CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Shun Wang,Yunting Wang,Xiaoye Zhou,Chaojie Liu,Yongyang Zhu
Nanoengineering has proved effective in tailoring thermodynamics and kinetics of LiBH 4 and improving its (de)hydrogenation under mild conditions. Constructing nanosized LiBH 4 on 2D graphene has been reported to enhance loading efficiency and hydrogen capacity. However, the chemical inertness of graphene makes it hard to alter the intrinsic characteristics of LiBH 4 , leading to limited performance improvement. Moreover, the structural stability of loaded LiBH 4 needs enhancement for longer cycle life. Herein, we develop a fluorinated porous graphene host in which the Li-philic fluorine atoms induce Li vacancies in LiBH 4 , reducing the reaction enthalpy and energy barrier for (de)hydrogenation; meanwhile, LiF formed in-situ acts as an interfacial bridge that stabilizes the nanostructure. An appreciable hydrogen release is achieved below 250 °C, with high capacity retention after 30 cycles. In addition, the porous channels ensure rapid hydrogen diffusion and superior kinetics in the compacted state, yielding a competitive volumetric hydrogen storage density of 76.2 g L −1 that is higher than liquefied hydrogen (~70 g L −1 ). This work presents feasible schemes for optimizing hydrogen storage performance of LiBH 4 and offers fresh insights on interfacial interaction mechanisms.
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Chengguo Yan,Jiaguang Zheng,Ao Xia,Qingbo Zhang,Meiling Lv,Zhenxuan Ma,Chao Su,Zhendong Yao
Among conventional hydrogen storage materials , LiBH 4 has been regarded as one of the best hydrogen transporters due to its relatively large hydrogen capacities. However, because of its extraordinarily high dehydrogenation temperatures, LiBH 4 was not suitable for hydrogen storage due to its stable thermodynamic features. Herein, we present a novel approach to LiBH 4 that uses solid-state multi-hydroxyl mannitol as a reactant, regulating hydrogen release below 69.9 °C. More than 7 wt% H 2 could be released with ultra-fast rates at 140 °C from the LiBH 4 -mannitol composite. XRD , FTIR , and SEM tests revealed that the reaction between mannitol (H δ+ ) and LiBH 4 (H δ− ) to produce hydrogen was accompanied by the generation of large amounts of heat in situ, which further promoted the decomposition of LiBH 4 for hydrogen production , exceeding the theoretical dehydrogenation amount of H δ+ - H δ− reaction. This work indicates possibilities for the development of fast and easy high-capacity hydrogen generation systems based on complex hydrides.
研究领域:
材料科学
·
无机化学
·
能源化学
·
氢能源存储
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DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2016
·
IF 3.014
Yufei Ma,Yuan Li,Ting Liu,Xin Zhao,Lu Zhang,Shumin Han,Yijing Wang
LiBH 4 is considered a promising hydrogen storage material for automotive applications ; however, its usage is limited because of unfavorable reversibility and sluggish kinetics. In this paper, we have improved the hydrogen storage properties of LiBH 4 by doping with a porous Li 3 BO 3 additive, which was prepared by a solid state synthesis method . The LiBH 4 –33 wt% Li 3 BO 3 composite was prepared via mechanical milling. The composite exhibited an acceptable hydrogenation/dehydrogenation rate, high hydrogen storage capacity and superior reversibility. The initial dehydrogenation temperature of the composite was 105 °C, which is 205 °C lower than that of the pristine LiBH 4 , and the hydrogen desorption capacity was 4.12 wt% at 450 °C within 2000 s. The composite maintained its hydrogen absorption capacity of 2.8 wt% with a narrow gap after 5 de/hydrogenation cycles at 400 °C and 5.0 MPa. The Li 3 BO 3 additive clearly enhanced the hydrogen storage properties of LiBH 4 and facilitated the decomposition and formation of [BH 4 ] − , thus accelerating de/rehydrogenation of LiBH 4 . At the same time, Li 3 BO 3 offered numerous porous channels that enhanced hydrogen circulation.
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DOI
高影响因子
Progress in Natural Science-Materials International
·
2018
·Vol. 28
·期 4
·529-533
·
IF 2.572
Zhenmin Ding,Yufei Ma,Dandan Peng,Lu Zhang,Yumeng Zhao,Yuan Li,Shumin Han
In this work, LiBH 4 –20 wt% PP composite was prepared by ball-milling with as-synthesized hierarchical pyrolysis polyaniline (PP) and LiBH 4 , and the hydrogen sorption performance as well as catalytic mechanism of the composite was studied. It is found that the onset desorption temperature of the composite decreases to 75 °C, almost 235 °C lower than that of the milled LiBH 4 . Moreover, the composite could release 4.1 wt% H 2 and rehydrogenate a total of 4.4 wt% H 2 when the temperature raiseds up to 400 °C, showing an outstanding reversibility, which even 3.9 wt% H 2 can be kept after five cycles. Through scanning electron microscopy (SEM) observation and X-ray diffraction (XRD) analysis, we found that the PP surface forms some nanoholes after hydrogenation-dehydrogenation cycles, which leads to the confinement of some LiBH 4 in the PP nanoporous structure, therefore, the hydrogen sorption kinetics and reversibility are significantly enhanced. In addition, we also found the oxygenic groups of the PP can react with LiBH 4 forming LiBO 2 and Li 3 BO 3 , where the containing Li–B–O bonds loaded in the porous structure of the PP catalyze the hydrogenation reaction of LiBH 4 .
研究领域:
材料科学
·
能源化学
·
纳米材料
·
固态储氢
·
催化化学
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DOI
高影响因子
International Journal of Minerals Metallurgy and Materials
·
2026
·Vol. 33
·期 5
·1461-1471
·
IF 8.8
Wang Fan,Geng Mingxiang,Bao Anyang,Lü Yujie,Huang Pengru,Liu Dongming
LiBH 4 , a solid-state hydrogen storage material with ultra-high theoretical hydrogen capacity, is seriously hindered for the practical applications by its high thermodynamic stability and slow hydrogen desorption kinetics. Herein, the dehydrogenation properties of LiBH 4 are remarkably improved by confinement in the porous (Cu,Ni)/Cu 2 O heterostructure (np-(Cu,Ni)/Cu 2 O), which was achieved using a novel two-step method containing dealloying of Mg–Cu–Ni precursor alloy to form the porous (Cu,Ni) solid solution, followed by micro-oxidation under air conditions. Hydrogen release from the constructed LiBH 4 @np-(Cu,Ni)/Cu 2 O (1:2, mass ratio) system begins at approximately 80°C and ends before 380°C, with 12.5wt% of hydrogen desorbed. Moreover, the apparent dehydrogenation activation energy has been reduced to 44.2 kJ/mol. After rehydrogenation at 400°C under 8 MPa hydrogen pressure, the LiBH 4 @np-(Cu,Ni)/Cu 2 O (1:2, mass ratio) system can release 3.6wt% of hydrogen during the second dehydrogenation process. These findings show that the synergistic effect of confinement and heterostructure catalysis provided by the porous metal derivatives can greatly enhance the hydrogen storage properties of LiBH 4 .
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DOI
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 16
·4380-4387
·
IF 9.405
Kang Chen,Liuzhang Ouyang,Hao Zhong,Jiangwen Liu,Hui Wang,Huaiyu Shao,Yao Zhang,Min Zhu
LiBH4 has excellent application potential as an off- or on-board hydrogen carrier for its unparalleled hydrogen capacity (18.5 wt%). However, the difficulty in recycling “one-pass” LiBH4 and the resulting high cost hamper its large-scale applications. Here, we report a facile and low-cost method for LiBH4 regeneration by ball milling its hydrolysis by-product (LiBO2·2H2O) and Mg under ambient conditions, where expensive H− stored in LiBH4 is entirely converted from cheap H+ in coordinated water. This scenario is reported for the first time without hydrides employed as hydrogen sources for the reduction process. Moreover, the yields for LiBH4 synthesized by this method may reach 40%. The cost of LiBH4 regeneration exhibits a 5-fold reduction over a previous study using NaBH4 as a raw material. Significantly, the as-purified product displays even better physicochemical properties than commercial LiBH4, for example, superior hydrolysis kinetics. Overall, a one-step approach, combining hydrogen production and storage in a closed cycle, is proposed in this work. Furthermore, the formation mechanism of LiBH4 is illustrated and the intermediate product, LiBH3(OH), is successfully observed for the first time during the regeneration course.
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2017
·
IF 3.582
Wei Zhang,Guang Xu,Lingjuan Chen,Shuyi Pan,Xu Jing,Jiasheng Wang,Shumin Han
Novel fluorinated graphene (FG) nano-sheets with three-dimensional (3D) porous structure were synthesized by one-pot hydrothermal reaction , and then ball milled with LiBH 4 to prepare the hydrogen storage composite material. The LiBH 4 with 20 wt.% FG composite begins to release hydrogen at 204 °C, 120 °C lower than that of pure LiBH 4 . Moreover, it can release 3.45 wt.% hydrogen at 400 °C within 1000 s, which is 2.57 times faster than pure LiBH 4 . The reversibility of the LiBH 4 –FG composite also has been enhanced, its absorption capacity still reaches 78.6% of initial hydrogen uptake at the 4th cycle. According to the phase composition analyses, F – can partially substitute the anionic H in LiBH 4 or LiH, resulting in a favorable thermodynamic modification. Additionally, the activation energy ( E a ) of hydrogen desorption of LiBH 4 is reduced from 181.80 kJ/mol to 130.87 kJ/mol. The remarkably improved hydrogen storage performances of LiBH 4 are largely attributed to the combined effects of the nano-modifying and the function of F anion of the FG.
研究领域:
材料科学
·
能源化学
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产品关联
DOI
高影响因子
MATERIALS CHEMISTRY AND PHYSICS
·
2024
·
IF 4.3
Kang Chen,Mili Liu,Yongan Li,Shiqian Zhao,Xinxuan Cheng,Jincheng Huang,Jing Zhao,Lang Gan,Yanjie Ren,Liuzhang Ouyang
Aluminum (Al) and lithium borohydride (LiBH 4 , LB for short) are highly promising candidates for chemical hydrogen storage . However, the direct utilization of Al–H 2 O reaction faces significant challenges due to the inherent issue of surface passivation , which prevents the ongoing reaction between Al and H 2 O. Additionally, the hydrolysis of LB is constrained to temperatures exceeding 0 °C, and the development of cost-effective catalysts that enable efficient hydrogen release from LB hydrolysis remains a bottleneck in realizing its practical application. Herein, we present an efficient noncatalytic hydrogen generation system utilizing Al and LB mixtures, enabling H 2 production over a broad temperature range using methanol, ethanol, or their mixtures as reaction solvents. Our results demonstrate that the H 2 generation kinetics of Al-LB composites can be precisely tailored by adjusting various parameters, such as LB content, ball-milling time, reaction temperature, and solution composition. In comparison with the traditional Al and its alloy systems , Al-LB composites exhibit remarkable performance in both hydrogen capacity and H 2 kinetics. For instance, the Al-50 % LB composite achieves a hydrogen yield of 2322 mL g −1 H 2 within 5 min (∼80 % fuel conversion). Specifically, with a 70 % LB content, the composite generates over 3100 mL g −1 H 2 within the same time, realizing nearly 90 % fuel conversion. Notably, the apparent activation energy of the Al-30 % LB and Al-50 % LB composites is determined to be 29.1 kJ mol −1 and 13.9 kJ mol −1 , much lower than that of Al-based hydrolyzable materials. These findings hold significant importance for the advancement of practical Al-based hydrogen generation systems designed for mobile or portable applications.
研究领域:
材料科学
·
能源化学
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产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2022
·Vol. 32
·期 43
·2205677
·
IF 19.924
Ziqiang Wu,Kaiwen Wang,Weiwei Sun,Zhipeng Li,Zhihong Ma,Yunfeng Zhu,Yongjin Zou,Yao Zhang
The safety issues oflithium-ion batteries provoke the development of highly secure solidelectrolytes. Hydride electrolytes owning the high electrochemical stabilityand anode compatibility may sufficiently relieve theconcerns of safety. However, the low ionic conductivity at room temperature hampersits further application. Herein, the strategy of defect-induced (BH 4 ) – deformation to achieve high ionicconductivity LiBH 4 /BN composite electrolyte is suggested. The theoreticalcalculations indicate that the volume of the (BH 4 ) – tetrahedron is expanded by 14%. Such atetrahedron deformation weakens the Li H interaction forces in LiBH 4 , and thus promotes the Li-ion migration. The LiBH 4 /BN composites are enabled to deliver lithium ionicconductivity of 1.15 × 10 –4 S cm –1 at 40 °C with a Li-ion transference number of 97%, persuading an excellent solidelectrolyte for all-solid-state batteries. The sub-surface of LiBH 4 offers the lowest migration barrier among all possiblechannels, paving the optimal way for Li-ion migration. Furthermore, the LiBH 4 /BN electrolytes supply excellent electrochemical stabilityand electrode compatibility. The utilized strategy of outfield induction (notonly defects) and ligand deformation (not only (BH 4 ) – ) may also be extended to other solid electrolytes.
研究领域:
材料科学
·
固态离子学
·
能源化学
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电化学
·
纳米材料
·
电池技术
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DOI
高影响因子
Chemistry-An Asian Journal
·
2015
·Vol. 10
·期 11
·2452-2459
·
IF 4.587
Yuepeng Pang,Yongfeng Liu,Xin Zhang,Qian Li,Mingxia Gao,Hongge Pan
Herein, an initial attempt to understand the relationships between hydrogen storage properties, reaction pathways, and material compositions in LiBH 4 – x Mg(AlH 4 ) 2 composites is demonstrated. The hydrogen storage properties and the reaction pathways for hydrogen release from LiBH 4 – x Mg(AlH 4 ) 2 composites with x =1/6, 1/4, and 1/2 were systematically investigated. All of the composites exhibit a four-step dehydrogenation event upon heating, but the pathways for hydrogen desorption/absorption are varied with decreasing LiBH 4 /Mg(AlH 4 ) 2 molar ratios. Thermodynamic and kinetic investigations reveal that different x values lead to different enthalpy changes for the third and fourth dehydrogenation steps and varied apparent activation energies for the first, second, and third dehydrogenation steps. Thermodynamic and kinetic destabilization caused by the presence of Mg(AlH 4 ) 2 is likely to be responsible for the different hydrogen desorption/absorption performances of the LiBH 4 – x Mg(AlH 4 ) 2 composites.
研究领域:
材料科学
·
氢气储存
·
固态化学
·
能源材料
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DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2017
·
IF 3.133
Qian Wen Bao,Jin Fang Liu,Bin Hong Liu,Zhou Peng Li
Two N-containing hydrocarbon based polymers polyacrylonitrile (PAN) and polyaniline (PANI) were found to be able to destabilize LiBH 4 , a potential hydrogen storage material , resulting in larger hydrogen capacities of more than 10 wt% with peak dehydrogenation temperatures around 344 °C. The results suggest that a co-destabilization effect was achieved through the interaction of B H and C H bonds, which was further enhanced due to the presence of nitrogen atoms in polymers. After rehydrogenation of the dehydrogenated products, LiBH 4 was found to be regenerated to a large extent in both of the LiBH 4 +polymer composites. Detailed analysis including XRD , FTIR , DSC-TG-MS, HRTEM , Raman, XPS and solid-state 11 B MAS NMR was performed to elucidate the dehydrogenation and rehydrogenation mechanisms in these composites. The results provide considerable information about interaction mechanisms among B H, C H, N H and C N bonds and also shed lights on the enhancement of LiBH 4 dehydrogenation and reversibility.
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DOI
高影响因子
RSC Advances
·
2013
·Vol. 4
·期 6
·3082-3089
·
IF 2.562
Weitong Cai,Hui Wang,Dalin Sun,Qingan Zhang,Xiangdong Yao,Min Zhu
Destabilization by the alkali metal hydroxides LiOH, NaOH, and KOH in the solid-state dehydrogenation of LiBH4 is reported. 6.5 wt% of hydrogen was liberated within 10 minutes at 250 °C. Destabilization originated from the interaction between H+ in [OH]− and H− in [BH4]−. A larger Pauling's electronegativity of the alkali metal (Li > Na > K) led to a greater acidity of the proton donor [OH]− site, and thus enhanced destabilization. The temperature of the predominant dehydrogenation was reduced to 207, 221, and 230 °C, for ball milled LiBH4–LiOH, 2LiBH4–NaOH, and 2LiBH4–KOH, respectively. The LiBH4: LiOH stoichiometry greatly affected the destabilization, by providing differing reaction pathways in LiBH4-xLiOH (x = 1, 1.36, 4). The incremental increase in the LiOH content of LiBH4-xLiOH increased the dehydrogenation rate, but the temperature increased from 207 °C (x = 1) to 250 °C (x = 4). 4.1 and 6.5 wt% of hydrogen was liberated within 10 minutes by LiBH4–LiOH and LiBH4–4LiOH, respectively. The incremental increase in dehydrogenation temperature was attributed to differing [BH4]−⋯[OH]− interactions, formed by the differing stoichiometric ratios.
研究领域:
材料科学
·
化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）