reaction Network for the Reprogramming of [BH4 ]- as Electron Transfer and Hydrogen Atom Transfer Reagent for Radical Chemistry.

We describe a unique catalytic system with an efficient coupling of Ti- and Cr-catalysis in a reaction network that allows the use of [BH4 ]- as stoichiometric hydrogen atom and electron donor in catalytic radical chemistry. The key feature is a relay hydrogen atom transfer from [BH4 ]- to Cr generating the active catalysts under mild conditions. This enables epoxide reductions, regiodivergent epoxide opening and radical cyclizations that are not possible with cooperative catalysis with radicals or by epoxide reductions via Meinwald rearrangement and ensuing carbonyl reduction. No typical SN 2-type reactivity of [BH4 ]- salts is observed.

Nucleophilic Substitution Reactions in the [B3H8]- Anion in the Presence of Lewis Acids.

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph3P, Ph2P-(CH2)2-PPh2 (dppe), Ph3As, Et3N, PhNH2, C5H5N, CH3CN, Ph2CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B3H7Nu] are obtained. It is found that the use of TiCl4, AlCl3, ZrCl4, HfCl4, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B3H7-HMXnx], which was detected by NMR spectroscopy. The structures of [Ph3P·B3H7] and [PhNH2·B3H7] were determined by X-ray diffraction.

Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes.

Thermodynamic hydricity (HDAMeCN) determined as Gibbs free energy (ΔG°[H]-) of the H- detachment reaction in acetonitrile (MeCN) was assessed for 144 small borane clusters (up to 5 boron atoms), polyhedral closo-boranes dianions [BnHn]2-, and their lithium salts Li2[BnHn] (n = 5-17) by DFT method [M06/6-311++G(d,p)] taking into account non-specific solvent effect (SMD model). Thermodynamic hydricity values of diborane B2H6 (HDAMeCN = 82.1 kcal/mol) and its dianion [B2H6]2- (HDAMeCN = 40.9 kcal/mol for Li2[B2H6]) can be selected as border points for the range of borane clusters' reactivity. Borane clusters with HDAMeCN below 41 kcal/mol are strong hydride donors capable of reducing CO2 (HDAMeCN = 44 kcal/mol for HCO2-), whereas those with HDAMeCN over 82 kcal/mol, predominately neutral boranes, are weak hydride donors and less prone to hydride transfer than to proton transfer (e.g., B2H6, B4H10, B5H11, etc.). The HDAMeCN values of closo-boranes are found to directly depend on the coordination number of the boron atom from which hydride detachment and stabilization of quasi-borinium cation takes place. In general, the larger the coordination number (CN) of a boron atom, the lower the value of HDAMeCN.

Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes.

The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH3 ]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy3 )2 HCl(H2 )] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.

Exploring Ternary and Quaternary Mixtures in the LiBH4 -NaBH4 -KBH4 -Mg(BH4 )2 -Ca(BH4 )2 System.

Binary combinations of borohydrides have been extensivly investigated evidencing the formation of eutectics, bimetallic compounds or solid solutions. In this paper, the investigation has been extended to ternary and quaternary systems in the LiBH4 -NaBH4 -KBH4 -Mg(BH4 )2 -Ca(BH4 )2 system. Possible interactions among borohydrides in equimolar composition has been explored by mechanochemical treatment. The obtained phases were analysed by X-ray diffraction and the thermal behaviour of the mixtures were analysed by HP-DSC and DTA, defining temperature of transitions and decomposition reactions. The release of hydrogen was detected by MS, showing the role of the presence of solid solutions and multi-cation compounds on the hydrogen desorption reactions. The presence of LiBH4 generally promotes the release of H2 at about 200 °C, while KCa(BH4 )3 promotes the release in a single-step reaction at higher temperatures.

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches.

Hydrogen technology has become essential to fulfill our mobile and stationary energy needs in a global low-carbon energy system. The non-renewability of fossil fuels and the increasing environmental problems caused by our fossil fuel-running economy have led to our efforts towards the application of hydrogen as an energy vector. However, the development of volumetric and gravimetric efficient hydrogen storage media is still to be addressed. LiBH4 is one of the most interesting media to store hydrogen as a compound due to its large gravimetric (18.5 wt.%) and volumetric (121 kgH2/m3) hydrogen densities. In this review, we focus on some of the main explored approaches to tune the thermodynamics and kinetics of LiBH4: (I) LiBH4 + MgH2 destabilized system, (II) metal and metal hydride added LiBH4, (III) destabilization of LiBH4 by rare-earth metal hydrides, and (IV) the nanoconfinement of LiBH4 and destabilized LiBH4 hydride systems. Thorough discussions about the reaction pathways, destabilizing and catalytic effects of metals and metal hydrides, novel synthesis processes of rare earth destabilizing agents, and all the essential aspects of nanoconfinement are led.

Synthesis of α-Chlorolactams by Cyanoborohydride-Mediated Radical Cyclization of Trichloroacetamides.

A cyanoborohydride-promoted radical cyclization methodology has been developed to access α-chlorolactams in a simple and efficient way using NaBH3 CN and trichloroacetamides easily available from allylic and homoallylic secondary amines. This methodology allowed the synthesis of a library of α-chlorolactams (mono- and bicyclic), which were tested for herbicidal activity, trans-3-chloro-4-methyl-1-(3-trifluoromethyl)phenyl-2-pyrrolidinone being the most active.

Deprotonation of a Hydridoborate Anion.

The first deprotonation of a borohydride anion was achieved by treatment of [BH(CN)3 ]- with strong non-nucleophilic bases, which resulted in the formation of alkali-metal salts of the tricyanoborate dianion B(CN)32- in up to 97 % yield and 99.5 % purity. [BH(CN)3 ]- is less acidic than (Me3 Si)2 NH but a stronger acid than iPr2 NH. Less sterically hindered, more nucleophilic bases such as PhLi and MeLi mostly attack a CN group under formation of imine dianions [RC(N)B(CN)3 ]2- , which can be hydrolyzed to ketones of the [RC(O)B(CN)3 ]- type. The boron-centered nucleophile B(CN)32- reacts with CO2 and CN+ reagents to give salts of the [B(CN)3 CO2 ]2- dianion and the tetracyanoborate anion [B(CN)4 ]- , respectively, in excellent yields.

Metal-Borohydride-Modified Zr(BH4 )4 ⋠8 NH3 : Low-Temperature Dehydrogenation Yielding Highly Pure Hydrogen.

Due to its high hydrogen density (14.8 wt %) and low dehydrogenation peak temperature (130 °C), Zr(BH4 )4 ⋅8 NH3 is considered to be one of the most promising hydrogen-storage materials. To further decrease its dehydrogenation temperature and suppress its ammonia release, a strategy of introducing LiBH4 and Mg(BH4 )2 was applied to this system. Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 composites showed main dehydrogenation peaks centered at 81 and 106 °C as well as high hydrogen purities of 99.3 and 99.8 mol % H2 , respectively. Isothermal measurements showed that 6.6 wt % (within 60 min) and 5.5 wt % (within 360 min) of hydrogen were released at 100 °C from Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , respectively. The lower dehydrogenation temperatures and improved hydrogen purities could be attributed to the formation of the diammoniate of diborane for Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 , and the partial transfer of NH3 groups from Zr(BH4 )4 ⋅8 NH3 to Mg(BH4 )2 for Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , which result in balanced numbers of BH4 and NH3 groups and a more active H(δ+) ⋅⋅⋅(-δ) H interaction. These advanced dehydrogenation properties make these two composites promising candidates as hydrogen-storage materials.

Facile formation of thermodynamically unstable novel borohydride materials by a wet chemistry route.

A novel wet synthetic method utilizing weakly coordinating anions that yields LiCl-free Zn-based materials for hydrogen storage has recently been reported. Here we show that this method may also be applied for the synthesis of the pure yttrium derivatives, M[Y(BH4)4] (M = K, Rb, Cs). Moreover, it can be extended to the preparation of previously unknown thermodynamically unstable derivatives, Li[Y(BH4)4] and Na[Y(BH4)4]. Importantly, these two H-rich phases cannot be accessed by standard dry (mechanochemical) or solid/gas synthetic methods due to the thermodynamic obstacles. Here we describe their crystal structures and selected important physicochemical properties.

Hydrogen storage materials: room-temperature wet-chemistry approach toward mixed-metal borohydrides.

The poor kinetics of hydrogen evolution and the irreversibility of the hydrogen discharge hamper the use of transition metal borohydrides as hydrogen storage materials, and the drawbacks of current synthetic methods obstruct the exploration of these systems. A wet-chemistry approach, which is based on solvent-mediated metathesis reactions of precursors containing bulky organic cations and weakly coordinating anions, leads to mixed-metal borohydrides that contain only a small amount of "dead mass". The applicability of this method is exemplified by Li[Zn2(BH4)5] and M[Zn(BH4)3] salts (M=Na, K), and its extension to other systems is discussed.

Nature-Inspired Strategy: Novel Borohydride-Based Solid Electrolytes Extracted from Cathode-Electrolyte Interphase.

As the core component of all-solid-state batteries, current solid-state electrolytes fail to simultaneously meet multiple demands, such as their own high performance, the chemical, electrochemical and mechanical compatibility of electrode interface. A fresh perspective is rather desired to guide the development of novel solid electrolytes with comprehensive performance. Herein, this work proposes a novel strategy to synthesize solid electrolytes extracted from cathode-electrolyte interphase (CEI), which is inspired by peach trees secreting peach gum to prevent further damage. A proof-of-concept, using LiBH4-Se and LiBH4-S as prototypes, confirms that as-synthesized electrolytes inherited and improved up the advantages of LiBH4 with unexpected compatibility toward multiple cathodes. It is believed that the family of new electrolytes will be continuously expanded under the guidance of this CEI-derived concept.

MYb(BH4)4 (M = K, Na) from laboratory X-ray powder data.

Two new borohydrides, potassium ytterbium tetraborohydride, KYb(BH4)4, and sodium ytterbium tetraborohydride, NaYb(BH4)4, have been synthesized via mechanochemical reactions in the solid state. The two compounds are isostructural and both crystallize in the Cmcm space group in the structure reported previously for NaSc(BH4)4 and KY(BH4)4. This crystal structure is composed of isolated homoleptic [Yb(BH4)4](-) anions surrounded by M(+) cations (M = Na, K). The packing of the M(+) cations and [Yb(BH4)4](-) anions is a distorted variant of the hexagonal NiAs structure type, with M(+) forming distorted trigonal prisms, i.e. M6. Each second prism surrounds a [Yb(BH4)4](-) anion, while the [Yb(BH4)4](-) anions are arranged into deformed octahedra around the M(+) cations.

The Preparation, Characterization, and Pressure-Influenced Dihydrogen Interactions of Tetramethylphosphonium Borohydride.

Tetramethylphosphonium borohydride was synthesized via an ion metathesis reaction in a weakly-coordinating aprotic environment. [(CH3)4P]BH4, in contrast to related [(CH3)4N]+ compounds which tend to crystallize in a tetragonal system, adopts the distorted wurtzite structure (P63mc), resembling some salts containing analogous ions of As and Sb. [(CH3)4P]BH4 decomposes thermally in several endo- and exothermic steps above ca. 240 °C. This renders it more stable than [(CH3)4N]BH4, with a lowered temperature of decomposition onset by ca. 20 °C and solely exothermic processes observed. Raman spectra measured at the 0-10 GPa range indicate that a polymorphic transition occurs within 0.53-1.86 GPa, which is further confirmed by the periodic DFT calculations. The latter suggests a phase transition around 0.8 GPa to a high-pressure phase of [(CH3)4N]BH4. The P63mc phase seems to be destabilized under high pressure by relatively closer dihydrogen interactions, including the C-H…H-C contacts.

Synergized Tricomponent All-Inorganics Solid Electrolyte for Highly Stable Solid-State Li-Ion Batteries.

Garnet-type oxide Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) features superior ionic conductivity and good stability toward lithium (Li) metal, but requires high-temperature sintering (≈1200 °C) that induces high fabrication cost, poor mechanical processability, and high interface resistance. Here, a novel high-performance tricomponent composite solid electrolyte (CSE) comprising LLZTO-4LiBH4 /xLi3 BN2 H8 is reported, which is prepared by ball milling the LLZTO-4LiBH4  mixture followed by hand milling with Li3 BN2 H8 . Green pellets fabricated by heating the cold-pressed CSE powders at 120 °C offer ultrafast room-temperature ionic conductivity (≈1.73 × 10-3  S cm-1  at 30 °C) and ultrahigh Li-ion transference number (≈0.9999), which enable the Li|Li symmetrical cells to cycle over 1600 h at 30 °C with only 30 mV of overpotential. Moreover, the Li|CSE|TiS2  full cells deliver 201 mAh g-1  of capacity with long cyclability. These outstanding performances are due to the low open porosity in the electrolyte pellets as well as the high intrinsic ionic conductivity and easy deformability of Li3 BN2 H8 .

Synthesis Method of Unsolvated Organic Derivatives of Metal Borohydrides.

A new, scalable, wet-chemistry single-pot method of synthesising pure unsolvated organic derivatives of metal borohydrides is presented. The metathetic reaction in a weakly coordinating solvent is exemplified by the synthesis of [(n-C4H9)4N][Y(BH4)4] and [Ph4P][Y(BH4)4] systems. For the latter compound, the crystal structure was solved and described. Organic borohydride salts obtained by the new method can find various applications, e.g., can be used as precursors in synthesis of hydrogen-rich mixed-metal borohydrides-promising materials for solid-state chemical storage of hydrogen.

Core-shell NaBH4 @Ni Nanoarchitectures: A Platform for Tunable Hydrogen Storage.

The core-shell approach has surfaced as an attractive strategy to make complex hydrides reversible for hydrogen storage; however, no synthetic method exists for taking advantage of this approach. Here, a detailed investigation was undertaken to effectively design freestanding core-shell NaBH4 @Ni nanoarchitectures and correlate their hydrogen properties with structure and chemical composition. It was shown that the Ni shell growth on the surface of NaBH4 particles could be kinetically and thermodynamically controlled. The latter led to varied hydrogen properties. Near-edge X-ray absorption fine structure analysis confirmed that control over the Ni0 /Nix By concentrations upon NiII reduction led to a destabilized hydride system. Hydrogen release from the sphere, cube, and bar-like core-shell nanoarchitectures occurred at around 50, 90, and 95 °C, respectively, compared to the bulk (>500 °C). This core-shell approach, when extended to other hydrides, could open new avenues to decipher structure-property correlation in hydrogen storage/generation.