Solid-state Hydrogen Storage Materials Research Articles

Synergistic effect of Pd single atoms and clusters on the de/re-hydrogenation performance of MgH2

Hydrogen storage plays a pivotal role in the hydrogen industry, yet its current status presents a bottleneck. Diverse strategies have emerged in recent years to address this challenge. MgH2 has stood out as a promising solid-state hydrogen storage material due to its impressive gravimetric and volumetric hydrogen density, but its practical application is hampered by elevated thermal stability and sluggish kinetics. In this study, we introduce a solution by synthesizing Pd metallene through a one-pot solvothermal method, revealing a distinctive highly curved lamellar structure with a thickness of around 1.6 nm. Incorporating this Pd metallene into MgH2 results in a composite system wherein the starting dehydrogenation temperature is significantly lowered to 439 K and complete dehydrogenation occurs at 583 K, releasing 6.14 wt.% hydrogen. The activation energy of dehydrogenation for MgH2 was reduced from 170.4 kJ mol–1 to 79.85 kJ mol–1 after Pd metallene decoration. The enthalpy of dehydrogenation of the MgH2–10 wt.% Pd sample was calculated to be 73 kJ mol–1 H2–1 and decreased by 4.4 kJ mol–1 H2–1 from that of dehydrogenation of pure MgH2 (77.4 kJ mol–1 H2–1). Theoretical calculations show that the average formation energy and average adsorption energy of hydrogen vacancies can be significantly reduced in the presence of both Pd clusters and Pd single atoms on the surface of MgH2/Mg, respectively. It suggests that the synergistic effect of in situ formed Pd single atoms and clusters significantly improves the hydrogenation and dehydrogenation kinetics. The identified active sites in this study hold potential as references for forthcoming multi-sized active site catalysts, underscoring a significant advancement toward resolving hydrogen storage limitations.

Phonon transport characteristics of α, β, and γ crystalline phases of magnesium hydride from first-principles-based anharmonic lattice dynamics

The superior gravimetric and volumetric hydrogen capacities of magnesium hydride (MgH2) make it a promising candidate material for solid-state hydrogen storage. However, the slow kinetics of hydrogen atoms and the high thermodynamic stability of MgH2 hinder its practical application. To address the challenging issue of adsorption–desorption in MgH2, structural engineering involving nanostructuring has been used to improve the hydrogen-storage characteristics of this material. However, although structural engineering and thermal management significantly influence material properties, no microscopic understanding of the heat conduction property of pristine MgH2 exists. Further advances in the thermal engineering of MgH2-based hydrogen-storage materials require a better understanding of heat conduction in pristine MgH2, particularly knowledge of how the crystalline phases of MgH2 depend on the hydrogen concentration and external pressure. This study uses first-principles-based anharmonic lattice dynamics to quantitatively investigate the intrinsic thermal conductivity of heat-carrying phonons in pristine MgH2 with three different crystalline phases α, β, and γ. The results show that the thermal conductivity of MgH2 depends on the crystalline phase and that the magnitude of the thermal conductivity increases in the order α, γ, and β. In contrast, the volumetric heat capacity and mean squared displacements of the constituent atoms are similar for all three phases. Furthermore, as observed for the pressure dependence of phonon transport, increasing the pressure reduces the thermal conductivity of all phases. However, for the γ and β phases, these reductions are relatively moderate because of the competing effects of group velocity and relaxation time, which have opposite dependencies on pressure. Finally, modal analysis indicates that the spectral features of the phonon transport properties under an applied external pressure are comparable to those at atmospheric pressure. These results should help tailor the heat dissipation of MgH2 while maintaining its hydrogen adsorption–desorption performance through structural engineering.

Mechanism of hydrogenation and dehydrogenation in Mg/Cu9Al4 @Mg and MgH2/Cu9Al4 @MgH2: A DFT and experimental investigation

The Cu9Al4 intermetallic has been found to enhance the hydrogenation and dehydrogenation capabilities of Mg. However, its impact on kinetics is unclear. In the present work, the hydrogenated and dehydrogenated mechanism were investigated by experimental and theoretical methods, including Density Functional Theory (DFT) and ab initio molecular dynamic (AIMD) simulations. Experimental results show that the addition of Cu9Al4 IMC can promote the hydrogenation and dehydrogenation kinetics of Mg, which the dehydrogenation rate of Cu9Al4 @MgH2 is 3 times that of MgH2. AIMD simulations illustrate that the electron properties of Cu9Al4 @Mg and Cu9Al4 @MgH2 are different from that of pure Mg and MgH2, which lead to the change of hydrogenated and dehydrogenated mechanism in Mg/Cu9Al4 @Mg and MgH2/Cu9Al4 @MgH2. Moreover, the diffusion coefficient of H atoms in Cu9Al4 @MgH2 is 4 times that in MgH2. The addition of Cu9Al4 IMC decreases the particle size of Cu9Al4 @Mg during ball milling and induces lattice distortion of Cu9Al4 @MgH2 during the dehydrogenation process. These changes may contribute to the enhancement of the dehydrogenation rate in Cu9Al4 @MgH2. This work complements the mechanism of IMC for improving the performance of hydrogen storage materials and provides a theoretical basis for the development of next-generation solid-state hydrogen storage materials.

Computational evaluation of comprehensive properties of MgX3H8 (X = Sc, Ti and Zr) as effective solid state hydrogen storage materials

In this study, structural, mechanical, electronic, dynamic, thermodynamic and hydrogen storage properties of MgX3H8 (X = Sc, Ti, Zr) were investigated by means of density functional theory which was not studied/reported experimentally or theoretically in the previous literature. This is the first thorough study about various properties of these materials. These materials were considered as promising potential host materials for solid state hydrogen storage. The evaluation of computed formation enthalpies of MgX3H8 (X = Sc, Ti, Zr), elastic constants, and phonon dispersion graphs revealed that MgX3H8 (X = Sc, Ti, Zr) is thermodynamically, mechanically, and dynamically stable and synthesizable. The analysis of B/G ratio, Cp and Poisson's ratio showed that MgSc3H8 is a brittle material whereas MgTi3H8 and MgZr3H8 are ductile materials. Moreover, anisotropy factor, machinability index, hardness, melting and Debye temperature of the materials were obtained and analysed in depth. The electronic band structures of MgX3H8 (X = Sc, Ti, Zr) illustrated metallic character since the bands (valence and conduction) intersect the Fermi level along the main symmetry directions. The phonon dispersion curves, and the partial state densities of the materials have positive frequencies, therefore, materials are dynamically stable in the cubic structure. The gravimetric hydrogen densities were calculated as 4.60 wt% for MgSc3H8, 4.38 wt% for MgTi3H8 and 2.56 wt% for MgZr3H8. The hydrogen desorption temperatures were computed as 239.54 K for MgSc3H8, 241.76 K for MgTi3H8 and 303.87 K for MgZr3H8. The mechanical properties of the materials suggest that they can be promising host materials for hydrogen storage.

Solvent- and catalyst-free reduction of CO2 with ammonia borane

The catalyst-free CO2 reduction with ammonia borane in the solid state is reported. Close to 40 mmol of CO2 per gram of ammonia borane can be reduced at 0.5 MPa and 60 °C to formamide in high yield, achieving a highly atom-economical process.

Improving the desorption properties of LiAlH4 by the addition of Ni0.6Zn0.4O

Lithium alanate (LiAlH4) is one of the most preferred materials for solid-state hydrogen storage materials owing to its relatively high hydrogen capacity (10.5 wt%). However, its high decomposition temperature and sluggish desorption kinetic restrict its potential application as a hydrogen storage medium for on-board hydrogen-powered applications. To overcome these problems, the impacts of Ni0.6Zn0.4O synthesized via a solid-state method on the desorption properties of LiAlH4 have been examined in this study. It was found that after the introduction of 10 wt% of Ni0.6Zn0.4O to LiAlH4, hydrogen started to release at 124 °C and 170 °C for the first two stages, respectively. Isothermal desorption kinetics also revealed that faster desorption kinetics can be observed at 90 °C for 120 min LiAlH4+10 wt% of Ni0.6Zn0.4O can desorb 3.1 wt% of H2, whereas undoped LiAlH4 can release approximately less than 0.5 wt% of H2 in the same time frame. According to the Kissinger method, the apparent activation energies for the first two steps of the LiAlH4+10 wt% of Ni0.6Zn0.4O composites have been found to be 73 kJ/mol and 85 kJ/mol, respectively, 32 kJ/mol and 40 kJ/mol less than milled LiAlH4. The in-situ formation of NiO and Zn or Zn-containing compounds during the heating process might contribute to the kinetic improvement of LiAlH4.

Magnesium nickel hydride monocrystalline nanoparticles for reversible hydrogen storage

Although Mg-based hydrides are extensively considered as a prospective material for solid-state hydrogen storage and clean energy carriers, their high operating temperature and slow kinetics are the main challenges for practical application. Here, a Mg–Ni based hydride, Mg2NiH4 nanoparticles (∼100 nm), with dual modification strategies of nanosizing and alloying is successfully prepared via a gas-solid preparation process. It is demonstrated that Mg2NiH4 nanoparticles form a unique chain-like structure by oriented stacking and exhibit impressive hydrogen storage performance: it starts to release H2 at ∼170 °C and completes below 230 °C with a saturated capacity of 3.32 wt% and desorbs 3.14 wt% H2 within 1800 s at 200 °C. The systematic characterizations of Mg2NiH4 nanoparticles at different states reveal the dehydrogenation behavior and demonstrate the excellent structural and hydrogen storage stabilities during the de/hydrogenated process. This research is believed to provide new insights for optimizing the kinetic performance of metal hydrides and novel perspectives for designing highly active and stable hydrogen storage alloys.

Facile dehydrogenation of MgH2 enabled by γ-graphyne based single-atom catalyst

Solid-state hydrogen storage is a promising roadmap for the safe and efficient utilization of hydrogen energy due to its moderate operating environment and high hydrogen storage density. However, as a representative solid-state hydrogen storage material, magnesium hydride (MgH2) is significantly limited in the commercial application due to its sluggish kinetics in the dehydrogenation process. Single-atom catalysts are a promising solution to this dilemma. However, the promising graphene-based single-atom catalysts are not yet sufficient to meet the dehydrogenation needs in engineering. To further address this dilemma, we designed a novel γ-graphyne based single-atom catalysts including eight 3d transition metals for promoting the dehydrogenation process of MgH2. Through using spin-polarized density functional theory calculations, we found that the energy barrier for MgH2 dehydrogenation has been significantly reduced even to 0.70 eV, which is far lower than the current graphene-based single-atom catalyst. In detail, the migration trajectory of hydrogen atom in the dehydrogenation process has been observed and confirmed using the ab initio molecular dynamics simulations. To investigate the intrinsic origin for its high catalytic activity of single-atom catalyst, we analyze the HMg bond activation mechanism through the electron localization function, charge density difference and crystal orbital Hamiltonian population. Finally, we found the relationship between energy barrier with electronic structure of single-atom catalyst, such as electrostatic potential and system electronegativity. This work can not only provide new ideas for the optimize of dehydrogenation catalyst, but also lay a theoretical foundation for the design of novel energy storage material.

Enhanced hydrogen storage properties of MgH2 with the co-addition of LiBH4 and YNi5 alloy

MgH2, as one of the typical solid-state hydrogen storage materials, has attracted extensive attention. However, the slow kinetics and poor cycle stability limit its application. In this work, LiBH4 and YNi5 alloy were co-added as additives to MgH2 via ball milling, thereby realizing an excellent dehydrogenation performance and good cycle stability at 300 °C. The MgH2-0.04LiBH4-0.01YNi5 composite can release 7 wt.% of hydrogen in around 10 min at 300 °C and still have a reversible hydrogen storage capacity of 6.42 wt.% after 110 cycles, with a capacity retention rate as high as 90.3 % based on the second dehydrogenation capacity. The FTIR results show that LiBH4 can reversibly absorb and desorb hydrogen throughout the hydrogen ab/desorption process, which contributes a portion of the reversible hydrogen storage capacity to the MgH2-0.04LiBH4-0.01YNi5 composite. Due to the small amount of LiBH4 and YNi5, the dehydrogenation activation energy of MgH2 did not decrease significantly, nor did the dehydrogenation enthalpy (∆H) change. However, the MgNi3B2 and in-situ formed YH3 during the hydrogen absorption/desorption cycles is not only beneficial to the improvement of the kinetics performance for MgH2 but also improves its cycle stability. This work provides a straightforward method for developing high reversible hydrogen capacity on Mg-based hydrogen storage materials with moderate kinetic performance.

The strain and sealing design of a portable hydrolysis reactor for hydrogen storage materials

Portable hydrolysis reactors for hydrogen storage material reactions are extremely important for the application of hydrogen energy since hydrolysis is a facile path to provide hydrogen. The strain and sealing components are extremely important for a hydrogen reactor. However, most researchers are focusing on the hydrogen storage materials for hydrolysis instead of the hydrolysis reactors. Herein, the structure of a hydrolysis reactor has been designed based on the strain distribution and sealing efficiency. The stress concentration on the threaded connection part and sealing effects have been analyzed using finite element analysis method. The stress concentration has been effectively reduced by increasing thread turns and wall thickness of thread. The stress concentration was also found to be affected by the thread types. Double sealing connection was adopted, where the sealing performance was found to increase with increase pressure in the reactor. This study provides a feasible design of a portable hydrolysis reactor for solid-state hydrogen storage materials.

Tailoring magnesium-based hydrides as potential and reversible materials for solid-state hydrogen storage: A first-principles study

Hydrogen is a promising candidate for green energy sources for future endeavors because of its abundance on Earth. Although its storage is a major challenge for the researchers of this era because of its unsafe and highly explosive nature. The structural, optoelectronic, thermoelectric, vibrational, thermodynamic properties and hydrogen storage capacity of XMgH3 ([Formula: see text], Ba) are carried out by using the full potential linearized augmented plane wave (FP-LAPW) method in the DFT framework. The theoretical study about these magnesium-based metal hydride perovskites, i.e., SrMgH3 and BaMgH3, declares them structurally stable compounds in space group Pm-3m. The optimization graph for SrMgH3 and BaMgH3 reflects the lowest ground state energy, i.e., −6759[Formula: see text]Ry and −16683[Formula: see text]Ry, respectively. Comparatively, BaMgH3 seems to be more stable. The electronic band structures and density of states declare them pure metallic due to zero band gap and overlapping of electronic states of the valence and the conduction bands. The electrical conductivity of BaMgH3 increases up to [Formula: see text] and thermal conductivity [Formula: see text] in the temperature range 100[Formula: see text]K to 1000[Formula: see text]K revealing the good metallic character of BaMgH3. The optical analysis portrays the absorption of compounds in the visible range along with valance shell electrons to the weak bond of hydrogen and dissociates hydrogen molecules at a certain intensity of light. BaMgH3 compound shows minimum scattering and maximum absorption of light in the visible region up to 3[Formula: see text]eV. The reflectivity peaks in the visible region 3.0[Formula: see text]eV show that 40% of light energy is absorbed due to the opaque nature of BaMgH3. Both these compounds are declared thermodynamically stable due to negative free energy such as −1.20[Formula: see text]eV for SrMgH3 and −1.50[Formula: see text]eV energy for BaMgH3 at 1000[Formula: see text]K, respectively. Moreover, the three acoustic modes showing zero imaginary phonon frequencies at [Formula: see text] symmetry points predict these compounds’ structural and thermodynamical stability. The gravimetric hydrogen storage concentration of SrMgH3 and BaMgH3 is determined as 2.637% and 1.836%, respectively.

Superior catalytic action of high-entropy alloy on hydrogen sorption properties of MgH2

Magnesium hydride (MgH2) is the mostly used material for solid-state hydrogen storage. However, their slow kinetics and highly unfavorable thermodynamics make them unsuitable for the practical applications. The current study describes the unusual catalytic action of a new class of catalyst, a high-entropy alloy (HEA) of Al20Cr16Mn16Fe16Co16Ni16 and its leached version, on the de/re-hydrogenation properties of MgH2. The onset desorption temperature of MgH2 was reduced significantly from 360 °C (for ball-milled MgH2) to 338 °C when it was catalyzed with a leached HEA-based catalyst. On the other hand, a fast de/re-hydrogenation kinetics of MgH2 was observed during the addition of leached HEA-based catalyst. It absorbed ∼6.1 wt% of hydrogen in just 2 min at a temperature of 300 °C under 10 atm hydrogen pressure and desorbed ∼5.4 wt% within 40 min. At moderate temperatures and low pressure, the HEA-based catalyst reduced desorption temperatures and improved re-hydrogenation kinetics. Even after 25 cycles of de/re-hydrogenation, the storage capacity of MgH2 catalyzed with the leached version of HEA degrades negligibly.

Room-Temperature Transient Hydrogen Uptake of MgH2 Induced by Nb-Doped TiO2 Solid-Solution Catalysts.

The practical applications of MgH2 as a high-density hydrogen carrier depend heavily on efficient and low-cost catalysts to accelerate the dehydriding/hydriding reactions at moderate temperatures. In the present work, this issue is addressed by synthesizing Nb-doped TiO2 solid-solution-type catalysts that dramatically improve the hydrogen sorption performances of MgH2. The catalyzed MgH2 can absorb 5 wt % of H2 even at room temperature for 20 s, release 6 wt % of H2 at 225 °C within 12 min, and the complete dehydrogenation can be achieved at 150 °C under a dynamic vacuum atmosphere. Density functional theory calculations reveal that Nb doping introduces Nb 4d orbitals with stronger interaction with H 1s into the density of states of TiO2. This considerably enhances both the adsorption and dissociation ability of the H2 molecule on the catalysts surface and the hydrogen diffusion across the specific Mg/Ti(Nb)O2 interface. The successful implementation of solid solution-type catalysts in MgH2 offers a demonstration and inspiration for the development of high-performance catalysts and solid-state hydrogen storage materials.

Ameliorating the re/dehydrogenation behaviour of MgH2 by zinc titanate addition

Magnesium hydride (MgH2) is the most feasible and effective solid-state hydrogen storage material, which has excellent reversibility but initiates decomposing at high temperatures and has slow kinetics performance. Here, zinc titanate (Zn2TiO4) synthesised by the solid-state method was used as an additive to lower the initial temperature for dehydrogenation and enhance the re/dehydrogenation behaviour of MgH2. With the presence of Zn2TiO4, the starting temperature for the dehydrogenation of MgH2 was remarkably lowered to around 290 °C–305 °C. In addition, within 300 s, the MgH2–Zn2TiO4 sample absorbed 5.0 wt.% of H2 and 2.2–3.6 wt.% H2 was liberated from the composite sample in 30 min, which is faster by 22–36 times than as-milled MgH2. The activation energy of the MgH2 for the dehydrogenation process was also downshifted to 105.5 kJ/mol with the addition of Zn2TiO4 indicating a decrease of 22% than as-milled MgH2. The superior behaviour of MgH2 was due to the formation of MgZn2, MgO and MgTiO3, which are responsible for ameliorating the re/dehydrogenation behaviour of MgH2. These findings provide a new understanding of the hydrogen storage behaviour of the catalysed-MgH2 system.

Promoting hydrogen industry with high-capacity Mg-based solid-state hydrogen storage materials and systems

Promoting hydrogen industry with high-capacity Mg-based solid-state hydrogen storage materials and systems

Enhancing hydrogen storage performance of MgH2 through the addition of BaMnO3 synthesized via solid-state method

Currently, magnesium hydride (MgH2) as a solid-state hydrogen storage material has become the subject of major research owing to its good reversibility, large hydrogen storage capacity (7.6 wt%) and affordability. However, MgH2 has a high decomposition temperature (>400 °C) and slow desorption and absorption kinetics. In this work, BaMnO3 was synthesized using the solid-state method and was used as an additive to overcome the drawbacks of MgH2. Interestingly, after adding 10 wt% of BaMnO3, the initial desorption temperature of MgH2 decreased to 282 °C, which was 138 °C lower than that of pure MgH2 and 61 °C lower than that of milled MgH2. For absorption kinetics, at 250 °C in 2 min, 10 wt% of BaMnO3-doped MgH2 absorbed 5.22 wt% of H2 compared to milled MgH2 (3.48 wt%). Conversely, the desorption kinetics also demonstrated that 10 wt% of BaMnO3-doped MgH2 samples desorbed 5.36 wt% of H2 at 300 °C within 1 h whereas milled MgH2 only released less than 0.32 wt% of H2. The activation energy was lowered by 45 kJ/mol compared to that of MgH2 after the addition of 10 wt% of BaMnO3. Further analyzed by using XRD revealed that the formation of Mg0·9Mn0·1O, Mn3O4 and Ba or Ba-containing enhanced the performance of MgH2.

Assisting Ni catalysis by CeO2 with oxygen vacancy to optimize the hydrogen storage properties of MgH2

Although MgH2 has been widely regarded as a promising material for solid-state hydrogen storage, its high operating temperature and slow kinetics pose a major bottleneck to its practical application. Here, a nanocomposite catalyst with interfacial coupling and oxygen defects, Ni/CeO2, is fabricated to promote H2 desorption and absorption properties of MgH2. The interface of Ni/CeO2 contributes to both strong mechanical coupling towards stabilizing partial Ni and electronic coupling towards inducing a high concentration of oxygen vacancies in CeO2. Theoretical calculations evidence that CeO2 with oxygen vacancy assist Ni in weakening the energy of Mg-H bond as well as enhancing the adsorption energy of Ni upon hydrogen atoms, and the extent of this assistance surprisingly increases with increasing oxygen vacancies concentration. As a result, an impressive performance is achieved by MgH2-5 wt.% Ni/CeO2 with onset desorption temperature of only 165 °C, and it absorbs approximately 80% hydrogen in just 800 s at 125 °C. The generation mechanism of intermediate active species concerning Ni/CeO2 in different states has been analyzed for the first time, and the relationship between interfacial coupling and phase evolution has been elucidated. Therefore, a mechanism of the catalysis-assisting effect regarding oxygen defects is proposed. It is believed that this work provides a unique perspective on the mechanism of interfacial coupling and the generation of defects in composite catalysts.

Dehydrogenation of Alkali Metal Aluminum Hydrides MAlH4 (M = Li, Na, K, and Cs): Insight from First-Principles Calculations

Complex aluminum hydrides with high hydrogen capacity are among the most promising solid-state hydrogen storage materials. The present study determines the thermal stability, hydrogen dissociation energy, and electronic structures of alkali metal aluminum hydrides, MAlH4 (M = Li, Na, K, and Cs), using first-principles density functional theory calculations in an attempt to gain insight into the dehydrogenation mechanism of these hydrides. The results show that the hydrogen dissociation energy (Ed-H2) of MAlH4 (M = Li, Na, K, and Cs) correlates with the Pauling electronegativity of cation M (χP); that is, the Ed-H2 (average value) decreases, i.e., 1.211 eV (LiAlH4) < 1.281 eV (NaAlH4) < 1.291 eV (KAlH4) < 1.361 eV (CsAlH4), with the increasing χP value, i.e., 0.98 (Li) > 0.93 (Na) > 0.82 (K) > 0.79 (Cs). The main reason for this finding is that alkali alanate MAlH4 at higher cation electronegativity is thermally less stable and held by weaker Al-H covalent and H-H ionic interactions. Our work contributes to the design of alkali metal aluminum hydrides with a favorable dehydrogenation, which is useful for on-board hydrogen storage.

Development of Materials for Solid State Hydrogen Storage

Series of high entropy alloys designed on Hume-Rothery criterion was prepared and the probability of the empirical approach to hydrogen storage materials preparation was investigated. Calculated HEA’s with equimolar compositions were selected from the list of alloys with limited VEC (valence electron concentration), ΔS and ΔH. The phase composition of prepared materials was compared with the prediction model and material characteristics such as chemical composition, and phase composition were studied. In this article material characterization of predicted high-entropy alloys with various prediction parameters values will be presented in terms of empirical prediction methods for solid-state hydrogen storage materials.

Boosting the Dehydrogenation Properties of LiAlH4 by Addition of TiSiO4

Given its significant gravimetric hydrogen capacity advantage, lithium alanate (LiAlH4) is regarded as a suitable material for solid-state hydrogen storage. Nevertheless, its outrageous decomposition temperature and slow sorption kinetics hinder its application as a solid-state hydrogen storage material. This research's objective is to investigate how the addition of titanium silicate (TiSiO4) altered the dehydrogenation behavior of LiAlH4. The LiAlH4-10 wt% TiSiO4 composite dehydrogenation temperatures were lowered to 92 °C (first-step reaction) and 128 °C (second-step reaction). According to dehydrogenation kinetic analysis, the TiSiO4-added LiAlH4 composite was able to liberate more hydrogen (about 6.0 wt%) than the undoped LiAlH4 composite (less than 1.0 wt%) at 90 °C for 2 h. After the addition of TiSiO4, the activation energies for hydrogen to liberate from LiAlH4 were lowered. Based on the Kissinger equation, the activation energies for hydrogen liberation for the two-step dehydrogenation of post-milled LiAlH4 were 103 and 115 kJ/mol, respectively. After milling LiAlH4 with 10 wt% TiSiO4, the activation energies were reduced to 68 and 77 kJ/mol, respectively. Additionally, the scanning electron microscopy images demonstrated that the LiAlH4 particles shrank and barely aggregated when 10 wt% of TiSiO4 was added. According to the X-ray diffraction results, TiSiO4 had a significant effect by lowering the decomposition temperature and increasing the rate of dehydrogenation of LiAlH4 via the new active species of AlTi and Si-containing that formed during the heating process.