Reversibly storing over 12 wt% H2 by a trilayered lithium borohydride nanocomposite commencing from 70ºC

Reversibly storing over 12 wt% H2 by a trilayered lithium borohydride nanocomposite commencing from 70ºC | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Reversibly storing over 12 wt% H 2 by a trilayered lithium borohydride nanocomposite commencing from 70ºC Hongge Pan, Yongfeng Liu, Wenxuan Zhang, Xin Zhang, Chaoqun Li, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5744222/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Mar, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Hydrogen storage in lithium borohydride (LiBH4) with high gravimetric and volumetric hydrogen densities has attracted intensive research interest. However, the high working temperatures and poor reversibility due to the high thermodynamic stability and kinetic barriers, limits its practical applications. Herein, we fabricate a unique trilayered nanostructure composed of layers of graphene support, Ni nanoclusters, and LiBH4 nanoparticles, through a layer-by-layer assembly approach. The Ni nanoclusters offer nucleation sites, separate LiBH4 nanoparticles from graphene, catalyze the formation of B-H bonds and eliminate the foaming effect. During hydrogenation, Ni cleaves H-H bonds and B clusters, creating additional hydrogen absorption sites and reducing the H adsorption energy of B, which lowers the hydrogen dissociation barrier, allowing reversible storage of approximately 12.27 wt% H2 by LiBH4 commencing from 70 ºC under 100 bar H2. This finding guides the design and fabrication of light-metal hydride nanostructures for practical on-board hydrogen storage applications. Physical sciences/Energy science and technology/Energy storage/Hydrogen storage/Chemical hydrogen storage Physical sciences/Materials science/Nanoscale materials/Synthesis and processing Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Hydrogen storage in lithium borohydride (LiBH 4 ) with high gravimetric and volumetric hydrogen densities has attracted intensive research interest. However, the high working temperatures and poor reversibility due to the high thermodynamic stability and kinetic barriers, limits its practical applications. Herein, we fabricate a unique trilayered nanostructure composed of layers of graphene support, Ni nanoclusters, and LiBH 4 nanoparticles, through a layer-by-layer assembly approach. The Ni nanoclusters offer nucleation sites, separate LiBH 4 nanoparticles from graphene, catalyze the formation of B-H bonds and eliminate the foaming effect. During hydrogenation, Ni cleaves H-H bonds and B clusters, creating additional hydrogen absorption sites and reducing the H adsorption energy of B, which lowers the hydrogen dissociation barrier, allowing reversible storage of approximately 12.27 wt% H 2 by LiBH 4 commencing from 70 ºC under 100 bar H 2 . This finding guides the design and fabrication of light-metal hydride nanostructures for practical on-board hydrogen storage applications. To power a sustainable civilization, hydrogen is a desirable alternative to conventional fossil fuels. 1-3 However, lack of safe, efficient, and economical hydrogen storage methods remains a roadblock to the wide use of hydrogen as a fuel. 4-6 Special attention has been paid to materials-based hydrogen storage, and among the choices, LiBH 4 with extremely high gravimetric (18.5 wt%) and volumetric (121 kg m -3 ) hydrogen densities has received intensive research interest. 7-9 However, high thermodynamic stability and kinetic barrier lead to high temperatures for reversible hydrogen storage by LiBH 4 . 10-11 A variety of strategies have been proposed to improve the hydrogen storage performance of LiBH 4 , including substitution of anions or cations, 12-15 formation of reactive composites, 16-19 catalysts 20-24 and nanostructuring. 25-39 In particular, the reduction of particle size to nanoscale through nanostructuring has proven very effective in lowering the operating temperatures and improving the reversibility of hydrogen cycling. Nanoconfinement is the most frequently used technique to increase specific surface areas, generate more boundaries and defects, all of which shorten mass transport path, accelerate desorption, and lower dehydrogenation temperatures compared to their bulk counterparts. 25- 39 In 2009, Cahen et al. loaded 33 wt% LiBH 4 into 4 nm-sized mesoporous carbon by solution impregnation in ethers. 26 Nanosized LiBH 4 displayed enhanced desorption kinetics with 3.4 wt% of hydrogen release within 90 min at 300 ºC. The encapsulation of LiBH 4 into carbon cages via melt infiltration induced remarkable reductions in operation temperatures since the hydrogen desorption commenced from 200 ºC and peaked at 320 ºC, and rehydrogenation was completed at 400 ºC under 50 bar H 2 . The desorption kinetics was further improved by using porous materials mixed with metal/metal oxides as host materials, especially for Ni decorated scaffolds. 29-35 The onset temperature for H 2 desorption was decreased to 250 °C after confining LiBH 4 into a porous carbon scaffold decorated with Ni nanoparticles. 31 The use of porous hollow carbon microspheres composed of carbon-coated Ni nanoparticles as scaffolds induced the release of 4 wt% H 2 within 30 min at 300 ºC. 32 Rehydrogenation was also significantly enhanced through adding Ni into the nanoporous carbon-confined LiBH 4 . 36 Alternatively, the use of graphene as a support improved the LiBH 4 loading up to 70 wt% because of low weight and high specific surface area. 37 Similarly, the peak dehydrogenation temperature was reduced to 346 °C from 470 °C when assembling 2-nm thick LiBH 4 on graphene with 69.1 wt% loading. 38 The Ni nanocrystals of 2-4 nm in size enabled graphene-supported LiBH 4 nanoparticles of 5-10 nm in size to reversibly desorb and absorb ~9.2 wt% H 2 at 300 °C up to 100 cycles. 39 However, the onset temperature for hydrogen uptake was measured to be 125 °C under 100 bar H 2 , which cannot be met by the waste heat from hydrogen fuel cells on board. 40 There remains a huge challenge to achieve such a breakthrough. To understand underlying reasons, we first conducted density functional theory (DFT) calculations to investigate the hydrogen adsorption behavior of B on different substrates and catalytic supports. The B₇₂ cluster ( Fig. 1a ) and its adsorption configurations on C ( Fig. 1b ) and Ni surfaces ( Fig. 1c) were optimized. The results reveal significant structural reorganization of the B cluster on the Ni surface, with partial B-B bond dissociation and adsorption at Ni hollow sites. In contrast, the interaction between B and the C substrate appears weaker, which could alter the hydrogen adsorption pathway and capability on B. Subsequent calculations of hydrogen adsorption energies ( E ads ) on B atoms in various coordination environments showed distinct behaviors. The hydrogen adsorption energy ( E ads ) was calculated using the following formula: where E total is the optimal energy for the total structure of the H atom after adsorption on the surface, and E system and E H2 are the optimal energies for the adsorption system and the individual hydrogen molecule, respectively. As shown in Fig. 1d and Supplementary Table 1 , two specific B sites exhibit the weakest (B2, E ads = 0.97 eV) and strongest (B1, E ads = -1.80 eV) hydrogen adsorption strengths within the pure B cluster. B atoms affected by C or Ni show weakened but still negative hydrogen adsorption energies, suggesting that H atoms can more readily adsorb/migrate to additional B sites and desorb or migrate after the reaction. Moreover, the structural breakdown of the B icosahedron on the Ni surface increases the availability of adsorption sites for H, while C tends to occupy adsorption sites, potentially hindering H migration on the B surface. This suggests that a layered assembly of C and B, designed to separate the two, could substantially enhance hydrogen adsorption performance while maintaining the benefits of graphene nanoconfinement and Ni catalysis. In terms of calculations, we designed and fabricated a unique trilayered LiBH 4 nanocomposite through a layer-by-layer assembly process as illustrated in Fig. 2 a. Here, the Ni nanocluster-decorated graphene (denoted as Grs-Ni) was first synthesized via heating a mixture of Ni(NO 3 ) 2 ·6H 2 O and few-layer graphene at 400 °C under Ar/H 2 . Transmission electron microscope (TEM) observation ( Fig. 2 b-f) indicated that Ni particles emerged on graphene and gradually increased in quantity and in size. X-ray diffraction (XRD) profiles prove the formation of cubic metallic Ni (PDF: 04-0850) ( Supplementary Fig. 1 a). Further X-ray photoelectron spectroscopy (XPS) analysis confirms the presence of metallic Ni ( Supplementary Fig. 1 b), and its particle size is less than 5 nm as in TEM images ( Supplementary Fig. 1 c), by taking Grs-10 wt% Ni (labelled as Grs-10Ni) as the representative sample. Subsequently, the graphene-Ni-LiBH 4 nanostructure (denoted as Grs-Ni-LiBH 4 ) was prepared by reacting n-butyl lithium (C 4 H 9 Li, n -BuLi) and triethylamine borane ((C 2 H 5 ) 3 NBH 3 , Et 3 N∙BH 3 ) in n-hexane under 50 bar H 2 using the prepared Grs-Ni as supports. After filtration, washing and drying, solid Grs-Ni-LiBH 4 powders were obtained. Here, Grs-Ni as the support was set to be 30 wt% of the resultant product. The characteristic diffraction peaks of LiBH 4 (PDF: 01-081-9182) were clearly identified in all samples by XRD ( Supplementary Fig. 2 a). Fourier transform infrared (FTIR) examination indicates the B-H vibrations of LiBH 4 at 2390, 2291, 2221 and 1122 cm -1 ( Supplementary Fig. 2 b). Scanning electron microscope (SEM) observation ( Fig. 2 g-k) displays plenty of nanoparticles on the sample surface. In comparison with pristine graphene ( Fig. 2 g), the presence of nanoparticulate Ni facilitate the growth of LiBH 4 nanoparticles ( Fig. 2 h and i), especially for the Grs-6Ni sample ( Fig. 2 i). This fact indicates that the nanosized Ni favors the nucleation and growth of LiBH 4 nanoparticles. Further increasing the Ni content to 10 wt% and 20 wt% led to more and much smaller LiBH 4 nanoparticles ( Fig. 2 j-k), which can be explained by the increased nucleation facilitated by nanoparticulate Ni. Comparison revealed that the Grs-10Ni-LiBH 4 sample, composed of 70 wt% LiBH 4 and 27 wt% Grs and 3 wt% Ni, delivers relatively smaller particles and much more uniform distribution. The layer-by-layer assembly nanostructure was further studied by TEM, energy dispersive spectroscopy (EDS), high-resolution TEM (HRTEM) and selected area electron diffraction (SAED) ( Fig. 3 ), by comparing the Grs-10Ni and the Grs-10Ni-LiBH 4 . As observed in the TEM image and corresponding EDS mapping, the Grs-10Ni sample shows that ~2-5 nm-sized metallic Ni particles anchored on the surface of graphene ( Fig. 3a ). In comparison, there is a strong correlation in special distribution of LiBH 4 and Ni in Grs-10Ni-LiBH 4 , indicating that LiBH 4 covers the nanocluster Ni layer of the Grs-10Ni ( Fig. 3b ). Further HRTEM and SAED results indicate the significant difference between Area 1 and 2 ( Fig. 3c ). The interplanar spacings of the (311) facet of Ni, the (020) facet of LiBH 4 and the (1 1 ( - ) 00) facet of graphene were clearly detected in Area 1. However, only Ni and graphene were identified in Area 2. The synthesized LiBH 4 particles was measured to be 40-80 nm in size. Thus, the obtained Grs-10Ni-LiBH 4 sample displays a distinct trilayer nanostructure, composed of a graphene support layer, a nanocluster Ni layer and a nanoparticulate LiBH 4 layer. The resultant trilayered nanocomposites were subjected to hydrogen desorption/absorption measurements in isothermal and non-isothermal modes. As shown in Fig. 4 a-c , the presence of Ni nanoclusters contributed a noticeable decrease in the dehydrogenation temperature of LiBH 4 . The dehydrogenation peak temperature was lowered from 360 °C to 330 °C when increasing x in the Grs- x Ni from 0 to 10 wt%, which is 105 °C lower than that of pristine LiBH 4 (435 °C) ( Fig. 4a ). While further increasing x to 20 wt%, the desorption curve maintained nearly unchanged. The reduction in the desorption temperatures was also confirmed by differential scanning calorimetry (DSC) examination ( Supplementary Fig. 3 ). In contrast to pristine LiBH 4 , no obvious melting endothermic peak was observed for the Grs- x Ni-containing samples, especially for the Grs-10Ni sample. The desorption hydrogen quantity of the Grs-10Ni-LiBH 4 sample was measured by a volumetric method to be 7.4 wt% with respect to the whole nanocomposite after being heated to 368 °C, with an onset temperature of 100 °C ( Fig. 4b ). It corresponds to ~10.5 wt% of H 2 from LiBH 4 since graphene and Ni releases no hydrogen, which is nearly 4 times that of pristine LiBH 4 (~2.7 wt%) under identical conditions. Isothermal examination revealed much faster hydrogen release from Grs-10Ni-LiBH 4 than that of pristine LiBH 4 and LiBH 4 -Grs samples. At 350 °C, approximately 8 wt% of H 2 was released within 35 min (~11.4 wt% H 2 /LiBH 4 ), while the pristine LiBH 4 only liberated ~1.7 wt% of H 2 ( Fig. 4c ). When operating at 300 °C, the average desorption rate of the Grs-10Ni-LiBH 4 was also twice that of the LiBH 4 -Grs sample as it released approximately 6.5 wt% of H 2 within 100 min, in contrast to 3.2 wt% from the Grs-LiBH 4 sample ( Fig. 4d ). The desorption activation energy was calculated to be 108.0 ± 6.0 kJ mol -1 for Grs-10Ni-LiBH 4 ( Fig. 4e ), reduced by approximately 40% and 7% with respect to pristine sample (182 ± 3.5 kJ mol -1 ) ( Supplementary Fig. 4 ) and Grs-LiBH 4 (116 ± 2.9 kJ mol -1 ) (Fig. 3f), respectively. These results indicated unambiguously the important role of Ni in catalyzing hydrogen desorption from LiBH 4 . Rehydrogenation of the dehydrogenated samples as a function of temperature was conducted under 100 bar H 2 . The presence of Ni nanoclusters distinctly reduced the rehydrogenation onset temperature of the dehydrogenated LiBH 4 ( Fig. 5a ). The optimal composition is Grs-10Ni-LiBH 4 because it started taking up hydrogen from 70 °C, which is ~245 °C lower than that of dehydrogenated pristine LiBH 4 (315 °C). To the best of our knowledge, this is the lowest onset hydrogenation temperature for LiBH 4 -based hydrogen storage materials ( Fig. 5b ). The total hydrogen uptake amounted to 8.2 wt% upon heating to and dwelling at 350 °C ( Supplementary Fig. 5 ), corresponding to ~12.27 wt% H 2 by LiBH 4 . Isothermal measurements indicated that the hydrogenation was completed within 300 min at 350 °C under 100 bar H 2 by the dehydrogenated Grs-10Ni-LiBH 4 ( Fig. 5c ). Hydrogen uptake amounted to 7.5 wt% H 2 within 500 min at 300 °C, in contrast to 5.0 wt% H 2 for LiBH 4 -Grs ( Supplementary Fig. 6 ) and zero for pristine LiBH 4 ( Fig. 5c ) under identical conditions. More encouragingly, Grs-10Ni-LiBH 4 reabsorbed ~8.1 wt% H 2 at 150 °C after a sufficient amount of time, which is nearly full hydrogenation ( Fig. 5d ). All these results indicate Ni nanoclusters favor the hydrogen cycling by LiBH 4 . In addition, it is worth highlighting that the hydrogenation onset temperature of 70 ºC is remarkably lower than that of 2–4 nm Ni-decorated LiBH 4 nanoparticles (5–10 nm) on graphene (125 °C) reported previously. 39 In contrast to the reported graphene-supported Ni-decorated LiBH 4 , 39 where LiBH 4 directly grow on graphene, herein LiBH 4 in the layer-by-layer assembled Grs-10Ni-LiBH 4 largely nucleates on Ni nanoclusters with less contact with graphene. As a result, the physical separation between LiBH 4 and graphene by Ni nanocluster layer is essential in facilitating the cleavage and formation of H-H and B-H bonds. The hydrogen cycling performance of Grs-10Ni-LiBH 4 was evaluated in isothermal mode ( Fig. 5e ). In contrast to pristine LiBH 4 , which displayed a rapid decay in the reversible capacity with only 40% remaining after 5 cycles, the reversible capacity of Grs-10Ni-LiBH 4 stayed at 8.1 wt% even after 30 cycles with negligible decay. Such superior cyclability is related to the stable morphology and nanostructure. As shown in Fig. 5f , the sample displayed the nearly same morphology after rehydrogenation and volume expansion was negligible for Grs-10Ni-LiBH 4 after dehydrogenation, which is completely different from pristine LiBH 4 ( Fig. 5g ). This is believed to be particularly favorable for stabilizing the hydrogen cycling ability. The desorption kinetics somewhat slowed down ( Supplementary Fig. 7 ), possibly due to the slight aggregation and growth in size ( Supplementary Fig. 8 ). The rate of decrease in reaction kinetics is still remarkably slower than that of the LiBH 4 -Grs ( Supplementary Fig. 7 ), further confirming the important role played by Ni nanoclusters in catalyzing hydrogen storage by LiBH 4 . Moreover, the Grs-10Ni-LiBH 4 sample delivered the fastest desorption kinetics for the 2 nd cycle of dehydrogenation ( Fig. 5h ). We further investigated the factors influencing the hydrogen storage reversibility in terms of morphology, nanostructure and composition. For Grs-10Ni-LiBH 4 nanocomposites, SEM observation revealed the stable macroscopic morphology featuring nanoparticles on the supports for both the dehydrogenated and the rehydrogenated samples ( Supplementary Fig. 9a - b ), confirming good morphological and nanostructural stability. This is in stark contrast to the Grs-6Ni-LiBH 4 and Grs-20Ni-LiBH 4 nanocomposites, which displayed the emergence of nanorods ( Supplementary Fig. 10 ), especially for their rehydrogenated samples ( Supplementary Fig. 10b , d ). This change makes the regenerated LiBH 4 break away from the Ni nanocluster layer, consequently losing catalytic activity. Moreover, metallic Ni was still identified by XPS after dehydrogenation and rehydrogenation at 300 ºC ( Supplementary Fig. 9 c ). FTIR results revealed the disappearance and reappearance of [BH 4 ] - group in LiBH 4 without any signs of [B 12 H 12 ] 2- ( Supplementary Fig. 9 d ), which was further confirmed by solid-state nuclear magnetic resonance (ss-NMR) spectra of 11 B ( Supplementary Fig. 9 e ). In addition, Ni-B species were not detected on the 300 ºC-dehydrogenated sample by XRD, XPS and NMR ( Supplementary Fig. 9c , e and 1 1 a ), but were observed in the 350 ºC-dehydrogenated sample ( Supplementary Fig. 11 a - b ), agreeing well with the previous report. 39 As a result, we believed that the stable trilayered nanostructure, small particle size, high catalytic activity, and effective separation of LiBH 4 from graphene are responsible for the significantly lowered operation temperatures and improved reversibility of Grs-10Ni-LiBH 4 prepared by layer-by-layer assembly. In the electronic analysis of Ni-B adsorption as shown in Fig. 6 a , we observed a significant accumulation of electrons at the Ni-B interface, primarily surrounding the B atoms. This electronic redistribution effectively compensates for the electron deficiency of the B clusters. At the same time, the electron transfer induced by Ni and the structural changes in B significantly affect the B-B bond. The crystal orbital Hamiltonian population method (COHP) analysis results ( Fig. 6 b-c ) indicate that the strength distribution of B-B bonding orbitals changes notably. Under the influence of Ni, the distribution of B-B bond strengths becomes more Gaussian, with both the average and minimum bond strengths decreasing. This facilitates the subsequent adsorption of H atoms onto B, eventually leading to the formation of the BH₄ group. Further partial density of states (PDOS) calculations in Fig. 6 d-f show that the adsorption of C on B leads to significant p -orbital hybridization, which causes the B valence band to shift away from the Fermi level. This shift is unfavorable for the electronic transfer during H atom adsorption. In contrast, the presence of Ni d -electrons reduces the electronic localization of B, enhancing the metallic character and electron-donating ability of the B atoms on the Ni surface. This provides an explanation for the observation, illustrated in Fig. 1 d , that Ni adsorption on B results in a reduction in the adsorption energy for the B atoms, in comparison to other systems. To investigate the hydrogen adsorption behavior of B clusters on the Ni surface, ab initio molecular dynamics (AIMD) simulations were performed at 500 K. Structural changes ( Supplementary Fig. 12 ) clearly reveal four distinct behaviors of H₂ within the system: H dissociation, hydrogen migration on the Ni surface, hydrogen migration from the Ni surface to the B surface, and H migration on the B surface (including migration of the B-H group). Transition state searches and kinetic energy barrier calculations for hydrogen adsorption were performed using the climbing-image nudged elastic band (CI-NEB) and improved dimer method (IDM) to quantitatively describe the enhanced hydrogen adsorption kinetics of B clusters on Ni. As shown in Fig 6g , the maximum thermodynamic energy change for hydrogen dissociation and migration on the Ni-B surface is -0.42 eV (H₂ dissociation on the Ni surface), with the highest reaction energy barrier being only 0.42 eV (H migration on the B surface). In contrast, for pure B cluster ( Fig 6h ), the H₂ dissociation and H migration processes exhibited a relatively low dissociation barrier of 0.48 eV, but involved a significant thermodynamic energy change of 3.18 eV. Furthermore, the H migration barrier for pure B clusters was as high as 2.90 eV, whereas for Ni-B, it was only 0.42 eV. This suggests that H atoms can migrate more easily on the B surface after dissociation, creating a chemical potential gradient that facilitates subsequent phase transition processes. Thus, the hydrogen overflow resulting from the direct contact between the Ni surface and B clusters, along with the separation of graphene and B clusters in the layered structure, leads to a reduction in the energy barriers for hydrogen dissociation and migration. This reduction in energy barriers is likely responsible for the improved hydrogen adsorption performance of the system. In summary, a trilayered nanostructured composite composed of graphene support layer, Ni nanocluster layer and LiBH 4 nanoparticle layer was fabricated by a layer-by-layer assembly strategy. Such unique trilayered nanostructure enables reversible storage of 12.27 wt% H 2 by LiBH 4 starting from 100 ºC for desorption and 70 ºC for absorption. More importantly, the dehydrogenated LiBH 4 can be nearly hydrogenated fully at 150 ºC under 100 bar H 2 . The Ni nanoclusters act as nucleation sites for LiBH 4 nanoparticles and also reduce the physical contact between LiBH 4 and the graphene support layer, favoring the recombination of B-H bonds and effectively eliminating the foaming upon thermal dehydrogenation. In particular, Ni can facilitate the cleavage of B clusters, thereby creating more hydrogen adsorption sites. The cleaved B clusters have weaker hydrogen adsorption energies, which significantly promotes the migration of hydrogen atoms on the B surface. In addition, the dissociation energy barrier for H 2 on the Ni surface is only 0.14 eV. These properties, which cannot be achieved by graphene, highlight the excellent role of Ni in the hydrogenation process by facilitating hydrogen splitting, adsorption and migration. Benefiting from unique trilayered nanostructure and high catalytic effectiveness, the significantly improved reversibility was also realized. This breakthrough sheds light on how to design light-metal borohydrides for practical hydrogen storage applications. However, the sluggish hydrogenation/dehydrogenation kinetics at low operating temperatures must be addressed before practical on-board hydrogen storage applications. Methods Materials and preparation Raw materials : Ni(NO 3 ) 2 ·6H 2 O (99.99%, Aladin), n-butyl lithium (C 4 H 9 Li, n-BuLi, 2.0 M in cyclohexane, Sigma-Aldrich), triethylamine borane ((C 2 H 5 ) 3 NBH 3 , 97%, Xiya), n-hexane (99%, Sinopharm Chemical Reagent Co.), few-layer graphene (99%, XFNano Inc.) and absolute ethanol (≥99.7, Sinopharm Chemical Reagent Co.) were purchased. Preparation of Grs - xNi : In a typical procedure, Ni(NO 3 ) 2 ·6H 2 O and few-layer graphene were ultrasonicated in 20 mL absolute ethanol for 20 min, and the mixture was then continuously stirred at 500 rpm for 8 hours at 60 °C. After stirring, the dry black powders were placed into a tubular furnace and heated at 400 °C for 2 hours with a ramp of 5 °C min -1 under 10% H 2 -90% Ar gas mixture at a flow rate of 30 mL min -1 . After natural cooling to room temperature, the final products named as graphene- x wt% Ni (Grs- x Ni) were obtained, where the x values are 0, 2, 6, 10 and 20. Preparation of Grs - xNi-LiBH 4 : The nanocomposites were synthesized via a hydrogen-assisted solvothermal reaction. Firstly, 30 mg of the as-prepared Grs- x Ni was mixed with 50 mL n-hexane. Then, 1.6 mL of 2.7 M C 4 H 9 Li solution (in hexane) and 645 μL of (C 2 H 5 ) 3 NBH 3 solution were added dropwise to the above solution under stirring. The mixture was exposed to ultrasonic waves generated by an ultrasonic horn with an output power of 600 W (20 kHz, FS600-N, SXSONIC Co., Ltd, Shanghai, China) in a Rosset cell. Ultrasonic waves were applied in the pulsed mode with cycles including 5 s pulses and 5 s relaxation, each lasting 30 minutes. After 4 cycles of ultrasound treatment, the mixture was then transferred into a 150 mL custom-made stainless-steel autoclave and heated at 100 °C for 3 h under 50 bar H 2 with constant stirring. After cooling to room temperature, the obtained products were collected by vacuum filtration, washed with n-hexane for several times, and dried at 90 °C through dynamic vacuum to remove triethylamine. The obtained samples were named as Grs- x Ni-LiBH 4 , x represents the mass ratio of Ni nanoparticles in the Grs-Ni support. Materials C haracterizations X-ray diffraction (XRD) characterizations were performed using a MiniFlex 600 diffractometer (Rigaku, Japan) with Cu Kα radiation (λ = 0.15406 nm, 40 kV and 15 mA). The XRD data were collected in a 0.05° increment between scattering angle of 10-90° (2θ) at room temperature. A custom-designed sample holder with a window covered by Scotch tape for transmission of X-ray was used to prevent the exposure to air. The FTIR spectra were recorded with a Bruker Tensor 27 unit (Germany) in the transmission mode. The test pellets were prepared by first mixing dried KBr with sample powders at a weight ratio of 200:1 and then cold pressing under 10 MPa. The spectra were created after 16 scans with 4 cm -1 of resolution. Scanning electron microscope (SEM, Hitachi SU8010) was employed to observe the morphologies. For SEM measurements, the powders were dispersed on electrically conducting adhesive tapes in a glove box and transferred into the SEM chamber under protective Ar using a custom holder. Transmission electron microscope (TEM) was performed using a HT-770 (Japan, Hitachi) TEM. For high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and energy-dispersive X-ray spectroscopy (EDS) examinations, the powders were dispersed on Cu grids which were then loaded in a double-tilt vacuum transfer holder (Gatan 648, USA and FEI Tecnai G2 F20 S-TWIN, USA). X-ray photoelectron spectroscopy (XPS) characterization was carried out on a photoelectron spectrometer (Thermo Scientific K-Alpha) with a monochromatic Al Kα (hν: 1486.6 eV) X-ray source and calibrated with the adventitious C peak at 284.8 eV as the reference. Solid-state 11 B and 7 Li magic angle spinning NMR analysis was performed on a Bruker AVANCE NEO 600WB spectrometer. The sample powders were packed into a SiO 2 NMR tube and sealed with a tightly fitted cap inside an Ar-filled glove box. The operating frequencies for 7 Li and 11 B were 233.34 and 192.64 MHz, respectively. The NMR shifts were reported in parts per million (ppm) referenced to BF 3 OEt 2 and LiClO 4 , respectively. Hydrogen cycling measurements A home-built temperature-programmed desorption (TPD) system attached to a mass spectrometer (MS) (Hiden QIC-20, England) was used for qualitative measurements of dehydrogenation, where pure Ar with a flow rate of 20 mL min -1 was used as a carrier gas. The sample was heated from room temperature to 600 °C at 2 °C min -1 . A custom-made Sievert’s-type equipment was used for the quantitative measurement under isothermal or non-isothermal conditions. Approximately 30 mg of sample was used for each measurement. The non-isothermal volumetric hydrogen release was conducted under primary vacuum (~ 10 -3 Torr) with the temperature ramping at 2 °C min -1 . The dehydrogenated sample was rehydrogenated from room temperature to 350 °C at a heating rate of 1 °C min -1 under 100 bar H 2 . The isothermal measurements were conducted by rapidly heating (10 °C min -1 ) the sample to a desired temperature, maintaining for a certain duration at this temperature. Thermal analysis was performed by differential scanning calorimetry (DSC) measurement on a NETZSCH DSC 200F3 unit. Approximately 2 mg of sample was loaded into an Al 2 O 3 crucible and heated from 30 °C to 600 °C at 2 °C min -1 . Theoretical calculations First-principles calculations were performed using the Vienna Ab initio Simulation Package (VASP). 47 The electronic and ionic interactions were described within the framework of the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. 48 Before selecting kinetic cut off energy and k-points grid, the extensive convergence test has been performed. The planewave basis-set cutoff was set to 500 eV, with convergence criteria of 10⁻⁵ eV for energy and 0.02 eV/Å for structural optimization forces. The Brillouin zones were sampled using 2×2×1 Monkhorst-Pack k-point meshes. A small B cluster was modeled using an octahedral cluster built from six B₁₂ units, and a Ni(110) surface with a 6×6 cubic cell containing four atomic layers was used as the slab model. Ab initio molecular dynamics (AIMD) simulations embedded in the VASP code were conducted using a time step of 1 fs in an NVT ensemble with a Nosé-Hoover thermostat. Simulations were run at 500 K to observe the dynamics of H atoms, with energy and force convergence set to 10 - ⁵ eV and 0.02 eV/Å, respectively. Transition states for hydrogen dissociation, adsorption, and migration were located using the climbing-image nudged elastic band (CI-NEB) method and the improved dimer method (IDM). 49-50 Bonding interactions were analyzed via the crystal orbital Hamilton population (COHP) method in the LOBSTER software package. 51-52 Declarations Data availability All data supporting the findings of this study are available within the article and its Supplementary Information files or available from the first authors and corresponding authors on reasonable request. Acknowledgements We gratefully acknowledge the financial support received from the National Outstanding Youth Foundation of China (52125104), the National Natural Science Foundation of China (52071285, 52001277), the Fundamental Research Funds for the Central Universities (226-2024-00075) and the National Youth Top-Notch Talent Support Program. W.X.Z. thanks Mrs. Na Zheng (State Key Laboratory of Chemical Engineering in Zhejiang University) for performing SEM. Author Contributions W.X.Z., X.Z., H.G.P. and Y.F.L. proposed the concept and designed the research. W.X.Z., X.Z. and Y.F.L. performed the experiments. C.Q.L. and G.L.X. performed the calculations. All authors contributed to the analyses and discussion of the results. W.X.Z., X.Z., Q.C.L., H.G.P. and Y.F.L. wrote the manuscript. Competing interests The authors declare no competing interests. Additional information Supplementary Information accompanies at http://www.nature.com/naturecommunications. Competing financial interests: The authors declare no competing financial interests. References Schlapbach, L. & Züttel, A. Hydrogen-storage materials for mobile applications. Nature 414 , 353-358 (2001). He, T., Pachfule, P., Wu, H., Xu, Q. & Chen, P. Hydrogen carriers. Nat. Rev. Mater. 1 , 16059 (2016). Krevor, S. et al. 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1","display":"","copyAsset":false,"role":"figure","size":298122,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCalculation of structural changes in Boron (B) and the corresponding Hydrogen (H) adsorption Energy. \u003c/strong\u003ea) The B\u003csub\u003e72\u003c/sub\u003e cluster structure consisting of B icosahedron. Adsorption structure of B\u003csub\u003e72\u003c/sub\u003e on b) graphene and c) Ni, respectively. The tangerine, gray, and blue spheres represent B, C, and Ni atoms respectively, while the pink and blue lines represent bonding between B atoms and between Ni atoms respectively. d) H adsorption energy at B sites in different coordination environments.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/fb0f6bcb24394e411f713e30.png"},{"id":82687571,"identity":"7214c8dc-7ada-44b7-be7d-2c36c5c852a1","added_by":"auto","created_at":"2025-05-14 07:09:53","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":869970,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePreparation and morphology of trilayered Grs-Ni-LiBH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanostructure.\u003c/strong\u003e a) Schematic illustration of the layer-by-layer assembly process, b-f) TEM images of the prepared Grs-\u003cem\u003ex\u003c/em\u003eNi, g-k) SEM images of the obtained Grs-\u003cem\u003ex\u003c/em\u003eNi-LiBH\u003csub\u003e4\u003c/sub\u003e nanostructure.\u003cem\u003e x\u003c/em\u003e in Grs-\u003cem\u003ex\u003c/em\u003eNi and Grs-\u003cem\u003ex\u003c/em\u003eNi-LiBH\u003csub\u003e4\u003c/sub\u003e are 0, 2, 6, 10 and 20, respectively.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/37968257920217396349758e.png"},{"id":82687919,"identity":"b79036c8-6732-487b-aac9-d25142d36648","added_by":"auto","created_at":"2025-05-14 07:17:53","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":868605,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMicroscopic studies on Grs-10Ni and Grs-10Ni-LiBH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e a) TEM image and corresponding EDS mapping of Grs-10Ni, b) TEM image and corresponding EDS mappings of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite, c) HRTEM image and corresponding SAED patterns of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/e32a04e7f9f9a426ae3aee23.png"},{"id":82687922,"identity":"3045e595-3b1b-426f-a889-3d9112ce9001","added_by":"auto","created_at":"2025-05-14 07:17:53","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":620885,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDehydrogenation performance of trilayered Grs-Ni-LiBH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanocomposites.\u003c/strong\u003e a) H\u003csub\u003e2\u003c/sub\u003e signals of TPD-MS, b) non-isothermal dehydrogenation curves of nano LiBH\u003csub\u003e4\u003c/sub\u003e and Grs-\u003cem\u003ex\u003c/em\u003eNi-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite, isothermal dehydrogenation curves of c) Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e and d) LiBH\u003csub\u003e4\u003c/sub\u003e-Grs nanocomposites, TPD curves under different heating rates and posted fitted Kissinger’s plots of e) Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e and f) LiBH\u003csub\u003e4\u003c/sub\u003e-Gr nanocomposites.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/a7e91b9430111bcd2e9c76fb.png"},{"id":82687578,"identity":"39c0d87a-dec1-4ab6-8095-1bca9d817452","added_by":"auto","created_at":"2025-05-14 07:09:53","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":588120,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eReversible hydrogen storage performance of Grs-Ni-LiBH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanocomposites.\u003c/strong\u003e a) Non-isothermal hydrogenation curves of nano LiBH\u003csub\u003e4\u003c/sub\u003e and Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite from room temperature to 350 °C, b) Comparison of onset hydrogenation temperature of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite with reported LiBH\u003csub\u003e4\u003c/sub\u003e systems, c) isothermal hydrogenation curves of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite and pristine LiBH\u003csub\u003e4\u003c/sub\u003e, d) isothermal hydrogenation curves of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite at 150 °C. e) the cycling performances of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e and pristine LiBH\u003csub\u003e4\u003c/sub\u003e, f) SEM, TEM images and corresponding EDS mappings of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e after rehydrogenation, g) digital images before (left) and after (right) dehydrogenation of pristine LiBH\u003csub\u003e4\u003c/sub\u003e and Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite, h) 2\u003csup\u003end\u003c/sup\u003e isothermal hydrogenation curves of Grs-\u003cem\u003ex\u003c/em\u003eNi-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/8ee9a1991f4603fe3ac0dac2.png"},{"id":82687574,"identity":"8f4b97a4-6e08-492b-9828-71dd8075ffe9","added_by":"auto","created_at":"2025-05-14 07:09:53","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":631238,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAnalysis of the electronic structure of C-Ni-B and the hydrogen dynamics on the Ni-B surface. \u003c/strong\u003ea) Charge density difference of Ni adsorbed B cluster with an isovalue of 0.01 e/Bohr\u003csup\u003e3\u003c/sup\u003e. The distribution of crystal orbital Hamiltonian population (COHP) integral values for B-B bonds in B clusters b) before and c) after Ni adsorption. Partial density of states (PDOS) for the d) B cluster and individual B atoms after adsorption on e) graphene and f) Ni surfaces. Relative energies and structures of hydrogen dissociation and migration on g) the Ni-B surface and h) the pure B cluster surface. The tangerine, white, and blue spheres represent B, H, and Ni atoms, respectively.\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/57e775dc401415533c5916c8.png"},{"id":107695709,"identity":"2981a4f0-7070-466e-bc31-038dfcc32e66","added_by":"auto","created_at":"2026-04-24 07:07:48","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4350579,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/e9f94922-efd6-435f-932d-43c445968f51.pdf"},{"id":82687570,"identity":"07f9ca68-301b-4f3f-8961-9ac2869e8e7c","added_by":"auto","created_at":"2025-05-14 07:09:53","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2523465,"visible":true,"origin":"","legend":"Supplementary information","description":"","filename":"SupplementaryInformation20250504.docx","url":"https://assets-eu.researchsquare.com/files/rs-5744222/v1/695505fced8dce280186db56.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eReversibly storing over 12 wt% H\u003csub\u003e2\u003c/sub\u003e by a trilayered lithium borohydride nanocomposite commencing from 70ºC\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eHydrogen storage in lithium borohydride (LiBH\u003csub\u003e4\u003c/sub\u003e) with high gravimetric and volumetric hydrogen densities has attracted intensive research interest. However, the high working temperatures and poor reversibility due to the high thermodynamic stability and kinetic barriers, limits its practical applications. Herein, we fabricate a unique trilayered nanostructure composed of layers of graphene support, Ni nanoclusters, and LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles, through a layer-by-layer assembly approach. The Ni nanoclusters offer nucleation sites, separate LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles from graphene, catalyze the formation of B-H bonds and eliminate the foaming effect. During hydrogenation, Ni cleaves H-H bonds and B clusters, creating additional hydrogen absorption sites and reducing the H adsorption energy of B, which lowers the hydrogen dissociation barrier, allowing reversible storage of approximately 12.27 wt% H\u003csub\u003e2\u003c/sub\u003e by LiBH\u003csub\u003e4\u003c/sub\u003e commencing from 70 \u0026ordm;C under 100 bar H\u003csub\u003e2\u003c/sub\u003e. This finding guides the design and fabrication of light-metal hydride nanostructures for practical on-board hydrogen storage applications.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo power a sustainable civilization, hydrogen is a desirable alternative to conventional fossil fuels.\u003csup\u003e1-3\u003c/sup\u003e However, lack of safe, efficient, and economical hydrogen storage methods remains a roadblock to the wide use of hydrogen as a fuel.\u003csup\u003e4-6\u003c/sup\u003e Special attention has been paid to materials-based hydrogen storage, and among the choices, LiBH\u003csub\u003e4\u003c/sub\u003e with extremely high gravimetric (18.5 wt%) and volumetric (121 kg m\u003csup\u003e-3\u003c/sup\u003e) hydrogen densities has received intensive research interest.\u003csup\u003e7-9\u003c/sup\u003e However, high thermodynamic stability and kinetic barrier lead to high temperatures for reversible hydrogen storage by LiBH\u003csub\u003e4\u003c/sub\u003e.\u003csup\u003e10-11\u003c/sup\u003e A variety of strategies have been proposed to improve the hydrogen storage performance of LiBH\u003csub\u003e4\u003c/sub\u003e, including substitution of anions or cations,\u003csup\u003e12-15\u003c/sup\u003e formation of reactive composites,\u003csup\u003e16-19\u003c/sup\u003e catalysts\u003csup\u003e20-24\u003c/sup\u003e and nanostructuring.\u003csup\u003e25-39\u003c/sup\u003e In particular, the reduction of particle size to nanoscale through nanostructuring has proven very effective in lowering the operating temperatures and improving the reversibility of hydrogen cycling.\u003c/p\u003e\n\u003cp\u003eNanoconfinement is the most frequently used technique to increase specific surface areas, generate more boundaries and defects, all of which shorten mass transport path, accelerate desorption, and lower dehydrogenation temperatures compared to their bulk counterparts.\u003csup\u003e25-\u003c/sup\u003e\u003csup\u003e39\u003c/sup\u003e In 2009, Cahen et al. loaded 33 wt% LiBH\u003csub\u003e4\u003c/sub\u003e into 4 nm-sized mesoporous carbon by solution impregnation in ethers.\u003csup\u003e26\u003c/sup\u003e Nanosized LiBH\u003csub\u003e4\u003c/sub\u003e displayed enhanced desorption kinetics with 3.4 wt% of hydrogen release within 90 min at 300 \u0026ordm;C. The encapsulation of LiBH\u003csub\u003e4\u003c/sub\u003e into carbon cages via melt infiltration induced remarkable reductions in operation temperatures since the hydrogen desorption commenced from 200 \u0026ordm;C and peaked at 320 \u0026ordm;C, and rehydrogenation was completed at 400 \u0026ordm;C under 50 bar H\u003csub\u003e2\u003c/sub\u003e. The desorption kinetics was further improved by using porous materials mixed with metal/metal oxides as host materials, especially for Ni decorated scaffolds.\u003csup\u003e29-35\u003c/sup\u003e The onset temperature for H\u003csub\u003e2\u003c/sub\u003e desorption was decreased to 250 \u0026deg;C after confining LiBH\u003csub\u003e4\u003c/sub\u003e into a porous carbon scaffold\u0026nbsp;decorated with Ni nanoparticles.\u003csup\u003e31\u003c/sup\u003e The use of porous hollow carbon microspheres composed of carbon-coated Ni nanoparticles as scaffolds induced the release of 4 wt% H\u003csub\u003e2\u003c/sub\u003e within 30 min at 300 \u0026ordm;C.\u003csup\u003e32\u003c/sup\u003e Rehydrogenation was also significantly enhanced through adding Ni into the nanoporous carbon-confined LiBH\u003csub\u003e4\u003c/sub\u003e.\u003csup\u003e36\u003c/sup\u003e Alternatively, the use of graphene as a support improved the LiBH\u003csub\u003e4\u003c/sub\u003e loading up to 70 wt% because of low weight and high specific surface area.\u003csup\u003e37\u003c/sup\u003e Similarly, the peak dehydrogenation temperature was reduced to 346 \u0026deg;C from 470 \u0026deg;C when assembling 2-nm thick LiBH\u003csub\u003e4\u003c/sub\u003e on graphene with 69.1 wt% loading.\u003csup\u003e38\u003c/sup\u003e The Ni nanocrystals of 2-4 nm in size enabled graphene-supported LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles of 5-10 nm in size to reversibly desorb and absorb ~9.2 wt% H\u003csub\u003e2\u003c/sub\u003e at 300 \u0026deg;C up to 100 cycles.\u003csup\u003e39\u003c/sup\u003e However, the onset temperature for hydrogen uptake was measured to be 125 \u0026deg;C under 100 bar H\u003csub\u003e2\u003c/sub\u003e, which cannot be met by the waste heat from hydrogen fuel cells on board.\u003csup\u003e40\u003c/sup\u003e There remains a huge challenge to achieve such a breakthrough.\u003c/p\u003e\n\u003cp\u003eTo understand underlying reasons,\u0026nbsp;we first conducted density functional theory (DFT) calculations to investigate the hydrogen adsorption behavior of B on different substrates and catalytic supports. The B₇₂ cluster (\u003cstrong\u003eFig. 1a\u003c/strong\u003e) and its adsorption configurations on C (\u003cstrong\u003eFig. 1b\u003c/strong\u003e) and Ni surfaces (\u003cstrong\u003eFig. 1c)\u0026nbsp;\u003c/strong\u003ewere optimized. The results reveal significant structural reorganization of the B cluster on the Ni surface, with partial B-B bond dissociation and adsorption at Ni hollow sites. In contrast, the interaction between B and the C substrate appears weaker, which could alter the hydrogen adsorption pathway and capability on B.\u0026nbsp;Subsequent calculations of hydrogen adsorption energies (\u003cem\u003eE\u003csub\u003eads\u003c/sub\u003e\u003c/em\u003e) on B atoms in various coordination environments showed distinct behaviors.\u0026nbsp;The hydrogen adsorption energy (\u003cem\u003eE\u003csub\u003eads\u003c/sub\u003e\u003c/em\u003e) was calculated using the following formula:\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003c/p\u003e\n\u003cp\u003ewhere \u003cem\u003eE\u003csub\u003etotal\u003c/sub\u003e\u003c/em\u003e is the optimal energy for the total structure of the H atom after adsorption on the surface, and \u003cem\u003eE\u003csub\u003esystem\u003c/sub\u003e\u003c/em\u003e and \u003cem\u003eE\u003csub\u003eH2\u003c/sub\u003e\u003c/em\u003e are the optimal energies for the adsorption system and the individual hydrogen molecule, respectively. As shown in\u0026nbsp;\u003cstrong\u003eFig. 1d\u003c/strong\u003e and \u003cstrong\u003eSupplementary Table\u003c/strong\u003e \u003cstrong\u003e1\u003c/strong\u003e, two specific B sites exhibit the weakest (B2, \u003cem\u003eE\u003csub\u003eads\u003c/sub\u003e\u003c/em\u003e = 0.97 eV) and strongest (B1, \u003cem\u003eE\u003csub\u003eads\u003c/sub\u003e\u003c/em\u003e = -1.80 eV) hydrogen adsorption strengths within the pure B cluster. B atoms\u0026nbsp;affected by C or Ni show weakened but still negative hydrogen adsorption energies, suggesting that H atoms can more readily adsorb/migrate to additional B sites and desorb or migrate after the reaction. Moreover, the structural breakdown of the B icosahedron on the Ni surface increases the availability of adsorption sites for H, while C tends to occupy adsorption sites, potentially hindering H migration on the B surface. This suggests that a layered assembly of C and B, designed to separate the two, could substantially enhance hydrogen adsorption performance while maintaining the benefits of graphene nanoconfinement and Ni catalysis.\u003c/p\u003e\n\u003cp\u003eIn terms of calculations, we designed and fabricated\u0026nbsp;a unique trilayered LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposite through a layer-by-layer assembly process as illustrated in \u003cstrong\u003eFig. 2\u003c/strong\u003ea. Here, the Ni nanocluster-decorated graphene (denoted as Grs-Ni) was first synthesized via heating a mixture of Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO and few-layer graphene at 400 \u0026deg;C under Ar/H\u003csub\u003e2\u003c/sub\u003e. Transmission electron microscope (TEM) observation (\u003cstrong\u003eFig. 2\u003c/strong\u003eb-f) indicated that Ni particles emerged on graphene and gradually increased in quantity and in size. X-ray diffraction (XRD) profiles prove the formation of cubic metallic Ni (PDF: 04-0850) (\u003cstrong\u003eSupplementary Fig. 1\u003c/strong\u003ea). Further X-ray photoelectron spectroscopy (XPS) analysis confirms the presence of metallic Ni (\u003cstrong\u003eSupplementary Fig. 1\u003c/strong\u003eb), and its particle size is less than 5 nm as in TEM images (\u003cstrong\u003eSupplementary Fig. 1\u003c/strong\u003ec), by taking Grs-10 wt% Ni (labelled as Grs-10Ni) as the representative sample. Subsequently, the graphene-Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanostructure (denoted as Grs-Ni-LiBH\u003csub\u003e4\u003c/sub\u003e) was prepared by reacting n-butyl lithium (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eLi, \u003cem\u003en\u003c/em\u003e-BuLi) and triethylamine borane ((C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003eNBH\u003csub\u003e3\u003c/sub\u003e, Et\u003csub\u003e3\u003c/sub\u003eN∙BH\u003csub\u003e3\u003c/sub\u003e) in n-hexane under 50 bar H\u003csub\u003e2\u003c/sub\u003e using the prepared Grs-Ni as supports. After filtration, washing and drying, solid Grs-Ni-LiBH\u003csub\u003e4\u003c/sub\u003e powders were obtained. Here, Grs-Ni as the support was set to be 30 wt% of the resultant product. The characteristic diffraction peaks of LiBH\u003csub\u003e4\u003c/sub\u003e (PDF: 01-081-9182) were clearly identified in all samples by XRD (\u003cstrong\u003eSupplementary Fig. 2\u003c/strong\u003ea). Fourier transform infrared (FTIR) examination indicates the B-H vibrations of LiBH\u003csub\u003e4\u003c/sub\u003e at 2390, 2291, 2221 and 1122 cm\u003csup\u003e-1\u003c/sup\u003e (\u003cstrong\u003eSupplementary Fig. 2\u003c/strong\u003eb). Scanning electron microscope (SEM) observation (\u003cstrong\u003eFig. 2\u003c/strong\u003eg-k) displays plenty of nanoparticles on the sample surface. In comparison with pristine graphene (\u003cstrong\u003eFig. 2\u003c/strong\u003eg), the presence of nanoparticulate Ni facilitate the growth of LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles (\u003cstrong\u003eFig. 2\u003c/strong\u003eh and i), especially for the Grs-6Ni sample (\u003cstrong\u003eFig. 2\u003c/strong\u003ei). This fact indicates that the nanosized Ni favors the nucleation and growth of LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles. Further increasing the Ni content to 10 wt% and 20 wt% led to more and much smaller LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles (\u003cstrong\u003eFig. 2\u003c/strong\u003ej-k), which can be explained by the increased nucleation facilitated by nanoparticulate Ni. Comparison revealed that the Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e sample, composed of 70 wt% LiBH\u003csub\u003e4\u003c/sub\u003e and 27 wt% Grs and 3 wt% Ni, delivers relatively smaller particles and much more uniform distribution.\u003c/p\u003e\n\u003cp\u003eThe layer-by-layer assembly nanostructure was further studied by TEM, energy dispersive spectroscopy (EDS), high-resolution TEM (HRTEM) and selected area electron diffraction (SAED) (\u003cstrong\u003eFig.\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e3\u003c/strong\u003e), by comparing the Grs-10Ni and the Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e. As observed in the TEM image and corresponding EDS mapping, the Grs-10Ni sample shows that ~2-5 nm-sized metallic Ni particles anchored on the surface of graphene (\u003cstrong\u003eFig. 3a\u003c/strong\u003e). In comparison, there is a strong correlation in special distribution of LiBH\u003csub\u003e4\u003c/sub\u003e and Ni in Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e, indicating that LiBH\u003csub\u003e4\u003c/sub\u003e covers the nanocluster Ni layer of the Grs-10Ni (\u003cstrong\u003eFig. 3b\u003c/strong\u003e). Further HRTEM and SAED results indicate the significant difference between Area 1 and 2 (\u003cstrong\u003eFig. 3c\u003c/strong\u003e). The interplanar spacings of the (311) facet of Ni, the (020) facet of LiBH\u003csub\u003e4\u003c/sub\u003e and the (1\u003cruby\u003e1\u003crp\u003e(\u003c/rp\u003e\n \u003crt\u003e-\u003c/rt\u003e\n \u003crp\u003e)\u003c/rp\u003e\n \u003c/ruby\u003e00) facet of graphene were clearly detected in Area 1. However, only Ni and graphene were identified in Area 2. The synthesized LiBH\u003csub\u003e4\u003c/sub\u003e particles was measured to be 40-80 nm in size. Thus, the obtained Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e sample displays a distinct trilayer nanostructure, composed of a graphene support layer, a nanocluster Ni layer and a nanoparticulate LiBH\u003csub\u003e4\u003c/sub\u003e layer.\u003c/p\u003e\n\u003cp\u003eThe resultant trilayered nanocomposites were subjected to hydrogen desorption/absorption measurements in isothermal and non-isothermal modes. As shown in \u003cstrong\u003eFig. 4\u003c/strong\u003e\u003cstrong\u003ea-c\u003c/strong\u003e, the presence of Ni nanoclusters contributed a noticeable decrease in the dehydrogenation temperature of LiBH\u003csub\u003e4\u003c/sub\u003e. The dehydrogenation peak temperature was lowered from 360 \u0026deg;C to 330 \u0026deg;C when increasing \u003cem\u003ex\u003c/em\u003e in the Grs-\u003cem\u003ex\u003c/em\u003eNi from 0 to 10 wt%, which is 105 \u0026deg;C lower than that of pristine LiBH\u003csub\u003e4\u003c/sub\u003e (435 \u0026deg;C) (\u003cstrong\u003eFig. 4a\u003c/strong\u003e). While further increasing \u003cem\u003ex\u003c/em\u003e to 20 wt%, the desorption curve maintained nearly unchanged. The reduction in the desorption temperatures was also confirmed by differential scanning calorimetry (DSC) examination (\u003cstrong\u003eSupplementary Fig. 3\u003c/strong\u003e). In contrast to pristine LiBH\u003csub\u003e4\u003c/sub\u003e, no obvious melting endothermic peak was observed for the Grs-\u003cem\u003ex\u003c/em\u003eNi-containing samples, especially for the Grs-10Ni sample. The desorption hydrogen quantity of the Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e sample was measured by a volumetric method to be 7.4 wt% with respect to the whole nanocomposite after being heated to 368 \u0026deg;C, with an onset temperature of 100 \u0026deg;C (\u003cstrong\u003eFig. 4b\u003c/strong\u003e). It corresponds to ~10.5 wt% of H\u003csub\u003e2\u003c/sub\u003e from LiBH\u003csub\u003e4\u003c/sub\u003e since graphene and Ni releases no hydrogen, which is nearly 4 times that of pristine LiBH\u003csub\u003e4\u003c/sub\u003e (~2.7 wt%) under identical conditions. Isothermal examination revealed much faster hydrogen release from Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e than that of pristine LiBH\u003csub\u003e4\u003c/sub\u003e and LiBH\u003csub\u003e4\u003c/sub\u003e-Grs samples. At 350 \u0026deg;C, approximately 8 wt% of H\u003csub\u003e2\u003c/sub\u003e was released within 35 min (~11.4 wt% H\u003csub\u003e2\u003c/sub\u003e/LiBH\u003csub\u003e4\u003c/sub\u003e), while the pristine LiBH\u003csub\u003e4\u003c/sub\u003e only liberated ~1.7 wt% of H\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eFig. 4c\u003c/strong\u003e). When operating at 300 \u0026deg;C, the average desorption rate of the Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e was also twice that of the LiBH\u003csub\u003e4\u003c/sub\u003e-Grs sample as it released approximately 6.5 wt% of H\u003csub\u003e2\u003c/sub\u003e within 100 min, in contrast to 3.2 wt% from the Grs-LiBH\u003csub\u003e4\u003c/sub\u003e sample (\u003cstrong\u003eFig. 4d\u003c/strong\u003e). The desorption activation energy was calculated to be 108.0 \u0026plusmn; 6.0 kJ mol\u003csup\u003e-1\u003c/sup\u003e for Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003eFig. 4e\u003c/strong\u003e), reduced by approximately 40% and 7% with respect to pristine sample (182 \u0026plusmn; 3.5 kJ mol\u003csup\u003e-1\u003c/sup\u003e) (\u003cstrong\u003eSupplementary Fig. 4\u003c/strong\u003e) and Grs-LiBH\u003csub\u003e4\u003c/sub\u003e (116 \u0026plusmn; 2.9 kJ mol\u003csup\u003e-1\u003c/sup\u003e) (Fig. 3f), respectively. These results indicated unambiguously the important role of Ni in catalyzing hydrogen desorption from LiBH\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eRehydrogenation of the dehydrogenated samples as a function of temperature was conducted under 100 bar H\u003csub\u003e2\u003c/sub\u003e. The presence of Ni nanoclusters distinctly reduced the rehydrogenation onset temperature of the dehydrogenated LiBH\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003eFig. 5a\u003c/strong\u003e). The optimal composition is Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e because it started taking up hydrogen from 70 \u0026deg;C, which is ~245 \u0026deg;C lower than that of dehydrogenated pristine LiBH\u003csub\u003e4\u003c/sub\u003e (315 \u0026deg;C). To the best of our knowledge, this is the lowest onset hydrogenation temperature for LiBH\u003csub\u003e4\u003c/sub\u003e-based hydrogen storage materials (\u003cstrong\u003eFig. 5b\u003c/strong\u003e). The total hydrogen uptake amounted to 8.2 wt% upon heating to and dwelling at 350 \u0026deg;C (\u003cstrong\u003eSupplementary Fig. 5\u003c/strong\u003e), corresponding to ~12.27 wt% H\u003csub\u003e2\u003c/sub\u003e by LiBH\u003csub\u003e4\u003c/sub\u003e. Isothermal measurements indicated that the hydrogenation was completed within 300 min at 350 \u0026deg;C under 100 bar H\u003csub\u003e2\u003c/sub\u003e by the dehydrogenated Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003eFig. 5c\u003c/strong\u003e). Hydrogen uptake amounted to 7.5 wt% H\u003csub\u003e2\u003c/sub\u003e within 500 min at 300 \u0026deg;C, in contrast to 5.0 wt% H\u003csub\u003e2\u003c/sub\u003e for LiBH\u003csub\u003e4\u003c/sub\u003e-Grs (\u003cstrong\u003eSupplementary Fig. 6\u003c/strong\u003e) and zero for pristine LiBH\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003eFig. 5c\u003c/strong\u003e) under identical conditions. More encouragingly, Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e reabsorbed ~8.1 wt% H\u003csub\u003e2\u003c/sub\u003e at 150 \u0026deg;C after a sufficient amount of time, which is nearly full hydrogenation (\u003cstrong\u003eFig. 5d\u003c/strong\u003e). All these results indicate Ni nanoclusters favor the hydrogen cycling by LiBH\u003csub\u003e4\u003c/sub\u003e. In addition, it is worth highlighting that the hydrogenation onset temperature of 70 \u0026ordm;C is remarkably lower than that of 2\u0026ndash;4 nm Ni-decorated LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles (5\u0026ndash;10 nm) on graphene (125 \u0026deg;C) reported previously.\u003csup\u003e39\u003c/sup\u003e In contrast to the reported graphene-supported Ni-decorated LiBH\u003csub\u003e4\u003c/sub\u003e,\u003csup\u003e39\u003c/sup\u003e where LiBH\u003csub\u003e4\u003c/sub\u003e directly grow on graphene, herein LiBH\u003csub\u003e4\u003c/sub\u003e in the layer-by-layer assembled Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e largely nucleates on Ni nanoclusters with less contact with graphene. As a result, the physical separation between LiBH\u003csub\u003e4\u003c/sub\u003e and graphene by Ni nanocluster layer is essential in facilitating the cleavage and formation of H-H and B-H bonds.\u003c/p\u003e\n\u003cp\u003eThe hydrogen cycling performance of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e was evaluated in isothermal mode (\u003cstrong\u003eFig. 5e\u003c/strong\u003e). In contrast to pristine LiBH\u003csub\u003e4\u003c/sub\u003e, which displayed a rapid decay in the reversible capacity with only 40% remaining after 5 cycles, the reversible capacity of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e stayed at 8.1 wt% even after 30 cycles with negligible decay. Such superior cyclability is related to the stable morphology and nanostructure. As shown in \u003cstrong\u003eFig. 5f\u003c/strong\u003e, the sample displayed the nearly same morphology after rehydrogenation and volume expansion was negligible for Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e after dehydrogenation, which is completely different from pristine LiBH\u003csub\u003e4\u003c/sub\u003e (\u003cstrong\u003eFig. 5g\u003c/strong\u003e). This is believed to be particularly favorable for stabilizing the hydrogen cycling ability. The desorption kinetics somewhat slowed down (\u003cstrong\u003eSupplementary Fig. 7\u003c/strong\u003e), possibly due to the slight aggregation and growth in size (\u003cstrong\u003eSupplementary Fig. 8\u003c/strong\u003e). The rate of decrease in reaction kinetics is still remarkably slower than that of the LiBH\u003csub\u003e4\u003c/sub\u003e-Grs (\u003cstrong\u003eSupplementary Fig. 7\u003c/strong\u003e), further confirming the important role played by Ni nanoclusters in catalyzing hydrogen storage by LiBH\u003csub\u003e4\u003c/sub\u003e. Moreover, the Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e sample delivered the fastest desorption kinetics for the 2\u003csup\u003end\u003c/sup\u003e cycle of dehydrogenation (\u003cstrong\u003eFig. 5h\u003c/strong\u003e).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWe further investigated the factors influencing the hydrogen storage reversibility in terms of morphology, nanostructure and composition. For Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposites, SEM observation revealed the stable macroscopic morphology featuring nanoparticles on the supports for both the dehydrogenated and the rehydrogenated samples (\u003cstrong\u003eSupplementary\u003c/strong\u003e \u003cstrong\u003eFig. 9a\u003c/strong\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e), confirming good morphological and nanostructural stability. This is in stark contrast to the Grs-6Ni-LiBH\u003csub\u003e4\u003c/sub\u003e and Grs-20Ni-LiBH\u003csub\u003e4\u003c/sub\u003e nanocomposites, which displayed the emergence of nanorods (\u003cstrong\u003eSupplementary Fig. 10\u003c/strong\u003e), especially for their rehydrogenated samples (\u003cstrong\u003eSupplementary Fig. 10b\u003c/strong\u003e\u003cstrong\u003e,\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e). This change makes the regenerated LiBH\u003csub\u003e4\u003c/sub\u003e break away from the Ni nanocluster layer, consequently losing catalytic activity. Moreover, metallic Ni was still identified by XPS after dehydrogenation and rehydrogenation at 300 \u0026ordm;C (\u003cstrong\u003eSupplementary\u003c/strong\u003e \u003cstrong\u003eFig. 9\u003c/strong\u003e\u003cstrong\u003ec\u003c/strong\u003e). FTIR results revealed the disappearance and reappearance of [BH\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e-\u003c/sup\u003e group in LiBH\u003csub\u003e4\u003c/sub\u003e without any signs of [B\u003csub\u003e12\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e]\u003csup\u003e2-\u003c/sup\u003e (\u003cstrong\u003eSupplementary\u003c/strong\u003e \u003cstrong\u003eFig. 9\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e), which was further confirmed by solid-state nuclear magnetic resonance (ss-NMR) spectra of \u003csup\u003e11\u003c/sup\u003eB (\u003cstrong\u003eSupplementary\u003c/strong\u003e \u003cstrong\u003eFig. 9\u003c/strong\u003e\u003cstrong\u003ee\u003c/strong\u003e). In addition, Ni-B species were not detected on the 300 \u0026ordm;C-dehydrogenated sample by XRD, XPS and NMR (\u003cstrong\u003eSupplementary Fig. 9c\u003c/strong\u003e\u003cstrong\u003e,\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ee and 1\u003c/strong\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e), but were observed in the 350 \u0026ordm;C-dehydrogenated sample (\u003cstrong\u003eSupplementary Fig. 11\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e), agreeing well with the previous report.\u003csup\u003e39\u003c/sup\u003e As a result, we believed that the stable trilayered nanostructure, small particle size, high catalytic activity, and effective separation of LiBH\u003csub\u003e4\u003c/sub\u003e from graphene are responsible for the significantly lowered operation temperatures and improved reversibility of Grs-10Ni-LiBH\u003csub\u003e4\u003c/sub\u003e prepared by layer-by-layer assembly.\u003c/p\u003e\n\u003cp\u003eIn the electronic analysis of Ni-B adsorption as shown in \u003cstrong\u003eFig. 6\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e, we observed a significant accumulation of electrons at the Ni-B interface, primarily surrounding the B atoms. This electronic redistribution effectively compensates for the electron deficiency of the B clusters. At the same time, the electron transfer induced by Ni and the structural changes in B significantly affect the B-B bond. The crystal orbital Hamiltonian population method (COHP) analysis results (\u003cstrong\u003eFig. 6\u003c/strong\u003e\u003cstrong\u003eb-c\u003c/strong\u003e) indicate that the strength distribution of B-B bonding orbitals changes notably. Under the influence of Ni, the distribution of B-B bond strengths becomes more Gaussian, with both the average and minimum bond strengths decreasing. This facilitates the subsequent adsorption of H atoms onto B, eventually leading to the formation of the BH₄ group. Further partial density of states (PDOS) calculations in \u003cstrong\u003eFig. 6\u003c/strong\u003e\u003cstrong\u003ed-f\u003c/strong\u003e show that the adsorption of C on B leads to significant \u003cem\u003ep\u003c/em\u003e-orbital hybridization, which causes the B valence band to shift away from the Fermi level. This shift is unfavorable for the electronic transfer during H atom adsorption. In contrast, the presence of Ni \u003cem\u003ed\u003c/em\u003e-electrons reduces the electronic localization of B, enhancing the metallic character and electron-donating ability of the B atoms on the Ni surface. This provides an explanation for the observation, illustrated in\u003cstrong\u003e\u0026nbsp;Fig. 1\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e, that Ni adsorption on B results in a reduction in the adsorption energy for the B atoms, in comparison to other systems.\u003c/p\u003e\n\u003cp\u003eTo investigate the hydrogen adsorption behavior of B clusters on the Ni surface, \u003cem\u003eab\u003c/em\u003e \u003cem\u003einitio\u003c/em\u003e molecular dynamics (AIMD) simulations were performed at 500 K. Structural changes (\u003cstrong\u003eSupplementary Fig. 12\u003c/strong\u003e) clearly reveal four distinct behaviors of H₂ within the system: H dissociation, hydrogen migration on the Ni surface, hydrogen migration from the Ni surface to the B surface, and H migration on the B surface (including migration of the B-H group). Transition state searches and kinetic energy barrier calculations for hydrogen adsorption were performed using the climbing-image nudged elastic band (CI-NEB) and improved dimer method (IDM) to quantitatively describe the enhanced hydrogen adsorption kinetics of B clusters on Ni. As shown in \u003cstrong\u003eFig 6g\u003c/strong\u003e, the maximum thermodynamic energy change for hydrogen dissociation and migration on the Ni-B surface is -0.42 eV (H₂ dissociation on the Ni surface), with the highest reaction energy barrier being only 0.42 eV (H migration on the B surface). In contrast, for pure B cluster (\u003cstrong\u003eFig 6h\u003c/strong\u003e), the H₂ dissociation and H migration processes exhibited a relatively low dissociation barrier of 0.48 eV, but involved a significant thermodynamic energy change of 3.18 eV. Furthermore, the H migration barrier for pure B clusters was as high as 2.90 eV, whereas for Ni-B, it was only 0.42 eV. This suggests that H atoms can migrate more easily on the B surface after dissociation, creating a chemical potential gradient that facilitates subsequent phase transition processes. Thus, the hydrogen overflow resulting from the direct contact between the Ni surface and B clusters, along with the separation of graphene and B clusters in the layered structure, leads to a reduction in the energy barriers for hydrogen dissociation and migration. This reduction in energy barriers is likely responsible for the improved hydrogen adsorption performance of the system.\u003c/p\u003e\n\u003cp\u003eIn summary, a\u0026nbsp;trilayered nanostructured composite composed of graphene support layer, Ni nanocluster layer and LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticle layer was fabricated by a layer-by-layer assembly strategy. Such unique trilayered nanostructure enables reversible storage of 12.27 wt% H\u003csub\u003e2\u003c/sub\u003e by LiBH\u003csub\u003e4\u003c/sub\u003e starting from 100 \u0026ordm;C for desorption and 70 \u0026ordm;C for absorption. More importantly, the dehydrogenated LiBH\u003csub\u003e4\u003c/sub\u003e can be nearly hydrogenated fully at 150 \u0026ordm;C under 100 bar H\u003csub\u003e2\u003c/sub\u003e. The Ni nanoclusters act as nucleation sites for LiBH\u003csub\u003e4\u003c/sub\u003e nanoparticles and also reduce the physical contact between LiBH\u003csub\u003e4\u003c/sub\u003e and the graphene support layer, favoring the recombination of B-H bonds and effectively eliminating the foaming upon thermal dehydrogenation. In particular, Ni can facilitate the cleavage of B clusters, thereby creating more hydrogen adsorption sites. The cleaved B clusters have weaker hydrogen adsorption energies, which significantly promotes the migration of hydrogen atoms on the B surface. In addition, the dissociation energy barrier for H\u003csub\u003e2\u003c/sub\u003e on the Ni surface is only 0.14 eV. These properties, which cannot be achieved by graphene, highlight the excellent role of Ni in the hydrogenation process by facilitating hydrogen splitting, adsorption and migration. Benefiting from unique trilayered nanostructure and high catalytic effectiveness, the significantly improved reversibility was also realized. This breakthrough sheds light on how to design light-metal borohydrides for practical hydrogen storage applications. However, the sluggish hydrogenation/dehydrogenation kinetics at low operating temperatures must be addressed before practical on-board hydrogen storage applications.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eMaterials and preparation\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cem\u003eRaw materials\u003c/em\u003e: Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO (99.99%, Aladin), n-butyl lithium (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eLi, n-BuLi, 2.0 M in cyclohexane, Sigma-Aldrich), triethylamine borane ((C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003eNBH\u003csub\u003e3\u003c/sub\u003e, 97%, Xiya), n-hexane (99%, Sinopharm Chemical Reagent Co.), few-layer graphene (99%, XFNano Inc.) and absolute ethanol (\u0026ge;99.7, Sinopharm Chemical Reagent Co.) were purchased.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003ePreparation of Grs\u003c/em\u003e\u003cem\u003e-\u003c/em\u003e\u003cem\u003exNi\u003c/em\u003e: In a typical procedure, Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO and few-layer graphene were ultrasonicated in 20 mL absolute ethanol for 20 min, and the mixture was then continuously stirred at 500 rpm for 8 hours at 60 \u0026deg;C. After stirring, the dry black powders were placed into a tubular furnace and heated at 400 \u0026deg;C for 2 hours with a ramp of 5 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e under 10% H\u003csub\u003e2\u003c/sub\u003e-90% Ar gas mixture at a flow rate of 30 mL min\u003csup\u003e-1\u003c/sup\u003e. After natural cooling to room temperature, the final products named as graphene-\u003cem\u003ex\u003c/em\u003e wt% Ni (Grs-\u003cem\u003ex\u003c/em\u003eNi)\u0026nbsp;were obtained, where the\u003cem\u003e\u0026nbsp;x\u003c/em\u003e values are 0, 2, 6, 10 and 20.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003ePreparation of Grs\u003c/em\u003e\u003cem\u003e-\u003c/em\u003e\u003cem\u003exNi-LiBH\u003csub\u003e4\u003c/sub\u003e\u003c/em\u003e: The nanocomposites were synthesized via a hydrogen-assisted solvothermal reaction. Firstly, 30 mg of the as-prepared Grs-\u003cem\u003ex\u003c/em\u003eNi was mixed with 50 mL\u0026nbsp;n-hexane. Then, 1.6 mL of 2.7 M C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eLi solution (in hexane) and 645 \u0026mu;L of (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003eNBH\u003csub\u003e3\u003c/sub\u003e solution were added dropwise to the above solution under stirring. The mixture was exposed to ultrasonic waves generated by an ultrasonic horn with an output power of 600 W (20 kHz, FS600-N, SXSONIC Co., Ltd, Shanghai, China) in a Rosset cell. Ultrasonic waves were applied in the pulsed mode with cycles including 5 s pulses and 5 s relaxation, each lasting 30 minutes. After 4 cycles of ultrasound treatment, the mixture was then transferred into a 150 mL custom-made stainless-steel autoclave and heated at 100 \u0026deg;C for 3 h under 50 bar H\u003csub\u003e2\u003c/sub\u003e with constant stirring. After cooling to room temperature, the obtained products were collected by vacuum filtration, washed with n-hexane for several times, and dried at 90 \u0026deg;C through dynamic vacuum to remove triethylamine. The obtained samples were named as Grs-\u003cem\u003ex\u003c/em\u003eNi-LiBH\u003csub\u003e4\u003c/sub\u003e, \u003cem\u003ex\u003c/em\u003e represents the mass ratio of Ni nanoparticles in the Grs-Ni support.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMaterials C\u003c/strong\u003e\u003cstrong\u003eharacterizations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eX-ray diffraction (XRD) characterizations were performed using a MiniFlex 600 diffractometer (Rigaku, Japan) with Cu K\u0026alpha; radiation (\u0026lambda; = 0.15406 nm, 40 kV and 15 mA). The XRD data were collected in a 0.05\u0026deg; increment between scattering angle of 10-90\u0026deg; (2\u0026theta;) at room temperature. A custom-designed sample holder with a window covered by Scotch tape for transmission of X-ray was used to prevent the exposure to air. The FTIR spectra were recorded with a Bruker Tensor 27 unit (Germany) in the transmission mode. The test pellets were prepared by first mixing dried KBr with sample powders at a weight ratio of 200:1 and then cold pressing under 10 MPa. The spectra were created after 16 scans with 4 cm\u003csup\u003e-1\u003c/sup\u003e of resolution. Scanning electron microscope (SEM, Hitachi SU8010) was employed to observe the morphologies. For SEM measurements, the powders were dispersed on electrically conducting adhesive tapes in a glove box and transferred into the SEM chamber under protective Ar using a custom holder. Transmission electron microscope (TEM) was performed using a HT-770 (Japan, Hitachi) TEM. For high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and energy-dispersive X-ray spectroscopy (EDS) examinations, the powders were dispersed on Cu grids which were then loaded in a double-tilt vacuum transfer holder (Gatan 648, USA and FEI Tecnai G2 F20 S-TWIN, USA). X-ray photoelectron spectroscopy (XPS) characterization was carried out on a photoelectron spectrometer (Thermo Scientific K-Alpha) with a monochromatic Al K\u0026alpha; (h\u0026nu;: 1486.6 eV) X-ray source and calibrated with the adventitious C peak at 284.8 eV as the reference. Solid-state \u003csup\u003e11\u003c/sup\u003eB and \u003csup\u003e7\u003c/sup\u003eLi magic angle spinning NMR analysis was performed on a Bruker AVANCE NEO 600WB spectrometer. The sample powders were packed into a SiO\u003csub\u003e2\u003c/sub\u003e NMR tube and sealed with a tightly fitted cap inside an Ar-filled glove box. The operating frequencies for \u003csup\u003e7\u003c/sup\u003eLi and \u003csup\u003e11\u003c/sup\u003eB were 233.34 and 192.64 MHz, respectively. The NMR shifts were reported in parts per million (ppm) referenced to BF\u003csub\u003e3\u003c/sub\u003eOEt\u003csub\u003e2\u003c/sub\u003e and LiClO\u003csub\u003e4\u003c/sub\u003e, respectively.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eHydrogen cycling measurements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eA home-built temperature-programmed desorption (TPD) system attached to a mass spectrometer (MS) (Hiden QIC-20, England) was used for qualitative measurements of dehydrogenation, where pure Ar with a flow rate of 20 mL min\u003csup\u003e-1\u003c/sup\u003e was used as a carrier gas. The sample was heated from room temperature to 600 \u0026deg;C at 2 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e. A custom-made Sievert\u0026rsquo;s-type equipment was used for the quantitative measurement under isothermal or non-isothermal conditions. Approximately 30 mg of sample was used for each measurement. The non-isothermal volumetric hydrogen release was conducted under primary vacuum (~ 10\u003csup\u003e-3\u003c/sup\u003e Torr) with the temperature ramping at 2 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e. The dehydrogenated sample was rehydrogenated from room temperature to 350 \u0026deg;C at a heating rate of 1 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e under 100 bar H\u003csub\u003e2\u003c/sub\u003e. The isothermal measurements were conducted by rapidly heating (10 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e) the sample to a desired temperature, maintaining for a certain duration at this temperature. Thermal analysis was performed by differential scanning calorimetry (DSC) measurement on a NETZSCH DSC 200F3 unit. Approximately 2 mg of sample was loaded into an Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e crucible and heated from 30 \u0026deg;C to 600 \u0026deg;C at 2 \u0026deg;C min\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eTheoretical calculations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFirst-principles calculations were performed using the Vienna Ab initio Simulation Package (VASP).\u003csup\u003e47\u003c/sup\u003e The electronic and ionic interactions were described within the framework of the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional.\u003csup\u003e48\u003c/sup\u003e Before selecting kinetic cut off energy and k-points grid, the extensive convergence test has been performed. The planewave basis-set cutoff was set to 500 eV, with convergence criteria of 10⁻⁵ eV for energy and 0.02 eV/\u0026Aring; for structural optimization forces. The Brillouin zones were sampled using 2\u0026times;2\u0026times;1 Monkhorst-Pack k-point meshes.\u003c/p\u003e\n\u003cp\u003eA small B cluster was modeled using an octahedral cluster built from six B₁₂ units, and a Ni(110) surface with a 6\u0026times;6 cubic cell containing four atomic layers was used as the slab model. Ab initio molecular dynamics (AIMD) simulations embedded in the VASP code were conducted using a time step of 1 fs in an NVT ensemble with a Nos\u0026eacute;-Hoover thermostat. Simulations were run at 500 K to observe the dynamics of H atoms, with energy and force convergence set to 10\u003csup\u003e-\u003c/sup\u003e⁵ eV and 0.02 eV/\u0026Aring;, respectively.\u003c/p\u003e\n\u003cp\u003eTransition states for hydrogen dissociation, adsorption, and migration were located using the climbing-image nudged elastic band (CI-NEB) method and the improved dimer method (IDM).\u003csup\u003e49-50\u003c/sup\u003e Bonding interactions were analyzed via the crystal orbital Hamilton population (COHP) method in the LOBSTER software package.\u003csup\u003e51-52\u003c/sup\u003e\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data supporting the findings of this study are available within the article and its Supplementary Information files or available from the first authors and corresponding authors on reasonable request.\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe gratefully acknowledge the financial support received from the National Outstanding Youth Foundation of China (52125104), the National Natural Science Foundation of China (52071285, 52001277), the Fundamental Research Funds for the Central Universities (226-2024-00075) and the National Youth Top-Notch Talent Support Program. W.X.Z. thanks Mrs. Na Zheng (State Key Laboratory of Chemical Engineering in Zhejiang University) for performing SEM.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eW.X.Z., X.Z., H.G.P. and Y.F.L. proposed the concept and designed the research. W.X.Z., X.Z. and Y.F.L. performed the experiments. C.Q.L. and G.L.X. performed the calculations. All authors contributed to the analyses and discussion of the results. W.X.Z., X.Z., Q.C.L., H.G.P. and Y.F.L. wrote the manuscript. \u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary Information\u003c/strong\u003e accompanies at http://www.nature.com/naturecommunications.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting financial interests:\u003c/strong\u003e The authors declare no competing financial interests.\u003c/p\u003e\n\n\n\n"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eSchlapbach, L. \u0026amp; Z\u0026uuml;ttel, A. Hydrogen-storage materials for mobile applications. \u003cem\u003eNature\u003c/em\u003e\u003cstrong\u003e414\u003c/strong\u003e, 353-358 (2001).\u003c/li\u003e\n\u003cli\u003eHe, T., Pachfule, P., Wu, H., Xu, Q. \u0026amp; Chen, P. 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Matter\u003c/em\u003e\u003cstrong\u003e32\u003c/strong\u003e, 015901 (2019).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5744222/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5744222/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Hydrogen storage in lithium borohydride (LiBH4) with high gravimetric and volumetric hydrogen densities has attracted intensive research interest. However, the high working temperatures and poor reversibility due to the high thermodynamic stability and kinetic barriers, limits its practical applications. Herein, we fabricate a unique trilayered nanostructure composed of layers of graphene support, Ni nanoclusters, and LiBH4 nanoparticles, through a layer-by-layer assembly approach. The Ni nanoclusters offer nucleation sites, separate LiBH4 nanoparticles from graphene, catalyze the formation of B-H bonds and eliminate the foaming effect. During hydrogenation, Ni cleaves H-H bonds and B clusters, creating additional hydrogen absorption sites and reducing the H adsorption energy of B, which lowers the hydrogen dissociation barrier, allowing reversible storage of approximately 12.27 wt% H2 by LiBH4 commencing from 70 ºC under 100 bar H2. This finding guides the design and fabrication of light-metal hydride nanostructures for practical on-board hydrogen storage applications.","manuscriptTitle":"Reversibly storing over 12 wt% H2 by a trilayered lithium borohydride nanocomposite commencing from 70ºC","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-14 07:09:48","doi":"10.21203/rs.3.rs-5744222/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b20e0d7b-e67d-4d55-ae0e-e9051ba07943","owner":[],"postedDate":"May 14th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":48504825,"name":"Physical sciences/Energy science and technology/Energy storage/Hydrogen storage/Chemical hydrogen storage"},{"id":48504826,"name":"Physical sciences/Materials science/Nanoscale materials/Synthesis and processing"}],"tags":[],"updatedAt":"2026-04-24T07:07:42+00:00","versionOfRecord":{"articleIdentity":"rs-5744222","link":"https://doi.org/10.1038/s41467-026-69059-y","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2026-03-10 04:00:00","publishedOnDateReadable":"March 10th, 2026"},"versionCreatedAt":"2025-05-14 07:09:48","video":"","vorDoi":"10.1038/s41467-026-69059-y","vorDoiUrl":"https://doi.org/10.1038/s41467-026-69059-y","workflowStages":[]},"version":"v1","identity":"rs-5744222","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5744222","identity":"rs-5744222","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}