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Journal articles on the topic 'LiBH4'

Author: Grafiati

Published: 9 March 2023

Last updated: 10 March 2023

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1

de Kort, Laura M., Valerio Gulino, Didier Blanchard, and Peter Ngene. "Effects of LiBF4 Addition on the Lithium-Ion Conductivity of LiBH4." Molecules 27, no. 7 (March 28, 2022): 2187. http://dx.doi.org/10.3390/molecules27072187.

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Complex hydrides, such as LiBH4, are a promising class of ion conductors for all-solid-state batteries, but their application is constrained by low ion mobility at room temperature. Mixing with halides or complex hydride anions, i.e., other complex hydrides, is an effective approach to improving the ionic conductivity. In the present study, we report on the reaction of LiBH4 with LiBF4, resulting in the formation of conductive composites consisting of LiBH4, LiF and lithium closo-borates. It is believed that the in-situ formation of closo-borate related species gives rise to highly conductive interfaces in the decomposed LiBH4 matrix. As a result, the ionic conductivity is improved by orders of magnitude with respect to the Li-ion conductivity of the LiBH4, up to 0.9 × 10−5 S cm−1 at 30 °C. The insights gained in this work show that the incorporation of a second compound is a versatile method to improve the ionic conductivity of complex metal hydrides, opening novel synthesis pathways not limited to conventional substituents.

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2

Chen, X. Y., Y. H. Guo, L. Gao, and X. B. Yu. "Improved dehydrogenation of LiBH4 supported on nanoscale SiO2 via liquid phase method." Journal of Materials Research 25, no. 12 (December 2010): 2415–21. http://dx.doi.org/10.1557/jmr.2010.0301.

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A wet loading method was developed to produce nano-sized LiBH4 combined with nano-SiO2 templates. The multicomponent LiBH4/SiO2 material synthesized by the wet method has been found to dehydrogenate at much lower temperatures than the pure LiBH4, as well as LiBH4/SiO2 mixtures prepared by ball milling. For example, the onset of dehydrogenation was decreased to about 200 °C for a wet-treated LiBH4/SiO2 mixture with a mass ratio of 1:1, and the majority of the hydrogen could be released below 350 °C. The improved dehydrogenation of the wet-treated LiBH4/SiO2 mixtures can be attributed to the destabilization of SiO2, resulting in the formation of lithium metasilicate (Li2SiO3) upon heating, and the confinement of LiBH4 to form nanoscale particles.

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3

Xu, Lan, Yu Wang, Ling tong Zhou, Wei Xia, Zhu jian Li, Mei Qiang Fan, and Yong Jin Zou. "Enhanced Hydrogen Generation by LiBH4 Hydrolysis in MOH/water Solutions (MOH: C2H5OH, C4H8O, C4H9OH, CH3COOH) for Micro Proton Exchange Membrane Fuel Cell Application." Journal of New Materials for Electrochemical Systems 17, no. 2 (May 15, 2014): 077–83. http://dx.doi.org/10.14447/jnmes.v17i2.427.

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LiBH4 has high hydrogen storage capacity, and its high gravimetric hydrogen density reaches 18.36%. However, LiBH4 exhibits poor hydrolysis performance in water because the abrupt ending caused by the agglomeration of its hydrolysis products limits its full utilization [1, 2]. In this paper, four kinds of organics, namely, ethanol, tetrahydrofuran, acetic acid, and butanol (referred to MOH) were added to water, and the effect of MOH species and amount on the hydrolysis performances of LiBH4 was evaluated. Results show that agglomeration can be avoided and that LiBH4 has a controllable hydrogen generation rate and high hydrogen generation amount inMOH/water solutions compared with that in pure water. The order in terms of the hydrolysis performance of LiBH4 in MOH/water solutions is as follows: acetic acid >butanol> tetrahydrofuran >ethanol. From XRD, SEM, and other analyses, the enhancement performance is explained by the diluting and solvent effects. Moreover, the addition of MOH alters the hydrolysis route of LiBH4. MOH acts as not only a carrier for water and LiBH4 but also as a reactant to form intermediate LiBH4·[MOH(H2O)x]y, which slows the hydrolysis kinetics of LiBH4. Hydrolysis conditions were optimized, and high hydrogen amount was achieved correspondingly. The experimental data presents the potential application of LiBH4 as a highly efficiency and stable hydrogen source for fuel cells.

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4

Leiner, Stefanie, Peter Mayer, and Heinrich Nöth. "Synthesis and Structures of LiBH4 Complexes with N-Heterocycles [1]." Zeitschrift für Naturforschung B 64, no. 7 (July 1, 2009): 793–99. http://dx.doi.org/10.1515/znb-2009-0703.

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LiBH4 solutions in diethyl ether or tetrahydrofuran react with N-methylmorpholine, Nmethylimidazole or piperidine not only with the formation of adducts LiBH4(L)n (n = 1 or 3) but also with formation of amine boranes BH3(L). While LiBH4 and N-methylimidazole form the 1 : 3 adduct 1, N-methylmorpholine produces the 1 : 1 adduct 2. In both cases the adducts contain hexacoordinated Li atoms. In 1 the Li atom is coordinated to three N atoms and three H atoms. However, in compound 2 the molecules are connected in the solid state with one another to form a two-dimensional polymer built from dimeric units (LiBH4)2 that are connected to adjacent dimeric units via the O and N atoms of the N-methylmorpholine ligand. Each of the Li atoms in 2 is connected to four H atoms via Li-H-B hydrogen bridges and an O and an N atom. The reaction of LiBH4 with piperidine leads to the compound (LiBH4)6(HNC5H10)16, 3, which consists of two independent LiBH4(HNC5H10)3 molecules and two others of composition (LiBH4)2(HNC5H10)5 containing penta- and hexacoordinated Li atoms.

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5

Puszkiel, Julián, Aurelien Gasnier, Guillermina Amica, and Fabiana Gennari. "Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches." Molecules 25, no. 1 (December 31, 2019): 163. http://dx.doi.org/10.3390/molecules25010163.

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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.

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6

He, Qing, Dongdong Zhu, Xiaocheng Wu, Duo Dong, Xiaoying Jiang, and Meng Xu. "The Dehydrogenation Mechanism and Reversibility of LiBH4 Doped by Active Al Derived from AlH3." Metals 9, no. 5 (May 13, 2019): 559. http://dx.doi.org/10.3390/met9050559.

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A detailed analysis of the dehydrogenation mechanism and reversibility of LiBH4 doped by as-derived Al (denoted Al*) from AlH3 was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD), scanning electronic microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The results show that the dehydrogenation of LiBH4/Al* is a five-step reaction: (1) LiBH4 + Al → LiH + AlB2 + “Li-Al-B-H” + B2H6 + H2; (2) the decomposition of “Li-Al-B-H” compounds liberating H2; (3) 2LiBH4 + Al → 2LiH + AlB2 + 3H2; (4) LiBH4 → LiH + B + 3/2H2; and (5) LiH + Al → LiAl + 1/2H2. Furthermore, the reversibility of the LiBH4/Al* composite is based on the following reaction: LiH + LiAl + AlB2 + 7/2H2 ↔ 2LiBH4 + 2Al. The extent of the dehydrogenation reaction between LiBH4 and Al* greatly depends on the precipitation and growth of reaction products (LiH, AlB2, and LiAl) on the surface of Al*. A passivation shell formed by these products on the Al* is the kinetic barrier to the dehydrogenation of the LiBH4/Al* composite.

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7

LIU, YONGFENG, HAI ZHOU, YUFAN DING, MINGXIA GAO, and HONGGE PAN. "LOW-TEMPERATURE HYDROGEN DESORPTION FROM LiBH4–TiF4 COMPOSITE." Functional Materials Letters 04, no. 04 (December 2011): 395–99. http://dx.doi.org/10.1142/s1793604711002305.

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Approximately 6.3 wt.% of hydrogen is released from a LiBH4–0.25TiF4 combination below 150°C. Hydrogen desorption from the LiBH4–0.25TiF4 combination undergoes a quite different reaction process with respect to the LiBH4–0.33TiF3 mixture due to the higher oxidation state of Ti4+ and the lower mean bond cleavage energy of Ti–F bonds in TiF4 . This finding provides a viable approach for significantly decreasing the dehydrogenation temperature of LiBH4 by optimizing the additives with high oxidation valency.

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8

Ghaani, Mohammad R., Michele Catti, and Niall J. English. "In Situ Synchrotron X-ray Diffraction Studies of Hydrogen-Desorption Properties of 2LiBH4–Mg2FeH6 Composite." Molecules 26, no. 16 (August 11, 2021): 4853. http://dx.doi.org/10.3390/molecules26164853.

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Adding a secondary complex metal hydride can either kinetically or thermodynamically facilitate dehydrogenation reactions. Adding Mg2FeH6 to LiBH4 is energetically favoured, since FeB and MgB2 are formed as stable intermediate compounds during dehydrogenation reactions. Such “hydride destabilisation” enhances H2-release thermodynamics from H2-storage materials. Samples of the LiBH4 and Mg2FeH6 with a 2:1 molar ratio were mixed and decomposed under three different conditions (dynamic decomposition under vacuum, dynamic decomposition under a hydrogen atmosphere, and isothermal decomposition). In situ synchrotron X-ray diffraction results revealed the influence of decomposition conditions on the selected reaction path. Dynamic decomposition of Mg2FeH6–LiBH4 under vacuum, or isothermal decomposition at low temperatures, was found to induce pure decomposition of LiBH4, whilst mixed decomposition of LiBH4 + Mg and formation of MgB2 were achieved via high-temperature isothermal dehydrogenation.

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9

Yan, Xia Yan, You Li, Jie Du, Xiao Na Luo, and Cheng Qin. "Preparation of High Weight Loading Lithium Borohydride in Carbon Aerogels." Advanced Materials Research 631-632 (January 2013): 287–90. http://dx.doi.org/10.4028/www.scientific.net/amr.631-632.287.

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We describe approaches using modified carbon aerogels for increasing the weight loading of LiBH4. Large pore volume carbon aerogels were prepared with a sol-gel method and a polymethyl methacrylate (PMMA) microsphere template. Compared to those without using templates, the pore volume has been up to 3.8 times with a PMMA template. After incorporation into carbon aerogels, the weight loading of LiBH4 has reached 80%. Nitrogen absorption/desorption measurements show that more than 95% free space of carbon aerogels has been incorporated with LiBH4. Rama spectra suggest that there is no PMMA or chemical reaction during the synthesis of LiBH4/carbon aerogel composites.

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10

Kim, Ji Woo, Kee-Bum Kim, Jae-Hyeok Shim, Young Whan Cho, and Kyu Hwan Oh. "Microstructural Characterization of Dehydrogenated Products of the LiBH4-YH3 Composite." Microscopy and Microanalysis 20, no. 6 (October 28, 2014): 1798–804. http://dx.doi.org/10.1017/s1431927614013373.

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AbstractThe dehydrogenated microstructure of the lithium borohydride-yttrium hydride (LiBH4-YH3) composite obtained at 350°C under 0.3 MPa of hydrogen and static vacuum was investigated by transmission electron microscopy combined with a focused ion beam technique. The dehydrogenation reaction between LiBH4 and YH3 into LiH and YB4 takes place under 0.3 MPa of hydrogen, which produces YB4 nano-crystallites that are uniformly distributed in the LiH matrix. This microstructural feature seems to be beneficial for rehydrogenation of the dehydrogenation products. On the other hand, the dehydrogenation process is incomplete under static vacuum, leading to the unreacted microstructure, where YH3 and YH2 crystallites are embedded in LiBH4 matrix. High resolution imaging confirmed the presence of crystalline B resulting from the self-decomposition of LiBH4. However, Li2B12H12, which is assumed to be present in the LiBH4 matrix, was not clearly observed.

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11

de Kort, Laura Maria, Petra E. de Jongh, and Peter Ngene. "(Digital Presentation) Nanoscaffold Porosity and Surface Chemistry Effects on Li-Ion Conductivity in Metal Hydride Nanocomposite Electrolytes." ECS Meeting Abstracts MA2022-01, no. 47 (July 7, 2022): 1977. http://dx.doi.org/10.1149/ma2022-01471977mtgabs.

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The development of energy storage technologies, such as rechargeable batteries, is crucial for the transition to a sustainable energy supply. Lithium-ion batteries are an effective means of energy storage, which is demonstrated by their wide application ranging from mobile phones to laptops and electric vehicles. Unfortunately, Li-ion batteries suffer from safety issues arising from their combustible organic electrolytes. All-solid-state batteries, in which the common liquid organic electrolyte is replaced by a solid-state electrolyte, could potentially lead to safer batteries with increased energy density.[1] Recently, metal hydrides (e.g. LiBH4 and LiCB11H12) have gained attention as promising solid electrolytes due to their electrochemical and thermal stability, low density and high ionic conductivity albeit at elevated temperatures. However, for successful incorporation of metal hydride electrolytes in all-solid-state batteries, sufficient ionic conductivity at room temperature is a prerequisite. Therefore, the development of strategies that enhance the room temperature conductivity in complex hydrides (10-8 S cm-1 for LiBH4) is of major importance. In this contribution, we combined two promising strategies to enhance ion mobility in metal hydrides, namely, partial ionic substitution[2] and nanoconfinement[3], which led to highly conductive metal hydride-based nanocomposites (Figure 1). Specifically, via partial ion substitution with LiNH2, followed by nanoconfinement in a mesoporous oxide scaffold, LiBH4-LiNH2/metal oxide nanocomposites with conductivities reaching 5x10-4 S cm-1 at 30 °C were obtained[4], compared to 2x10-8 S cm-1 for pure LiBH4. Interestingly, the conductivity of the LiBH4-LiNH2/metal oxide nanocomposites is strongly influenced by the chemical and physical nature of the mesoporous metal oxide. We systematically studied the influence of the scaffold properties on the conductivity of nanoconfined LiNH2-substituted LiBH4 using mesoporous silica scaffolds (SBA-15) with varying surface chemistry and pore structure. The conductivity varied over three orders of magnitude when tuning both the porosity and surface chemistry of the metal oxide scaffold.[5] Our study reveals that the LiBH4-LiNH2/metal oxide conductivity is affected by the chemical nature of the scaffold, similar to LiBH4/metal oxide nanocomposites. A conductivity improvement of a factor of two is achieved by changing the SiO2 (SBA-15) surface chemistry through alumination (Figure 2a). On the other hand, different from nanoconfined LiBH4, the conductivity of LiBH4-LiNH2/metal oxide nanocomposites is largely dictated by the pore structure of the scaffold, especially the pore volume (Figure 2b). Notably, the conductivity can be varied from 4x10-7 S cm-1 to 5x10-4 S cm-1 by increasing the scaffold pore volume from 0.51 to 1.00 cm3 g-1. Our work demonstrates that the origin of the conductivity enhancement in anion-substituted complex hydride-based nanocomposite electrolytes is different from other nanoconfined complex hydrides, e.g. LiBH4. In particular, for nanoconfined LiBH4-LiNH2, the conductivity improvement is attributed to stabilization of a highly conductive phase inside the scaffold pores, rather than the formation of a conductive interfacial layer at the hydride/oxide interface as observed for nanoconfined LiBH4. Thus, it is clear that the conductivity of metal hydride-based nanocomposite ion conductors is closely linked to the properties of scaffold material. The fundamental insights on the influence of scaffold properties on ion mobility in nanocomposite materials could be applicable to other cation- and anion substituted ion conductors as well. Thereby, this work provides useful insights for the design novel solid-state electrolytes with excellent ionic conductivity, crucial for the development of next generation batteries. References [1] Janek, Jürgen, and Zeier, Wolfgang G. "A solid future for battery development." Nature Energy 1.9 (2016): 1-4. [2] Maekawa, Hideki, et al. "Halide-stabilized LiBH4, a room-temperature lithium fast-ion conductor." Journal of the American Chemical Society 131.3 (2009): 894-895. [3] Blanchard, Didier, et al. "Nanoconfined LiBH4 as a fast lithium ion conductor." Advanced Functional Materials 25.2 (2015): 184-192 [4] Zettl, Roman, et al. "Combined Effects of Anion Substitution and Nanoconfinement on the Ionic Conductivity of Li-Based Complex Hydrides." The Journal of Physical Chemistry C 124.5 (2020): 2806-2816. [5] de Kort, Laura M., et al. "The effect of nanoscaffold porosity and surface chemistry on the Li-ion conductivity of LiBH4–LiNH2/metal oxide nanocomposites." Journal of Materials Chemistry A 8.39 (2020): 20687-20697. Figure 1

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12

Palade, Petru, Cezar Comanescu, and Cristian Radu. "Synthesis of Nickel and Cobalt Ferrite-Doped Graphene as Efficient Catalysts for Improving the Hydrogen Storage Kinetics of Lithium Borohydride." Materials 16, no. 1 (January 2, 2023): 427. http://dx.doi.org/10.3390/ma16010427.

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Featuring a high hydrogen storage content of up to 20 wt%, complex metal borohydrides remain promising solid state hydrogen storage materials, with the real prospect of reversible behavior for a zero–emission economy. However, the thermodynamic barriers and sluggish kinetics are still barriers to overcome. In this context, nanoconfinement has provided a reliable method to improve the behavior of hydrogen storage materials. The present work describes the thermodynamic and kinetic enhancements of LiBH4 nanoconfined in MFe2O4 (M=Co, Ni) ferrite-catalyzed graphene host. Composites of LiBH4-catalysts were prepared by melt infiltration and investigated by X-ray diffraction, TEM, STEM-EDS and TPD. The role of ferrite additives, metal precursor treatment (Ar, Ar/H2) and the effect on hydrogen storage parameters are discussed. The thermodynamic parameters for the most promising composite LiBH4-graphene-NiFe2O4 (Ar) were investigated by Kissinger plot method, revealing an EA = 127 kJ/mol, significantly lower than that of neat LiBH4 (170 kJ/mol). The reversible H2 content of LiBH4-graphene-NiFe2O4 (Ar) after 5 a/d cycles was ~6.14 wt%, in line with DOE’s target of 5.5 wt% storage capacity, while exhibiting the lowest desorption temperature peak of 349 °C. The composites with catalysts treated in Ar have lower desorption temperature due to better catalyst dispersion than using H2/Ar.

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13

Miyazaki, Reona, Dai Kurihara, Daiki Hayashi, Seiya Furughori, Masatoshi Shomura, and Takehiko Hihara. "Post-anneal effect on the structural and Li+ conduction properties in NaI - LiBH4 system." MRS Advances 2, no. 7 (2017): 389–94. http://dx.doi.org/10.1557/adv.2017.19.

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ABSTRACTIn the present work, NaI – LiBH4 system fabricated by ball milling were post annealed and their variation of Li+ ion conductivity were investigated. From the change of lattice parameters by post annealing, it was suggested that unreacted LiBH4 existed in as-milled sample further dissolved into NaI, which implied an enhancement of the sample homogeneity. On the other hand, the segregation of LiI was anticipated when ball milled 15NaI·LiI (BH4 free sample) was annealed at 423 K. Li+ conductivity was decreased by post anneal process and compositional dependence of an activation energy for Li+ conduction was indicated for the homogeneous NaI – LiBH4 system.

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14

Zeng, Liang, Hiroki Miyaoka, Takayuki Ichikawa, and Yoshitsugu Kojima. "Hydrogen Exchange Effect in MgH₂-LiBH₄ System." Materials Science Forum 654-656 (June 2010): 2855–58. http://dx.doi.org/10.4028/www.scientific.net/msf.654-656.2855.

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MgH2-LiBH4 system is one of the promising hydrogen storage materials. In the system, it was found that there was a mutual interaction between the two hydrides, but its mechanism has not been clarified yet. In this work, we found an “H-D” exchange between MgD2 and LiBH4 during heating. IR absorption spectroscopy revealed that the peak of “B-D” vibration appeared at 275 °C below the melting and hydrogen desorption of the system, indicating that this exchange proceeded even in solid phases. The hydrogen desorption properties of the composite of catalyst-doped MgH2 and LiBH4 under inert gas were investigated by mass spectroscopy. The results showed that the hydrogen desorption temperature of the first step was over 300 °C, in spite of catalyst-doped MgH2 can release hydrogen at 200 °C. The above results might suggest the hydrogen desorption from catalyst-doped MgH2 is somehow suppressed by the exchange effect between MgH2 and LiBH4.

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15

Yu, Xuebin, Guanglin Xia, Zaiping Guo, and Huakun Liu. "Dehydrogenation/rehydrogenation mechanism in aluminum destabilized lithium borohydride." Journal of Materials Research 24, no. 8 (August 2009): 2720–27. http://dx.doi.org/10.1557/jmr.2009.0328.

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LiBH4/Al mixtures with various mol ratios were prepared by ball milling. The hydrogen storage properties of the mixtures were evaluated by differential scanning calorimetry/thermogravimetry analyses coupled with mass spectrometry measurements. The phase compositions and chemical state of elements for the LiBH4/Al mixtures before and after hydrogen desorption and absorption reactions were assessed via powder x-ray diffraction, infrared spectroscopy, and x-ray photoelectron spectroscopy. Dehydrogenation results revealed that LiBH4 could react with Al to form AlB2 and AlLi compounds with a two-step decomposition, resulting in improved dehydrogenation. The rehydrogenation experiments were investigated at 600 °C with various H2 pressure. It was found that intermediate hydride was formed firstly at a low H2 pressure of 30 atm, while LiBH4 could be reformed completely after increasing the pressure to 100 atm. Absorption/desorption cycle results showed that the dehydrogenation temperature increased and the hydrogen capacity degraded with the increase of cycle numbers.

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16

Le, Thi Thu, Claudio Pistidda, Julián Puszkiel, Chiara Milanese, Sebastiano Garroni, Thomas Emmler, Giovanni Capurso, Gökhan Gizer, Thomas Klassen, and Martin Dornheim. "Efficient Synthesis of Alkali Borohydrides from Mechanochemical Reduction of Borates Using Magnesium–Aluminum-Based Waste." Metals 9, no. 10 (September 29, 2019): 1061. http://dx.doi.org/10.3390/met9101061.

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Lithium borohydride (LiBH4) and sodium borohydride (NaBH4) were synthesized via mechanical milling of LiBO2, and NaBO2 with Mg–Al-based waste under controlled gaseous atmosphere conditions. Following this approach, the results herein presented indicate that LiBH4 and NaBH4 can be formed with a high conversion yield starting from the anhydrous borates under 70 bar H2. Interestingly, NaBH4 can also be obtained with a high conversion yield by milling NaBO2·4H2O and Mg–Al-based waste under an argon atmosphere. Under optimized molar ratios of the starting materials and milling parameters, NaBH4 and LiBH4 were obtained with conversion ratios higher than 99.5%. Based on the collected experimental results, the influence of the milling energy and the correlation with the final yields were also discussed.

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17

Patodia, Tarun, Mukesh Kumar Gupta, Rini Singh, Takayuki Ichikawa, Ankur Jain, and Balram Tripathi. "Electrochemical Performance of Graphene-Modulated Sulfur Composite Cathodes Using LiBH4 Electrolyte for All-Solid-State Li-S Battery." Energies 14, no. 21 (November 5, 2021): 7362. http://dx.doi.org/10.3390/en14217362.

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All-solid-state Li-S batteries (use of solid electrolyte LiBH4) were prepared using cathodes of a homogeneous mixture of graphene oxide (GO) and reduced graphene oxide (rGO) with sulfur (S) and solid electrolyte lithium borohydride (LiBH4), and their electrochemical performance was reported. The use of LiBH4 and its compatibility with Li metal permits the utilization of Li anode that improves the vitality of composite electrodes. The GO-S and rGO-S nanocomposites with different proportions have been synthesized. Their structural and morphological characterizations were performed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the results are presented. The electrochemical performance was tested by galvanostatic charge-discharge measurements at a 0.1 C-rate. The results presented here demonstrate the successful implementation of GO-S composites in an all-solid-state battery.

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18

Javadian, Payam, SeyedHosein Payandeh GharibDoust, Hai-Wen Li, Drew A. Sheppard, Craig E. Buckley, and Torben R. Jensen. "Reversibility of LiBH4 Facilitated by the LiBH4–Ca(BH4)2 Eutectic." Journal of Physical Chemistry C 121, no. 34 (August 21, 2017): 18439–49. http://dx.doi.org/10.1021/acs.jpcc.7b06228.

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19

Zhong, Yang, Xuefei Wan, Zhao Ding, and Leon L. Shaw. "New dehydrogenation pathway of LiBH4 + MgH2 mixtures enabled by nanoscale LiBH4." International Journal of Hydrogen Energy 41, no. 47 (December 2016): 22104–17. http://dx.doi.org/10.1016/j.ijhydene.2016.09.195.

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20

Soulié, J.-Ph, G. Renaudin, R. Černý, and K. Yvon. "Lithium boro-hydride LiBH4." Journal of Alloys and Compounds 346, no. 1-2 (November 2002): 200–205. http://dx.doi.org/10.1016/s0925-8388(02)00521-2.

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21

Gomes, S., H. Hagemann, and K. Yvon. "Lithium boro-hydride LiBH4." Journal of Alloys and Compounds 346, no. 1-2 (November 2002): 206–10. http://dx.doi.org/10.1016/s0925-8388(02)00668-0.

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22

He, Qing, Dongdong Zhu, Xiaocheng Wu, Duo Dong, Meng Xu, and Zhaofei Tong. "Hydrogen Desorption Properties of LiBH4/xLiAlH4 (x = 0.5, 1, 2) Composites." Molecules 24, no. 10 (May 15, 2019): 1861. http://dx.doi.org/10.3390/molecules24101861.

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A detailed analysis of the dehydrogenation mechanism of LiBH4/xLiAlH4 (x = 0.5, 1, 2) composites was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM), along with kinetic investigations using a Sievert-type apparatus. The results show that the dehydrogenation pathway of LiBH4/xLiAlH4 had a four-step character. The experimental dehydrogenation amount did not reach the theoretical expectations, because the products such as AlB2 and LiAl formed a passivation layer on the surface of Al and the dehydrogenation reactions associated with Al could not be sufficiently carried out. Kinetic investigations discovered a nonlinear relationship between the activation energy (Ea) of dehydrogenation reactions associated with Al and the ratio x, indicating that the Ea was determined both by the concentration of Al produced by the decomposition of LiAlH4 and the amount of free surface of it. Therefore, the amount of effective contact surface of Al is the rate-determining factor for the overall dehydrogenation of the LiBH4/xLiAlH4 composites.

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23

Saldan, Ivan. "A prospect for LiBH4 as on-board hydrogen storage." Open Chemistry 9, no. 5 (October 1, 2011): 761–75. http://dx.doi.org/10.2478/s11532-011-0068-9.

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AbstractIn contrast to the traditional metal hydrides, in which hydrogen storage involves the reversible hydrogen entering/exiting of the host hydride lattice, LiBH4 releases hydrogen via decomposition that produces segregated LiH and amorphous B phases. This is obviously the reason why lithium borohydride applications in fuel cells so far meet only one requirement — high hydrogen storage capacity. Nevertheless, its thermodynamics and kinetics studies are very active today and efficient ways to meet fuel cell requirements might be done through lowering the temperature for hydrogenation/dehydrogenation and suitable catalyst. Some improvements are expected to enable LiBH4 to be used in on-board hydrogen storage.

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24

Cai, Rong, Li Xian Sun, Fen Xu, Yong Jin Zou, and Hai Liang Chu. "LiBH₄ Confined in Nitrogen-Doped Ordered Mesoporous Carbons for Hydrogen Storage." Materials Science Forum 852 (April 2016): 858–63. http://dx.doi.org/10.4028/www.scientific.net/msf.852.858.

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Nitrogen-doped ordered mesoporous carbon has been synthesized and used to confine LiBH4 to improve its dehydrogenation properties. The carbon has a high BET specific surface up to 448.25 m2/g with pore size centered at 1.2 and 4.1 nm. The effects of ball milling time and speed on de-hydrogenation were investigated. The onset hydrogen desorption temperature of LiBH4 is reduced to 100 °C by addition 40 wt% carbon, and it can release hydrogen of 8.3 wt% at 380 °C. Furthermore, cyclic dehydrogenation is studiedto estimate the stability of the samples in the present work.

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25

Martínez, Alejandra A., Aurelien Gasnier, and Fabiana C. Gennari. "From Iron to Copper: The Effect of Transition Metal Catalysts on the Hydrogen Storage Properties of Nanoconfined LiBH4 in a Graphene-Rich N-Doped Matrix." Molecules 27, no. 9 (May 3, 2022): 2921. http://dx.doi.org/10.3390/molecules27092921.

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Incipient wetness impregnation was employed to decorate two N-doped graphene-rich matrixes with iron, nickel, cobalt, and copper nanoparticles. The N-doped matrix was wetted with methanol solutions of the corresponding nitrates. After agitation and solvent evaporation, reduction at 800 °C over the carbon matrix promoted the formation of nanoparticles. The mass of the metal fraction was limited to 5 wt. % to determine if limited quantities of metallic nanoparticles catalyze the hydrogen capture/release of nanoconfined LiBH4. Isotherms of nitrogen adsorption afforded the textural characterization of the matrixes. Electronic microscopy displayed particles of definite size, evenly distributed on the matrixes, as confirmed by X-ray diffraction. The same techniques assessed the impact of LiBH4 50 vol. % impregnation on nanoparticle distribution and size. The hydrogen storage properties of these materials were evaluated by differential scanning calorimetry and two cycles of volumetric studies. X-ray diffraction allowed us to follow the evolution of the material after two cycles of hydrogen capture-release. We discuss if limited quantities of coordination metals can improve the hydrogen storage properties of nanoconfined LiBH4, and which critical parameters might restrain the synergies between nanoconfinement and the presence of metal catalysts.

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26

Yang, Guoyu, Chen Xie, Yongtao Li, Hai-Wen Li, Dongming Liu, Jianguo Chen, and Qingan Zhang. "Enhancement of the ionic conductivity of lithium borohydride by silica supports." Dalton Transactions 50, no. 42 (2021): 15352–58. http://dx.doi.org/10.1039/d1dt02864b.

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27

Ley, Morten B., Elsa Roedern, and Torben R. Jensen. "Eutectic melting of LiBH4–KBH4." Phys. Chem. Chem. Phys. 16, no. 44 (2014): 24194–99. http://dx.doi.org/10.1039/c4cp03207a.

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28

Züttel, A., S. Rentsch, P. Fischer, P. Wenger, P. Sudan, Ph Mauron, and Ch Emmenegger. "Hydrogen storage properties of LiBH4." Journal of Alloys and Compounds 356-357 (August 2003): 515–20. http://dx.doi.org/10.1016/s0925-8388(02)01253-7.

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29

El Kharbachi, Abdelouahab, Eugenio Pinatel, Ioana Nuta, and Marcello Baricco. "A thermodynamic assessment of LiBH4." Calphad 39 (December 2012): 80–90. http://dx.doi.org/10.1016/j.calphad.2012.08.005.

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30

Mauron, Philippe, Florian Buchter, Oliver Friedrichs, Arndt Remhof, Michael Bielmann, Christoph N. Zwicky, and Andreas Züttel. "Stability and Reversibility of LiBH4." Journal of Physical Chemistry B 112, no. 3 (January 2008): 906–10. http://dx.doi.org/10.1021/jp077572r.

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31

Singh, Kishore, Yuchen Yao, Takayuki Ichikawa, Ankur Jain, and Rini Singh. "Zinc as a Promising Anodic Material for All-Solid-State Lithium-Ion Batteries." Batteries 8, no. 9 (September 5, 2022): 113. http://dx.doi.org/10.3390/batteries8090113.

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Electrochemical energy storage is considered a remarkable way to bridge the gap between demand and supply due to intermittent renewable energy production. All-solid-state batteries are an excellent alternative and are known to be the safest class of batteries. In the present scenario to accomplish the energy demands, high-capacity and stable anodes are warranted and can play a vital role in technology upgradation. Among the variety of anodes, alloying-type anodes are superior due to their high gravimetric capacity and stability. In the present work, zinc metal was implemented as electrode material in an all-solid-state lithium-ion battery. This anode material was tested with two different solid-state electrolytes, i.e., lithium borohydride (LiBH4) and halide-stabilized LiBH4 (i.e., LiBH4.LiI). In a coin cell, Li foil was placed as a counter electrode. The establishment of a reaction mechanism during the charging and discharging was obtained through X-ray diffraction (XRD) and cyclic voltammetry (CV). Systematic studies using the temperature dependence performance were also conducted. The volumetric density with both electrolytes was found at more than 3000 mAh/cm3. The coulombic efficiency for the electrode material was also observed at ~94%. These impressive numbers present zinc electrodes as a promising material for future electrode material for all-solid-state Li-ion batteries.

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32

Chaber, Paweł, Grzegorz Tylko, Jakub Włodarczyk, Paweł Nitschke, Anna Hercog, Sebastian Jurczyk, Jakub Rech, Jerzy Kubacki, and Grażyna Adamus. "Surface Modification of PHBV Fibrous Scaffold via Lithium Borohydride Reduction." Materials 15, no. 21 (October 25, 2022): 7494. http://dx.doi.org/10.3390/ma15217494.

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In this study, lithium borohydride (LiBH4) reduction was used to modify the surface chemistry of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibers. Although the most common reaction employed in the surface treatment of polyester materials is hydrolysis, it is not suitable for fiber modification of bacterial polyesters, which are highly resistant to this type of reaction. The use of LiBH4 allowed the formation of surface hydroxyl groups under very mild conditions, which was crucial for maintaining the fibers’ integrity. The presence of these groups resulted in a noticeable improvement in the surface hydrophilicity of PHBV, as revealed by contact angle measurements. After the treatment with a LiBH4 solution, the electrospun PHBV fibrous mat had a significantly greater number of viable osteoblast-like cells (SaOS-2 cell line) than the untreated mat. Moreover, the results of the cell proliferation measurements correlated well with the observed cell morphology. The most flattened SaOS-2 cells were found on the surface that supported the best cell attachment. Most importantly, the results of our study indicated that the degree of surface modification could be controlled by changing the degradation time and concentration of the borohydride solution. This was of great importance since it allowed optimization of the surface properties to achieve the highest cell-proliferation capacity.

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33

Peng, Jiamin, Yuwei Song, Yingying Wang, Zhenxing Liu, and Xuenian Chen. "Catalyst-free reductions of nitriles to amino-boranes using sodium amidoborane and lithium borohydride." Organic Chemistry Frontiers 9, no. 6 (2022): 1536–40. http://dx.doi.org/10.1039/d1qo01904j.

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The combination of sodium amidoborane (NaAB) and lithium borohydride (LiBH4) (mixed at a 1 : 3 molar ratio) can efficiently reduce various nitriles into amine-boranes at room temperature without catalysts.

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34

Borgschulte, A., A. Züttel, P. Hug, A. M. Racu, and J. Schoenes. "Hydrogen−Deuterium Exchange in Bulk LiBH4." Journal of Physical Chemistry A 112, no. 21 (May 2008): 4749–53. http://dx.doi.org/10.1021/jp711902p.

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35

Corey, Robert L., David T. Shane, Robert C. Bowman, and Mark S. Conradi. "Atomic Motions in LiBH4 by NMR." Journal of Physical Chemistry C 112, no. 47 (November 5, 2008): 18706–10. http://dx.doi.org/10.1021/jp807910p.

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36

Talyzin, A. V., O. Andersson, B. Sundqvist, A. Kurnosov, and L. Dubrovinsky. "High-pressure phase transition in LiBH4." Journal of Solid State Chemistry 180, no. 2 (February 2007): 510–17. http://dx.doi.org/10.1016/j.jssc.2006.10.032.

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37

Züttel, A., P. Wenger, S. Rentsch, P. Sudan, Ph Mauron, and Ch Emmenegger. "LiBH4 a new hydrogen storage material." Journal of Power Sources 118, no. 1-2 (May 2003): 1–7. http://dx.doi.org/10.1016/s0378-7753(03)00054-5.

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38

Ding, Zhao, Shaoyuan Li, Yang Zhou, Zhiqian Chen, Weijie Yang, Wenhui Ma, and Leon Shaw. "LiBH4 for hydrogen storage - New perspectives." Nano Materials Science 2, no. 2 (June 2020): 109–19. http://dx.doi.org/10.1016/j.nanoms.2019.09.003.

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39

Martelli, Pascal, Arndt Remhof, Andreas Borgschulte, Philippe Mauron, Dirk Wallacher, Ewout Kemner, Margarita Russina, Flavio Pendolino, and Andreas Züttel. "BH4−Self-Diffusion in Liquid LiBH4." Journal of Physical Chemistry A 114, no. 37 (September 23, 2010): 10117–21. http://dx.doi.org/10.1021/jp105585h.

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40

Blanchard, D., Q. Shi, C. B. Boothroyd, and T. Vegge. "Reversibility of Al/Ti Modified LiBH4." Journal of Physical Chemistry C 113, no. 31 (July 2009): 14059–66. http://dx.doi.org/10.1021/jp9031892.

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41

Hirota, Eizi, and Yoshiyuki Kawashima. "Internal Motion in Lithium Tetrahydroborate LiBH4." Journal of Molecular Spectroscopy 181, no. 2 (February 1997): 352–56. http://dx.doi.org/10.1006/jmsp.1996.7191.

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42

Martelli, Pascal, Arndt Remhof, Andreas Borgschulte, Ralf Ackermann, Thierry Strässle, Jan Peter Embs, Matthias Ernst, Motoaki Matsuo, Shin-Ichi Orimo, and Andreas Züttel. "Rotational Motion in LiBH4/LiI Solid Solutions." Journal of Physical Chemistry A 115, no. 21 (June 2, 2011): 5329–34. http://dx.doi.org/10.1021/jp201372b.

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43

Trück, J., E. Hadjixenophontos, Yug Joshi, G. Richter, P. Stender, and G. Schmitz. "Ionic conductivity of melt-frozen LiBH4 films." RSC Advances 9, no. 66 (2019): 38855–59. http://dx.doi.org/10.1039/c9ra06821j.

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44

Vajo, John J., Sky L. Skeith, and Florian Mertens. "Reversible Storage of Hydrogen in Destabilized LiBH4." Journal of Physical Chemistry B 109, no. 9 (March 2005): 3719–22. http://dx.doi.org/10.1021/jp040769o.

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45

Vajeeston, P., P. Ravindran, and H. Fjellvåg. "Nanostructures of LiBH4: a density-functional study." Nanotechnology 20, no. 27 (June 17, 2009): 275704. http://dx.doi.org/10.1088/0957-4484/20/27/275704.

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46

Orimo, Shin-Ichi, Yuko Nakamori, Nobuko Ohba, Kazutoshi Miwa, Masakazu Aoki, Shin-ichi Towata, and Andreas Züttel. "Experimental studies on intermediate compound of LiBH4." Applied Physics Letters 89, no. 2 (July 10, 2006): 021920. http://dx.doi.org/10.1063/1.2221880.

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47

Zou, Hongyang, Anton Gradišek, Samuel B. Emery, John J. Vajo, and Mark S. Conradi. "LiBH4 in Aerogel: Ionic Motions by NMR." Journal of Physical Chemistry C 121, no. 28 (July 11, 2017): 15114–19. http://dx.doi.org/10.1021/acs.jpcc.7b04520.

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48

Mosegaard, Lene, Bitten Møller, Jens-Erik Jørgensen, Ulrike Bösenberg, Martin Dornheim, Jonathan C. Hanson, Yngve Cerenius, et al. "Intermediate phases observed during decomposition of LiBH4." Journal of Alloys and Compounds 446-447 (October 2007): 301–5. http://dx.doi.org/10.1016/j.jallcom.2007.03.057.

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49

Yang, Jun, Andrea Sudik, Donald J. Siegel, Devin Halliday, Andy Drews, Roscoe O. Carter, Christopher Wolverton, et al. "Hydrogen storage properties of 2LiNH2+LiBH4+MgH2." Journal of Alloys and Compounds 446-447 (October 2007): 345–49. http://dx.doi.org/10.1016/j.jallcom.2007.03.145.

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50

Aoki, M., K. Miwa, T. Noritake, G. Kitahara, Y. Nakamori, S. Orimo, and S. Towata. "Destabilization of LiBH4 by mixing with LiNH2." Applied Physics A 80, no. 7 (January 27, 2005): 1409–12. http://dx.doi.org/10.1007/s00339-004-3194-9.

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