Multiscale study of the structure and hydrogen storage capacity of an aluminum metal-organic framework

First-principles calculations based on density functional theory and Grand Canonical Monte Carlo (GCMC) simulations are carried out to study the structure of a new Aluminum Metal-Organic Framework, MOF-519, and the possibility of storing molecular hydrogen therein. The optimized structure of the inorganic secondary building unit (SBU) of MOF-519 formed by eight octahedrally coordinated aluminum atoms is presented. The different storage sites of H₂ inside the SBU and the BTB ligand are explored. Our results reveal that the SBU exhibits two different favorable physisorption sites with adsorption energies of ?12.2 kJ/mol and ?1.2 kJ/mol per hydrogen molecule. We have also shown that each phenyl group of BTB has three stable H₂ adsorption sites with adsorption energies between ?6.7 kJ/mol and ?11.37 kJ/mol. Using GCMC simulations; we calculated the molecular hydrogen (H₂) gravimetric and volumetric uptake for the SBU and MOF-519. At 77 K and 100 bar pressure, the hydrogen uptake capacity of SBU is considerably enhanced, reaching 16 wt.%. MOF-519 has a high gravimetric uptake, 10 wt.% at 77 K and 4.9 wt.% at 233 K. It has also a high volumetric capacity of 65 g/L at 77 K and 20.3 g/L at 233 K, indicating the potential of this MOF for hydrogen storage applications.     

Synthesis and hydrogen adsorption properties of a new iron based porous metal-organic framework

A new metal-organic framework [Fe₃O(OOC-C₆H₄-COO)₃(H₂O)₃]Cl·(H₂O)_x was synthesized with a specific surface area of 2823 m²/g and a lattice parameter of 88.61 Å. Isostructural with MIL-101, this compound exhibits similar hydrogen adsorption properties, with maximum adsorption capacity of 5.1wt.% H at 77 K. The adsorption enthalpy of hydrogen for MIL-101 and ITIM-1 (MIL-101Fe) at zero coverage was calculated for a wide temperature range of 77 K ÷ 324 K, considering corrections for the variation of hydrogen gas entropy with the temperature. The resulted adsorption enthalpy is 9.4 kJ/mol for MIL-101, in excellent agreement with the value reported in literature from microcalorimetric measurements, and a value of 10.4 kJ/mol at zero coverage was obtained for ITIM-1 (MIL-101Fe).     

Reinforce the dehydrogenation process of LiAlH4 by accumulating porous activated carbon

Herein, it is reported that activated carbon (AC) alters the hydrogen storage behavior of lithium alanate (LiAlH₄) prepared by the ball milling technique. Notable improvements in onset decomposition temperature and desorption kinetics are attained for LiAlH₄ added 10 wt.% of AC composite compared to as-received and as-milled LiAlH₄. The onset decomposition temperature of LiAlH₄-10 wt.% AC dropped to 100 °C and 160 °C for the first and second steps. The composite also released 3.4 wt.% of hydrogen after 90 min compared to as-received and as-milled which is less than 0.2 wt.% of hydrogen within the same period. The XRD result discovered an additional peak of the Li₃AlH₆ and Al compounds appeared after the milling process, concluding that LiAlH₄ becomes unstable after the addition of AC. FTIR measurement has verified the presence of the Li₃AlH₆ and carbon bonding in the LiAlH₄-10 wt.% AC composite. The composite's activation energy (E_a) for the first and second steps is 70 kJ/mol and 85 kJ/mol, respectively. These values decrease from as-milled LiAlH₄ for both steps, demonstrating the catalytic effect of AC in this system. FESEM images illustrate that after ball milling, the particle size of LiAlH₄-10 wt.% AC composite decreases. The considerable improvement in the hydrogen storage characteristic of the LiAlH₄-10 wt.% AC composite is thought to be the collaborative role of amorphous carbon.     

Activated carbons with appropriate micropore size distribution for hydrogen adsorption

We measured hydrogen storage on five well-known commercial carbon materials (CCMs) and we compared their performances to those obtained on our lab-made activated carbons (ACs). H₂ uptake of our lab-made ACs was always higher than that of CCMs of similar S_BET, our best AC reached 6 wt.% H₂ excess adsorption at 77 K and 4 MPa. We calculated the contribution of four ranges of pores (<0.5 nm; 0.5-0.7 nm, 0.7-2 nm and >2 nm) to the H₂ excess adsorption for the 14 carbon materials considered in this study. We clearly demonstrated that: (i) the superiority in H₂ excess adsorption of lab-made ACs over the CCMs is related to their pore size distribution; (ii) H₂ uptakes higher than 3 wt.% are due to pores with diameter wider than 0.7 nm.     

Structure, morphology and hydrogen storage properties of a Ti0.97Zr0.019V0.439Fe0.097Cr0.045Al0.026Mn1.5 alloy

The Ti_0.97Zr_0.019V_0.439Fe_0.097Cr_0.045Al_0.026Mn_1.5 alloy is a hexagonal C14 Laves phase material that reversibly stores hydrogen under ambient temperatures. Structural changes are studied by XRD and SEM with regard to hydrogenation and dehydrogenation cycling at 25, 40 and 60 °C. The average particle size is reduced after hydrogenation and dehydrogenation cycling through decrepitation. The maximum hydrogen capacity at 25 °C is 1.71 ± 0.01 wt. % under 78 bar H₂, however the hydrogen sorption capacity decreases and the plateau pressure increases at higher temperatures. The enthalpy (ΔH) and entropy (ΔS) of hydrogen absorption and desorption have been calculated from a van’t Hoff plot as −21.7 ± 0.1 kJ/mol H₂ and −99.8 ± 0.2 J/mol H₂/K for absorption and 25.4 ± 0.1 kJ/mol H₂ and 108.5 ± 0.2 J/mol H₂/K for desorption, indicating the presence of a significant hysteresis effect.     

Adsorption and compression contributions to hydrogen storage in activated anthracites

We prepared activated carbons (ACs) that are among the best adsorbents for hydrogen storage. These ACs were prepared from anthracites and have surface areas (S_BET) as high as 2772 m² g⁻¹. Anthracites activated with KOH presented the highest adsorption capacities with a maximum of 5.3 wt.% at 77 K and 4 MPa. Non-linearity between hydrogen uptake at 77 K and pore texture was confirmed, as soon as their S_BET exceeded the theoretical limiting value of (geometrical) surface area, i.e., S_BET > 2630 m² g⁻¹. We separated adsorption and compression contributions to total hydrogen storage. The amount of hydrogen stored is significantly increased by adsorption only at moderate pressure: 3 MPa and 0.15 MPa at 298 and 77 K, respectively. Hydrogen adsorption on ACs at high pressure, above 30 MPa at 298 K and 8 MPa at 77 K, has not interest because more gas can be stored by simply compression in the same tank volume.     

Boron nitride substrate-induced reversible hydrogen storage in bilayer solid matrix via interlayer spacing

By using first-principles methods, we perform a theoretical investigation of adsorption of hydrogen molecules between bilayer solid matrix layers (bilayer boron nitride sheets (BBN) and graphene/boron nitride heterobilayers (GBN)) with variable interlayer distance (ILD). We find that the H₂ adsorption energy has a minimum by expanding the interlayer spacing, along with further interlayer expansion, arising from many H₂ binding states and electrostatic interaction induced by the polar nature of B–N bonds. To determine if successive addition of H₂ molecules is indeed possible using the minimal H₂ adsorption energy as the reference state, we then simulate the hydrogen storage capacity of BBN and GBN with different stacking types, and find that the GBN with Bernal stacking is superior for reversible hydrogen storage. Up to eight H₂ molecules can be adsorbed with the average adsorption energy of −0.20 eV/H₂, corresponding to ∼7.69 wt % hydrogen uptake.     

Superior hydrogen storage properties of MgH2–10 wt.% TiC composite

The hydrogen storage performance of MgH₂–10 wt.% TiC composite was investigated. The additive TiC nanoparticle led to a pronounced improvement in the de/hydrogenation kinetics of MgH₂. The composite could dehydrogenate 6.3 wt.% at 573 K while the milled MgH₂ only released 4.9 wt.% of hydrogen at the same condition. The improvement came from that the activation energy of dehydrogenation was decreased from 191.27 kJ mol⁻¹ to 144.62 kJ mol⁻¹ with the TiC additive. The MgH₂–10 wt.% TiC composite also absorbed 6.01 wt.% (or 5.1 wt.%) of hydrogen under 1 MPa H₂ at 573 K (or 473 K) in 3000 s. Even at 1 MPa H₂ and 373 K, it could absorb 4.1 wt.% of hydrogen, but milled MgH₂ could not absorb hydrogen at this condition. Additionally, the composite had good cycling stability, and its hydrogen capacity only decreased 3.3% of the first run after 10 de/hydrogenation cycles. The improved hydrogen storage properties were explained to the TiC particles embedded in the MgH₂, which provided the pathways for the hydrogen diffusion into the MgH₂–10 wt.% TiC composite.     

H2 adsorption on Cu(I)-ZSM-5: Exploration of Cu(I)-exchange in solution

A new Cu(I)-exchange method for zeolites in liquid media (acetonitrile) was developed with Cu/Al ratios surpassing 0.5 with ZSM-5 crystals containing pure Cu(I) cations without impurities such as Cl ions. The method resulted in a higher Cu/Al ratio (0.78) for mesoporous [B]-ZSM-5 when compared to microporous [Al]-ZSM-5 and [B]-ZSM-5 (0.55 and 0.66 respectively). H₂ storage capacities of these Cu(I)-exchanged zeolites were investigated at 323 K along with their differential heat of H₂ adsorption using adsorption calorimetry. H₂ storage capacities as high as 0.03 wt. % at 323 K and 40 kPa were achieved on [Al] and [B]-ZSM-5 and mesoporous [B]-ZSM-5 showed an outstanding H₂/Cu ratio of 1.03 at 323 K and below 100 kPa. Coverage-dependent differential adsorption heats were found to be ranging from 95 kJ/mol to 5 kJ/mol with observed values of 30–10 kJ/mol for H₂/Cu ratios between 0.05 and 0.15.     

Enhanced hydrogen properties of MgH2 by Fe nanoparticles loaded hollow carbon spheres

In the present investigation, we have reported the synergistic effect of Fe nanoparticles and hollow carbon spheres composite on the hydrogen storage properties of MgH₂. The onset desorption temperature for MgH₂ catalyzed with hollow carbon spheres and Fe nanoparticle (MgH₂-Fe-HCS) system has been observed to be 225.9 °C with a hydrogen storage capacity of 5.60 wt %. It could be able to absorb 5.60 wt % hydrogen within 55 s and desorb 5.50 wt % hydrogen within 12 min under 20 atm H₂ pressure at 300 °C. The desorption activation energy of MgH₂-Fe-HCS has been found to be 84.9 kJ/mol, whereas the desorption activation energies for as received MgH₂, Hollow carbon sphere catalyzed MgH₂ and Fe catalyzed MgH₂ are found to be 130 kJ/mol, 103 kJ/mol, and 94.2 kJ/mol respectively. MgH₂-Fe-HCS composite lowered the change in enthalpy of hydrogen desorption from MgH₂ by 20.02 kJ/mol as compared to pristine MgH₂. MgH₂-Fe-HCS shows better cyclability up to 24 cycles of hydrogenation and dehydrogenation of MgH₂. The mechanism for the better catalytic action of Fe and HCS on MgH₂ has also been discussed.     

ZrO2@Nb2CTx composite as the efficient catalyst for Mg/MgH2 based reversible hydrogen storage material

While Mg/MgH₂ system has a high hydrogen storage capacity, its sluggish hydrogen desorption rate has hindered practical applications. Herein, we report that the hydrogen absorption and desorption kinetics of Mg/MgH₂ system can be significantly improved by using the synergetic effect between Nb₂CT_x MXene and ZrO₂. The catalyst of Nb₂CT_x MXene loading with ZrO₂ (ZrO₂@Nb₂CT_x) is successfully synthesized, and the dehydrogenation activation energy of MgH₂ becomes as low as 60.0 kJ/mol H₂ when ZrO₂@Nb₂CT_x is used as the catalyst, which is far smaller than the case of ZrO₂ (94.8 kJ/mol H₂) and Nb₂CT_x MXene (125.6 kJ/mol H₂). With the addition of ZrO₂@Nb₂CT_x catalyst, MgH₂ can release about 6.24 wt.% and 5.69 wt.% of hydrogen within 150 s at 300 °C and within 900 s even at 240 °C, respectively. Moreover, it realizes hydrogen absorption at room temperature, which can uptake 2.98 wt.% of hydrogen within 1800 s. The catalytic mechanism analysis demonstrates that the in-situ formed nanocomposites can weaken the Mg–H bonding and provide more hydrogen diffusion channels, enabling the dissociation and recombination of hydrogen under milder reaction conditions.     

Hydrogen adsorption with micro-structure deformation in nanoporous carbon under ultra-high pressure

Hydrogen adsorption with micro-structure deformation under ultra-high pressure in nanoporous carbon (NPC) has been studied. This study proposed a new ultra-high pressurization (UHP) method. It produces a gas atmosphere of over 100 MPa utilizing the cold isostatic pressing (CIP) device. NPC materials were pressurized under a hydrogen atmosphere at 100–400 MPa. NPC fabricated from rice husk via KOH activation possesses a high surface area achieving 3500 cm²/g and a micropore volume of over 2.0 cm³/g. The maximum hydrogen uptake reached 3.2 wt% (77 K, 0.1 MPa). Then, NPC materials were treated with 100–400 MPa pressurization in the hydrogen atmosphere. NPC showed a preferred deformation behavior of 1.1–1.2 nm after pressurization, which is the optimum size for hydrogen adsorption. Additionally, the maximum micropore volume increased to 2.51 cm³/g. However, the hydrogen uptake shows a slight decrease to 3.0 wt%. The isosteric heat of adsorption maintained at 8.0–10.3 kJ/mol.     

Hydro-catalytic treatment of organoamine boranes for efficient thermal dehydrogenation for hydrogen production

This study aims to present the hydro-catalytic treatment of organoamine boranes for efficient thermal dehydrogenation for hydrogen production. Organoamine boranes, methylamine borane (MeAB), and ethane 1,2 diamine borane (EDAB), known as ammonia borane (AB) carbon derivatives, are synthesized to be used as a solid-state hydrogen storage medium. Thermal dehydrogenation of MeAB and EDAB is performed at 80 °C, 100 °C, and 120 °C under different conditions (self, catalytic, and hydro-catalytic) for hydrogen production and compared with AB. For this purpose, a cobalt-doped activated carbon (Co-AC) catalyst is fabricated. The physicochemical properties of Co-AC catalyst is investigated by well-known techniques such as ATR/FT-IR, XRD, XPS, ICP-MS, BET, and TEM. The synthesized Co-AC catalyst obtained in nano CoOOH structure (20 nm, 12% Co wt) is formed and well-dispersed on the activated carbon support. It has indicated that Co-AC exhibits efficient catalytic activity towards organoamine boranes thermal dehydrogenation. Hydrogen release tests show that hydro-catalytic treatment improves the thermal dehydrogenation kinetics of neat MeAB, EDAB, and AB. Co-AC catalyzed hydro-treatment for thermal dehydrogenation of MeAB and EDAB acceleras the hydrogen release from 0.13 mL H₂/min to 46.12 mL H₂/min, from 0.16 mL H₂/min to 38.06 mL H₂/min, respectively at 80 °C. Moreover, hydro-catalytic treatment significantly lowers the H₂ release barrier of organoamine boranes thermal dehydrogenation, from 110 kJ/mol to 19 kJ/mol for MeAB and 130 kJ/mol to 21 kJ/mol for EDAB. In conclusion, hydro and catalytic treatment presents remarkable synergistic effect in thermal dehydrogenation and improves the hydrogen release kinetics.     

Density functional studies on the hydrogen storage capacity of boranes and alanes based cages

The hydrogen storage (H-storage) capacity of various boranes and alanes have been investigated using density functional theory (DFT) based M05-2X method employing 6–31+G** basis set. The changes in the H-storage capacities of borane and alane upon substitution of antipodal atoms in the cages by C, Si, and N have also been investigated. It is found from the calculations that a maximum of 20 H₂ molecules can be adsorbed on the deltahedron faces of these cages. The maximum gravimetric density has been observed for boranes when compared to alanes. The H-storage capacity of closo-borane dianion [B₁₂H₁₂]²⁻, monocarborane [CB₁₁H₁₂]¹⁻, dicarborane [C₂B₁₀H₁₂], and closo-azaborane [NB₁₁H₁₂] cages is almost similar (∼22 wt.%). Among these cages, B_BB dianion show higher binding energy (BE) and BE per H₂ molecule (BE/nH₂) which are 181.06 and 9.03 kJ/mol, respectively. In the case of alanes, dicarbalane [C₂Al₁₀H₁₂] has maximum H-storage capacity of 11.6 wt.%. Based on these findings, a new MOF with carborane (MOF-5_CC) as linker has been designed. The calculation on the new MOF-5B_CC reveals that it has H-storage capacity of 6.4 wt.% with BE/nH₂ of 3.02 kJ/mol.     

Modeling and analyzing the hydriding kinetics of Mg-LaNi5 composites by Chou model

Chou model was used to analyze the influences of LaNi₅ content, preparation method, temperature and initial hydrogen pressure on the hydriding kinetics of Mg-LaNi₅ composites. Higher LaNi₅ content could improve hydriding kinetics of Mg but not change hydrogen diffusion as the rate-controlling step, which was validated by characteristic reaction time t_c. The rate-controlling step was hydrogen diffusion in the hydriding reaction of Mg-30 wt.% LaNi₅ prepared by microwave sintering (MS) and hydriding combustion synthesis (HCS), and surface penetration was the rate-controlling step of sample prepared by mechanical milling (MM). Rising temperature and initial hydrogen pressure could accelerate the absorption rate. The rate-controlling step of Mg-30 wt.% LaNi₅ remained hydrogen diffusion at temperatures ranging from 302 to 573 K, while that of Mg-50 wt.% LaNi₅ changed from surface penetration to hydrogen diffusion with increasing initial hydrogen pressure ranging from 0.2 to 1.5 MPa. Apparent activation energies of absorption for Mg-30 wt.% LaNi₅ prepared by MS and MM were respectively 25.2 and 28.0 kJ/mol H₂ calculated by Chou model. Kinetic curves fitted and predicted by Chou model using temperature and hydrogen pressure were well exhibited.     

Hydrogen storage on pyrolyzed chicken feather fibers

Pyrolyzed chicken feather fibers (PCFF) that were prepared by two-step process (215 °C/15 h + 400-450 °C/1 h) demonstrated a significant H₂ adsorption uptake due to their microporous nature. Considering their large availability, cost and H₂ storage capability, PCFF can be a significant, environmentally friendly and bio-renewable candidate to address the H₂ storage problem. A wide range of microporosities was obtained when the second step pyrolysis temperature was maintained between 400 and 450 °C for 0.5-2 h. The optimal H₂ storage was obtained using 1 h pyrolysis in this temperature range. The maximum excess H₂ storage capacity was 1.5 wt% at 77 K and at pressures below 2 MPa. The notable H₂ adsorption of PCFF below 1 MPa can be justified by the abundance of microporosity, and the nanopores available for H₂ penetration. The estimated adsorption energy for PCFFs, 5-6 kJ/mol was in the range of typical physisorption materials indicating the easy recovery of H₂.     

Analysis of adsorption equilibrium of hydrogen on graphene sheets

The adsorption equilibrium of hydrogen on graphene sheets (GS) was studied based on a sample of GS with S_BET = 300 m²/g at the temperatures of 77.15 K–293.15 K and the pressures of 0 MPa–6 MPa. In the meantime, the adsorptions (Excess adsorption measurements) of hydrogen on granular coconut shell SAC-02 activated carbon (S_BET = 2074 m²/g) and carbon nanofiber (CNFs, S_BET = 205 m²/g) were investigated at the pressures of 0–8 MPa and the temperature of 77.15 K. The outcomes from experiments were used to determine the parameters in Toth equation by way of Non-linear fit. The absolute adsorption amounts of hydrogen on the GS, which were calculated from the equation, were used to calculate the isosteric heat of hydrogen adsorption by use of adsorption isosteres.     

The effects of the micrometric and nanometric iron (Fe) additives on the mechanical and thermal dehydrogenation of lithium alanate (LiAlH4), its self-discharge at low temperatures and rehydrogenation

LiAlH₄ containing 5 wt.% of nanometric Fe (n-Fe) shows a profound mechanical dehydrogenation by continuously desorbing hydrogen (H₂) during high energy ball milling reaching ∼3.5 wt.% H₂ after 5 h of milling. In contrast, no H₂ desorption is observed during low energy milling of LiAlH₄ containing n-Fe. Similarly, no H₂ desorption occurs during high energy ball milling for LiAlH₄ containing micrometric Fe (μ-Fe) and, for comparison, both the micrometric and nanometric Ni (μ-Ni and n-Ni) additive. X-ray diffraction studies show that ball milling results in a varying degree of the lattice expansion of LiAlH₄ for both the Fe and Ni additives. A volumetric lattice expansion larger than 1% results in the profound destabilization of LiAlH₄ accompanied by continuous H₂ desorption during milling according to reaction: LiAlH₄ (solid) → 1/3Li₃AlH₆ + 2/3Al + H₂. It is hypothesized that the Fe ions are able to dissolve in the lattice of LiAlH₄ by the action of mechanical energy, replacing the Al ions and forming a substitutional solid solution. The quantity of dissolved metal ions depends primarily on the total energy of milling per unit mass of powder generated within a prescribed milling time, the type of additive ion e.g. Fe vs. Ni and on the particle size (micrometric vs. nanometric) of metal additive. For thermal dehydrogenation the average apparent activation energy of Stage I (LiAlH₄ (solid) → 1/3Li₃AlH₆ + 2/3Al + H₂) is reduced from the range 76 to 96 kJ/mol for the μ-Fe additive to about 60 kJ/mol for the n-Fe additive. For Stage II dehydrogenation (1/3Li₃AlH₆ → LiH+1/3Al + 0.5H₂) the average apparent activation energy is within the range 77–93 kJ/mol, regardless of the particle size of the Fe additive (μ-Fe vs. n-Fe). The n-Fe and n-Ni additives, the latter used for comparison, provide nearly identical enhancement of dehydrogenation rate during isothermal dehydrogenation at 100 °C. Ball milled (LiAlH₄ + 5 wt.% n-Fe) slowly self-discharges up to ∼5 wt.% H₂ during storage at room temperature (RT), 40 and 80 °C. Fully dehydrogenated (LiAlH₄ + 5 wt.% n-Fe) has been partially rehydrogenated up to 0.5 wt.% H₂ under 100 bar/160°C/24 h. However, the rehydrogenation parameters are not optimized yet.     

Structures and properties of Mg–La–Ni ternary hydrogen storage alloys by microwave-assisted activation synthesis

It is a challenge to prepare a material meeting two conflicting criteria – absorbing hydrogen strongly enough to reach a stable thermodynamic state and desorbing hydrogen at moderate temperature with a fast reaction rate. With the guide of the Mg–La–Ni phase diagram, microwave sintering (MS) was successfully applied to preparing Mg–La–Ni ternary hydrogen storage alloys from the powder mixture of Mg, La and Ni. Their phase structures, morphologies and hydrogen absorption and desorption (A/D) properties have been studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-isotherm (PCI) and differential scanning calorimetry (DSC). The metal hydride of 70 Mg–9.72 La–20.28 Ni (wt pct) has the best comprehensive hydriding and dehydriding (H/D) properties, which can absorb 4.1 wt.% H₂ in 600 s and desorb 3.9 wt.% H₂ in 1500 s at 573 K. The DSC results reveal its onset temperatures of hydrogen A/D are the lowest among all the samples, which are 671.4 and 600.9 K. Its activation energy of dehydriding reaction is 113.5 kJ/mol H₂, which is the smallest among all the samples. Also, Chou model was used to analyze the reaction kinetic mechanism.     

Rb and Cs doping effects in sodium borohydride: Density functional theory for hydrogen (H2) storage purpose

Fuel cell technology based on stationary and mobile applications is needing new hydrogen storage materials equipped with huge gravimetric and volumetric hydrogen densities. Examining the fundamental properties of hydrides is an important part of such process, mainly to understand the structure change's impact on the hydrogen storage. Herein, we applied ab-initio density functional theory using full potential linear augmented plane method to explore the effect of rubidium and cesium doping in sodium borohydride, NaBH₄. The electronic structure calculations exposed the semiconducting nature of NaBH₄ and derived doped structures NaRbBH₄ and NaCsBH₄. The hydrogen (H₂) storage capacity is found 10.66 wt %, 3.27 wt % and 2.36 wt % within a reasonable free energy of ?28.514 kJ/mol, ?29.709 kJ, ?28.51 kJ/mol for NaBH₄, NaRbBH₄ and NaCsBH₄ respectively from quasi-harmonic approximation. Also, we extracted the heat capacity and Debye temperature from vibrational analysis based on phonon calculation. The discovered features show the potential use of presented sodium borohydrides for practical H₂ storage devices.