Hydrogen Storage Applications Research Articles

Study of alkaline metals hydrides RbXH3 (X = Mg/Ca/Sr/Ba) for green energy and hydrogen storage applications

The potential of hydrogen as an energy source has positioned hydrogen storage as a prominent research domain in the current era. Innovative perovskite compounds have emerged as a focal point for investigating hydrogen storage applications. In this study, we have investigated the RbXH3 (X = Mg/Ca/Sr/Ba) perovskite hydrides by density functional theory (DFT). Our exploration encompasses the analysis of electronic structures, mechanical stability, elastic properties, and optical and thermoelectric response. The cubic crystal structures of RbXH3 are revealed, with lattice constants of 4.13, 4.54, 4.82, and 5.17 Å for X = Mg, Ca, Sr, and Ba, respectively. Electronic structure calculations indicate ionic bonding with a wide bandgap reduced with increasing size of X. Mechanical stability, essential for meeting the Born stability criterion, is scrutinized, whereas Pugh criteria suggest a ductile and hard nature for these materials. Thermoelectric characteristics regarding electrical and thermal conductivity, Seebeck coefficient, and power factors are elaborated. The figure of merit emphasizes their suitability for thermoelectric devices. The Gravimetric ratios indicate the hydrogen storage capability, potentially contributing to various transportation and power applications.

Computational study to investigate effectiveness of titanium substitution in CaFeH3 perovskite-type hydride: An approach towards advanced hydrogen storage system

In recent years, there has been increased interest in hydrogen storage due to the numerous advantages hydrogen offers as an energy source. This study explores the structural, hydrogen storage, electronic, elastic, mechanical, and optical properties of Ca1-xTixFeH3 through DFT. After Ti substitution in the host material, structure phase transformation occurs: cubic → pseudo-cubic → cubic. Study compounds are thermodynamically stable and experimentally synthesizable according to the calculated negative formation energies. Gravimetric hydrogen storage capacities for different concentrations of Ti (x = 0, 0.11, 0.33, 0.55, 1) were calculated as 2.963, 2.938, 2.843, and 2.753 wt%, respectively. The investigation focuses on understanding the material's BS, Fermi level, and DOS, elucidating its metallic characteristics, and non-zero DOS at the Fermi level contributing to electrical and thermal conductivity. Elemental partial density of states reveals hybridization effects with Ti doping, affecting the valence band's atomic contributions. Using cubic symmetry, C11, C12, and C14 elastic constants were used to describe mechanical characteristics, and the Born criteria were met. Thus, mechanical stability was demonstrated for these compounds. Optical analyses exhibit changes concerning Ti concentrations and energy levels, including absorption spectra, conductivity, reflectivity, dielectric function, refractive index, energy loss function, and extinction coefficient. These findings shed light on the material's response to incident radiation and potential applications in hydrogen storage and optoelectronic devices.

First-principles investigation of Irida-graphene decorated with alkali metal for reversible hydrogen storage

Irida-graphene (IG) is a novel stable graphene allotrope, which exhibits metallic property. Based on first principles calculations, the potential of IG decorated with alkali metal atoms in reversible hydrogen storage has been investigated. Compared with graphene, IG has stronger binding on alkali metal atoms. For Li, Na, and K decorated IG, the polarization mechanism plays a crucial role in the adsorption of H2, the adsorption energies of H2 are −0.286, −0.209 and −0.183 eV/H2, and the hydrogen gravimetric densities can reach 7.1, 7.8 and 5.2 wt%, respectively, indicating that K decorated IG is not suitable as a hydrogen storage medium. The desorption temperatures calculated are 365 K and 267 K for stored H2 on Li/IG and Na/IG, respectively, and ab inito MD simulation suggest that Li/IG and Na/IG are stable at high temperature, thus Li and Na decorated IG have the potential application for reversible hydrogen storage.

Investigation of gas residuals in sandstone formations via X-ray core-flooding experiments: Implication for subsurface hydrogen storage

The production and utilization of hydrogen (H2) as a clean energy source offer a promising solution towards achieving net-zero carbon emissions. Utilizing sandstone formations for geological hydrogen storage presents a viable option for the practical implementation of the hydrogen economy, offering both safe and large-scale containment capabilities. Accurate assessment of gas displacement behavior in porous media plays a critical role in understanding gas saturation, gas residual, and long-term storage duration. However, there are limited studies available on dynamic displacements for hydrogen storage applications. This study aims to enhance the understanding of gas flow behavior in sandstone rocks for different gas types and determine the role of capillary pressure and gas wettability during hydrogen storage. A series of gas core-flooding experiments are performed on a brine-saturated sandstone core sample using three different gases (CO2, CH4, and H2). X-ray scanning technique is applied to detect the gas saturation and gas residual after the core-flooding experiments. The results indicate that the average gas saturation ranges between 25 and 40%, with zero gas residual for all gases, suggesting that the gas residuals in this clean sandstone sample are unaffected by the gas type. Initially, the capillary pressure profile for the sample displayed low brine saturation at 200 psi, indicating very low capillary pressure in the sample due to the high permeability and large pore radius, despite the strong water-wetting behavior of the sample. Moreover, the obtained results indicate the high potential for gas recovery (especially for hydrogen during withdrawal cycles), and the high displacement efficiency in sandstone rocks. The reported low gas residual suggests that the wettability of the rock is not affected by gas injection, and it appears that the wettability and capillary pressure are not the controlling factors for gas storage in this sandstone sample. This observation suggests that the structural trapping mechanism is most likely to be the dominant trapping mechanism in this shallow high permeable sandstone rock. Also, the injection of cushion gases such as CO2 and CH4 indicated similar results to hydrogen injection, due to the low capillary pressure and high permeability in this sandstone sample. The findings of this study can greatly enhance the understanding of gas injection, displacement behavior, and gas residuals in sandstone rocks related to underground hydrogen storage.

Probabilistic Techno-Economic Assessment of Medium-Scale Photoelectrochemical Fuel Generation Plants.

Photoelectrochemical (PEC) systems are promising approaches for sustainable fuel processing. PEC devices, like conventional photovoltaic-electrolyzer (PV-EC) systems, utilize solar energy for splitting water into hydrogen and oxygen. Contrary to PV-EC systems, PEC devices integrate the photoabsorber, the ionic membrane, and the catalysts into a single reactor. This integration of elements potentially makes PEC systems simpler in design, increases efficiency, offers a cost advantage, and allows for implementation with higher flexibility in use. We present a detailed techno-economic evaluation of PEC systems with three different device designs. We combine a system-level techno-economic analysis based on physical performance models (including degradation) with stochastic methods for uncertainty assessments, also considering the use of PV and EC learning curves for future cost scenarios. For hydrogen, we assess different PEC device design options (utilizing liquid or water vapor as reactant) and compare them to conventional PV-EC systems (anion or cation exchange). We show that in the current scenario, PEC systems (with a levelized cost of hydrogen of 6.32 $/kgH2 ) located in southern Spain are not yet competitive, operating at 64% higher costs than the PV-driven anion exchange EC systems. Our analysis indicates that PEC plants' material and size are the most significant factors affecting hydrogen costs. PEC designs operating with water vapor are the most economical designs, with the potential to cost about 10% less than PV-EC systems and to reach a 2 $/kgH2 target by 2040. If a sunlight concentrator is incorporated, the PEC-produced hydrogen cost is significantly lower (3.59 $/kgH2 in the current scenario). Versions of the concentrated PEC system that incorporate reversible operation and CO2 reduction indicate a levelized cost of storage of 0.2803 $/kWh for the former and a levelized cost of CO of 0.546 $/kgCO for the latter. These findings demonstrate the competitiveness and viability of (concentrated) PEC systems and their versatile use cases. Our study shows the potential of PEC devices and systems for hydrogen production (current and future potential), storage applications, and CO production, thereby highlighting the importance of sustainable and cost-effective design considerations for future advancements in technology development in this field.

Hydrogen molecule adsorption on triazine carbon nitride nanosheet decorated with Rh, Ir, Pd, and Pt elements for hydrogen storage applications

As materials for hydrogen storage is one of the most popular form of energy storage materials, therefore hydrogen storage materials has been widely explored. As the active of platinum-group elements, their decoration on the surface of triazine-based graphitic carbon nitride nanosheet as affective hydrogen storage could be explored. Adsorption of hydrogen molecules on the Rh-, Ir-, Pd-, and Pt-decorated onto triazine-based graphitic carbon nitride nanosheets was therefore studied using the periodic DFT method. Based on the most stable configurations of metal-decorated triazine-based graphitic carbon nitride nanosheets, their adsorption abilities on hydrogen molecules are in orders: H2/Ir–g–C3N4 > > H2/Rh–g–C3N4 > H2/Pt–g–C3N4 > H2/Pd–g–C3N4 derivatives for single hydrogen molecule adsorption, and 2H2/Ir–g–C3N4 > > 2H2/Rh–g–C3N4 > > 2H2/Pt–g–C3N4 ~ 2H2/Pt–g–C3N4 derivatives for the second step of the hydrogen molecule adsorption. The Ir–decorated derivative was found as the best hydrogen storage property and its stepwise adsorption energies of three hydrogen molecules of −3.10 eV, −1.23 eV and − 0.03 eV were obtained. All the metal-decorated derivatives were suggested as hydrogen storage materials.

Light-Driven De/Rehydrogenation of a LiH Surface under Ambient Conditions.

Lithium hydride (LiH), a saline hydride with a hydrogen density of 12.6 wt %, is highly thermostable, which hinders its extensive application in hydrogen storage. In this study, we demonstrate a distinct photodecomposition of LiH under ambient conditions. Ultraviolet-visible (UV-vis) illumination induces hydrogen release and creates surface hydrogen vacancies on LiH. The subsequent H- migration enables hydrogen desorption and the accumulation of vacancies at the subsurface, resulting in the generation of metallic Li clusters. Rehydrogenation, on the contrary, can be charged under UV-vis illumination in 1 bar H2. Such phenomena show that the thermodynamic and kinetic limits in the re/dehydrogenation of LiH can be broken under illumination, which allows hydrogen storage over the LiH surface at temperatures ∼600 K lower than those of the corresponding thermal process. This work provides new insights into the interaction of semiconducting hydrides and photons and opens an avenue for the development and optimization of materials for hydrogen storage and related photodriven reactions.

Hydrogen unclogging of caprock

Kerogen has a lower affinity to hydrogen than methane; thus, it allows hydrogen to flow more easily, but it is unclear how the permeabilities of hydrogen and methane differ. This study determines the single-phase permeability of hydrogen and compares it with methane permeability in organic-rich caprock. It takes into account adsorption to the pore wall and slippage at the boundary. It implements the two processes at 370 K for pressures from 500 to 4000 psi to obtain the hydraulic conductance of a sub-100-nm conduit. It then relates them to the macroscopic behavior via network modeling. Lower pressures represent depleted gas reservoirs in the subsurface. Decreasing pore pressure enhances hydrogen transport by reducing its adsorption to the pore wall and transitioning its behavior from continuum to discrete particles, leading to first- or second-order slippage. The results show that hydrogen conductance, qin−situ (H2), is always larger than the reference conductance without adsorption and slippage (q0). Hydrogen permeability, kin−situ (H2), is also larger than methane permeability, kin−situ (CH4), while the permeability values differ by 70% − 130%, depending on the pore pressure. This study also determines the conduit size corresponding to the ratio of hydrogen permeability to methane permeability at in-situ conditions by comparing it with the ratio of hydraulic conductance of hydrogen to methane. The results have applications in underground hydrogen storage by indicating how hydrogen flow changes with pressure in ultra-tight formations.

Stable nature of [BH4]− ions in deliquescence thin-film NaBH4 and humidity control of their decomposition toward hydrogen supply and storage application

In this study, we investigated the deliquescence of NaBH4 thin films under atmospheric conditions toward their hydrogen supply application. Upon exposed to air, the film deliquesced along with generating hydrogen due to the decomposition of [BH4]- ions, but the decomposition rate was slow enough for a sizable amount of [BH4]- ions remained stable in the deliquesced film. As a result, a reversible deliquescence-recrystallization cycle in the NaBH4 thin film could be achieved through control of humidity. Molecular dynamics simulations suggested that Na+ and [BH4]- ions tended to neighbor each other with almost the same intra-distance as that in the crystal. A kind of such local ordered structures in deliquesced NaBH4 may prevent an excess hydration and subsequent decomposition of [BH4]- ions and is responsible for the stability of [BH4]- ions, enabling the reversible deliquescence-recrystallization cycle. These combined experimental and theoretical insights offer new perspectives on controlling hydrogen release from borohydrides based on humidity conditions in the thin film form.

Preparation and investigation of TbCrO3/montmorillonite-K10 nanocomposite electrode for electrochemical hydrogen storage application

The limited resources of fossil fuels and the increase in human’s demand for energy have made the use of alternative green energies like hydrogen very important. In this regard, achieving superior specific capacity and high-performance electrochemical hydrogen storage requires the structural design and development of highly active electrode material with cooperative influence of “spillover”, “redox”, and “physisorption” mechanisms. The aim of this report is to fabricate a binary TbCrO3/montmorillonite-K10 (TC/MMT) nanocomposite and to skillfully ensure its electrochemical ability for hydrogen storage in 2.0 M KOH electrolyte, for the first time. A facile sonochemical strategy was presented to successfully form uniform orthorhombic TC nanoparticles with varying tetradentate Schiff base ligands derived from salicylaldehyde and relative diamines as well as the molar ratio of H2Salbn to Tb3+. Characterization analyses displayed that the nucleation and growth process of TC samples can be well controlled by a molar ratio of H2Salbn:Tb3+ = 1:1 within the range of 17–72 nm. Furthermore, implementation of a well-organized MMT-based nanocomposite with various amounts of nano-TC perovskites was evaluated on the structural and electrochemical features. The greatly enhanced hydrogen storage capacity of TC/MMT nanocomposites was acquired as 734.3 mAh/g after 15 cycles, when 10.0 % of perovskite oxide is induced by MMT layers. Moreover, architecture of pristine TC and MMT electrodes possessed a 936.87 and 341.52 mAh/g discharge capacities at the same situation. These merits allow a promising potential application of the nanocomposite electrodes containing rare-earth chromite oxide and clay substrates in electrochemical energy-storage devices.

Fabrication and design of four-component Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite as new active materials for high performance electrochemical hydrogen storage application

Considering the growth of the population and the demand for clean and renewable energy systems such as hydrogen, the development and optimization of the active materials for advanced electrochemical hydrogen storage require considerable effort. The goal of this research was to synthesize a four-component Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite through a series of multiple steps. In order to examine the physicochemical characteristics of the sample, a variety of techniques were employed, including field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), Brunauer- Emmett–Teller (BET), Fourier-transform infrared (FT-IR) and vibrating sample magnetometer (VSM). Among these features are the morphological characteristics, structure properties, porosity, and the magnetic properties of the Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite. In addition, as-synthesized materials were investigated for electrochemical performance as potential electrochemical hydrogen storage materials. A chronopotentiometer (ChP), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and linear polarization method were used to study the hydrogen storage efficiency of as-schemed materials. A hydrogen storage capacity of approximately 225 mAhg−1 was determined for the Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite after one cycle at a constant current of 1 mA, while this value was calculated for the Bi2S3, CuFe2O4 and Bi2S3/CuFe2O4 samples at 292 mAhg−1, 433 mAhg−1, and 276 mAhg−1, respectively. A quadruple Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite showed excellent discharge capacity after 15 cycles in comparison with other samples. According to our calculations, this value is 1200 mAhg−1, while Bi2S3, CuFe2O4 and Bi2S3/CuFe2O4 nanostructures have capacities of 750 mAhg−1, 800 mAhg-1 and 1000 mAhg-1, respectively. In view of the demonstrated superior electrochemical properties of the Bi2S3/CuFe2O4/CuO/Cu2O nanocomposite, it has a very promising future for electrochemical hydrogen storage.

Mechanical processing and thermal stability of the equiatomic high entropy alloy TiVZrNbHf under vacuum and hydrogen pressure

This study investigates the potential of nanostructuring the equiatomic high entropy alloy TiVZrNbHf by high-pressure torsion to improve its already promising hydrogen absorption properties. The detailed microstructural analysis of the material after processing demonstrates that a homogenous single-phase nanocrystalline structure can be obtained despite shear band development. Due to the metastable character of many high entropy alloys, this analysis was complemented by investigating the thermal stability of the alloy under both vacuum and hydrogen pressure. For the latter, the material was characterized via in situ X-ray diffraction during hydrogen charging at 500 °C, giving a detailed insight into the phase evolution during initial absorption and subsequent cycling. These experiments evidenced the inherent metastability of TiVZrNbHf, which resulted in its decomposition into a bcc, hcp, and C14 Laves phase under both vacuum and hydrogen atmospheres. Despite decomposition, the material retained its nanocrystalline structure under hydrogen pressure, presumably due to hydride formation, while significant grain growth occurred under vacuum. These findings deepen the understanding of the deformation and hydrogen charging behavior of this promising high entropy alloy, suggesting an approach for engineering such alloys for enhanced stability and performance, particularly in solid-state hydrogen storage applications.

A Computational Study of Metal Hydrides Based on Rubidium for Developing Solid‐State Hydrogen Storage

AbstractIn this work, we explore the physical properties of RbXH3 (X=Cr, Zr) perovskite hydrides for solid‐state hydrogen storage. The structural, mechanical, electronic, optical, and hydrogen storage properties were theoretically investigated using density functional theory and CASTEP software. The selected candidates were fully relaxed and optimized in the cubic phase space group Pm‐3 m. The structural phase stability was verified by means of thermodynamic, dynamic and mechanical stabilities. Mechanical analyses based on Poisson's ratio (ν), G/B ratio, and Cauchy pressure show that RbCrH3 and RbZrH3 exhibit brittle behavior with preference of ionic bonding. The electronic structures unveil half‐metallicity in RbCrH3 compound and metallic‐like behavior in RbZrH3. Furthermore, optical calculations were also conducted to gain additional insights into the physical properties of RbXH3 compounds. The gravimetric hydrogen storage (Cwt %) capacities have been calculated as 2.09 wt % and 1.64 wt % for RbCrH3 and RbZrH3, respectively. The hydrogen desorption temperatures have been obtained as 545.11 K and 548.15 K for RbCrH3 and RbZrH3, respectively. Our calculation propose RbCrH3 hydride as potential material for hydrogen storage application.

Destabilizing high-capacity high entropy hydrides via earth abundant substitutions: From predictions to experimental validation

The vast chemical space of high entropy alloys (HEAs) makes trial-and-error experimental approaches for materials discovery intractable and often necessitates data-driven and/or first principles computational insights to successfully target materials with desired properties. In the context of materials discovery for hydrogen storage applications, a theoretical prediction-experimental validation approach can vastly accelerate the search for substitution strategies to destabilize high-capacity hydrides based on benchmark HEAs, e.g. TiVNbCr alloys. Here, machine learning predictions, corroborated by density functional theory calculations, predict substantial hydride destabilization with increasing substitution of earth-abundant Fe content in the (TiVNb)75Cr25-xFex system. The as-prepared alloys crystallize in a single-phase bcc lattice for limited Fe content x < 7, while larger Fe content favors the formation of a secondary C14 Laves phase intermetallic. Short range order for alloys with x < 7 can be well described by a random distribution of atoms within the bcc lattice without lattice distortion. Hydrogen absorption experiments performed on selected alloys validate the predicted thermodynamic destabilization of the corresponding fcc hydrides and demonstrate promising lifecycle performance through reversible absorption/desorption. This demonstrates the potential of computationally expedited hydride discovery and points to further opportunities for optimizing bcc alloy ↔ fcc hydrides for practical hydrogen storage applications.

Exploring Nanomaterials for Hydrogen Storage: Advances, Challenges, and Perspectives.

Hydrogen energy heralded for its environmentally friendly, renewable, efficient, and cost-effective attributes, stands poised as the primary alternative to fossil fuels in the future. Despite its great potential, the low volumetric density presents a formidable challenge in hydrogen storage. Addressing this challenge necessitates exploring effective storage techniques for a sustainable hydrogen economy. Solid-state hydrogen storage in nanomaterials (physically or chemically) holds promise for achieving large-scale hydrogen storage applications. Such approaches offer benefits, including safety, compactness, lightness, reversibility, and efficient generation of pure hydrogen fuel under mild conditions. This article presents solid-state nanomaterials, specifically nanoporous carbons (activated carbon, carbon fibers), metal-organic frameworks, covalently connected frameworks, nanoporous organic polymers, and nanoscale metal hydrides. Furthermore, new developments in hydrogen fuel cell technology for stationary and mobile applications have been demonstrated. The review outlines significant advancements thus far, identifies key barriers to practical implementation, and presents a perspective for future sustainable energy research. It concludes with recommendations to enhance hydrogen storage performance for cost-effective and long-lasting utilization.

Tailoring hydrogen storage performance in γ-graphyne through valence band modulation of adsorbed Li via doping and strain

Hydrogen storage is indeed fundamental to utilizing H2 effectively, and porous carbon materials have emerged as highly promising supports for this purpose. γ-Graphyne (γGy) possesses abundant chemical bonds, considerable porosity, and exceptional chemical stability, positioning it as a promising candidate for hydrogen storage and transport applications. In this study, we conducted density functional theory calculations to investigate the potential of Li- and Na-loaded γGy as hydrogen storage materials. Our findings reveal that the hydrogen storage capacity (HSC) of Na-loaded γGy falls significantly short of expectations, whereas Li-loaded γGy demonstrates a notably higher HSC. Subsequently, our calculations indicate that B-doping of γGy does not promote favorable HSC, whereas N-doping exhibits a beneficial effect. Furthermore, we observed that tensile strain favors the hydrogen storage properties of 4Li@γGy and 4Li@N-γGy, while compressive strain enhances the hydrogen storage characteristics of 4Li@B-γGy. Notably, we discovered the capacity to adjust the valence band center of Li (ɛVB), consequently influencing the hydrogen storage performance of γGy. Our investigation suggests that increased overlap between ɛVB in Li-loaded graphyne and the effective alignment of H2 and the supporting structure augments the binding force between Li and H2, thereby amplifying the HSC.

The contribution of 515-nm green laser L-PBF to the thermal performance of lattice-based heat exchangers for hydrogen storage applications

The contribution of 515-nm green laser L-PBF to the thermal performance of lattice-based heat exchangers for hydrogen storage applications

State of the Art on Relative Permeability Hysteresis in Porous Media: Petroleum Engineering Application

This paper delivers an examination of relative permeability hysteresis in porous media in the field of petroleum engineering, encompassing mathematical modeling, experimental studies, and their practical implications. It explores two-phase and three-phase models, elucidating the generation of scanning curves and their applications in various porous materials. Building on the research of traditional relative permeability hysteresis models, we have incorporated literature on forward calculations of relative permeability based on digital rock core models. This offers a new perspective for studying the hysteresis effect in relative permeability. Additionally, it compiles insights from direct relative permeability and flow-through experiments, accentuating the methodologies and key findings. With a focus on enhanced oil recovery (EOR), carbon capture, utilization and sequestration (CCUS), and hydrogen storage applications, the paper identifies existing research voids and proposes avenues for future inquiry, laying the groundwork for advancing recovery techniques in oil and gas sectors.

Degree based hybrid topological indices and entropies of hydrogen bonded benzo-trisimidazole frameworks

Hydrogen bonded organic frameworks, especially those comprising of benzo-trisimidazole are porous molecular materials facilitated by hydrogen-bonds. As these materials find several applications in catalysis, hydrogen storage, and environmental remediation through sequestration, we have investigated the topological and entropy properties of these novel covalent organic frameworks. We have obtained the analytical expressions for vertex degree based topological indices in order to characterize their topological complexities. Our computations reveal that there are isentropic hydrogen bonded networks. Furthermore we demonstrate the utility of variations of hybrid arithmetic, geometric, harmonic and Zagreb degree based topological and entropy indices of these networks.

Computational investigation of NLi4-cluster decorated phosphorene for reversible hydrogen storage

The use of lithium-decorated phosphorene for hydrogen storage is significantly limited due to metal aggregation on substrates. Despite considerable research and effort in the literature to address this issue, no one has succeeded in enhancing the capacity of phosphorene through metal atom decoration. Based on density functional theory (DFT) and AIMD simulations, superalkali NLi4-decorated black phosphorene monolayer is developed as a new hydrogen storage solid-state material. Our results show that the NLi4-cluster exhibits a significant binding energy of −3.18 eV when attached to one side of the phosphorene on a stable site, indicating a strong affinity between the NLi4-cluster and phosphorene surfaces. Moreover, 2(NLi4)@phosphorene can store up to 30H2 molecules with a suitable average hydrogen adsorption-energy and a maximum hydrogen storage capacity of 6.8 wt%. Using the van't Hoff equation and increasing the pressure, we find that the desorption temperature is higher than the critical point for hydrogen. AIMD simulations at different temperatures demonstrate the thermal stability of the hydrogenated 2(NLi4)@phosphorene and the H2 desorption process. The findings of the present study suggest the potential utilization of the 2(NLi4)@phosphorene adsorptive material for hydrogen storage applications.