Journal of Magnesium and Alloys
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2021
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IF 10.088
Kang Chen,Hao Zhong,Liuzhang Ouyang,Fen Liu,Hui Wang,Jiangwen Liu,Huaiyu Shao,Min Zhu
LiBH 4 has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity, which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversion via anodic oxidation reaction of direct borohydride fuel cells (DBFCs). However, the realization of practical hydrogen applications heavily depends on the effective synthesis of high-purity LiBH 4 and recycling of the spent fuels (LiBO 2 ·xH 2 O). The present work demonstrates a convenient and high-efficiency solvent-free strategy for regenerating LiBH 4 with a maximum yield close to 80%, by retrieving its by-products with MgH 2 as a reducing agent under ambient conditions. Besides, the hydrogen released from the regeneration course can completely compensate the demand for consumed MgH 2 . The isotopic tracer method reveals that the hydrogen stored in LiBH 4 comes from both MgH 2 and coordinated water bound to LiBO 2 . Here, the expensive MgH 2 can be substituted with the readily available and cost-effective MgH 2 −Mg mixtures to simplify the regeneration route. Notably, LiBH 4 catalyzed by CoCl 2 can stably supply hydrogen to proton exchange membrane fuel cell (PEMFC), thus powering a portable prototype vehicle. By combining hydrogen storage, production and utilization in a closed cycle, this work offers new insights into deploying boron-based hydrides for energy applications.
研究领域:
能源化学
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材料科学
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
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IF 13.273
Xin Zhang,Wenxuan Zhang,Lingchao Zhang,Zhenguo Huang,Jianjiang Hu,Mingxia Gao,Hongge Pan,Yongfeng Liu
Lithium borohydride (LiBH 4 ) exhibits poor hydrogen storage reversibility because of phase separation between LiH and B due to foaming during thermal dehydrogenation. Herein, we report that by synthesizing nanostructured LiBH 4 without any supports, the foaming and phase separation can be effectively suppressed, and consequently, the hydrogen storage reversibility of LiBH 4 can be considerably improved. Using a facile single-pot solvothermal approach, a hierarchical porous nanostructured LiBH 4 composed of 50–60 nm-sized primary nanoparticles is synthesized. The resulting neat nano-LiBH 4 reversibly desorbs and absorbs approximately 12 wt% of H at 400 °C and under 100 bar H 2 . The superior hydrogen storage performance is attributed to the effective inhibition of foaming upon heating. The formation of LiH and B prior to melting, which can be associated with the largely reduced particle sizes and porous agglomeration structure, plays a crucial role in suppressing foaming. Our findings offer a new strategy for the preparation of nanoscaled freestanding borohydrides, and also important insights into the development of highly reversible metal borohydrides for hydrogen storage applications.
研究领域:
材料科学
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能源存储
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2026
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IF 9.1
Shixuan He,Dongdong Li,Guizhao Zhu,Xingqing Duan,Jinting Chen,Bogu Liu,Yawei Li,Haixiang Huang,Haoyuan Zheng,Xinhua Wang,Hong Li,Ying Wu
The practical application of LiBH 4 for solid-state hydrogen storage is hindered by its sluggish kinetics and high thermodynamic stability. To address these challenges, we constructed a multiphase catalytic system within LiBH 4 by incorporating nano-BaTiO 3 and carbon nanotubes (CNTs) through ball milling. The composite of LiBH 4 , 20 wt% BaTiO 3 and 20 wt% CNTs exhibits significantly enhanced dehydrogenation properties, with an initial temperature as low as 223 °C and a peak desorption temperature of 353 °C, releasing 8.2 wt% H 2 at 500 °C. The modified composite demonstrates markedly improved reversibility and kinetics, evidenced by a retained capacity of 4.1 wt% after the 6th cycle and a substantially decreased activation energy of 123 kJ mol −1 . During the first dehydrogenation, LiBH 4 reacts in-situ with BaTiO 3 to form Li 3 BO 3 , BaB 6 , and TiO 2 phases. These products, in conjunction with CNTs, form a multifunctional catalytic framework. Among them, BaB 6 serves as the nucleation site, TiO 2 acts as the active catalyst, and Li 3 BO 3 facilitates ion transport, collectively enhancing the reaction kinetics and cycling stability of LiBH 4 . Meanwhile, the CNTs provides dual functions of confinement and excellent thermal conductivity, which suppressing particle aggregation and enhancing thermal diffusion rate. Consequently, the composite exhibits a lower decomposing temperature, rapider kinetics, and enhances reversibility compared with the as-milled LiBH 4 . This work provides an effective strategy of in-situ engineering a multiphase interface to attain high-performance solid-state hydrogen storage materials.
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高影响因子
RSC Advances
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2018
·Vol. 8
·期 35
·19353-19361
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IF 2.936
Guang Xu,Wei Zhang,Ying Zhang,Xiaoxia Zhao,Ping Wen,Di Ma
Fe3O4 nanoclusters anchored on porous reduced graphene oxide (Fe3O4@rGO) have been synthesized by a one-step hydrothermal route, and then ball milled with LiBH4 to prepare a hydrogen storage composite with a low onset dehydrogenation temperature, and improved dehydrogenation kinetics and rehydrogenation reversibility. The LiBH4–20 wt% Fe3O4@rGO composite begins to release hydrogen at 74 °C, which is 250 °C lower than for ball-milled pure LiBH4. Moreover, the composite can release 3.36 wt% hydrogen at 400 °C within 1000 s, which is 2.52 times as high as that of pure LiBH4. Importantly, it can uptake 5.74 wt% hydrogen at 400 °C under 5 MPa H2, and its hydrogen absorption capacity still reaches 3.73 wt% after 5 de/rehydrogenation cycles. The activation energy (Ea) of the hydrogen desorption of the composite is decreased by 79.78 kJ mol−1 when 20 wt% Fe3O4@rGO is introduced into LiBH4 as a destabilizer and catalyst precursor, showing enhanced thermodynamic properties. It could be claimed that not only the destabilization of Fe3O4, but also the active Li3BO3 species formed in situ, as well as the wrapping effect of the graphene, synergistically improve the hydrogen storage properties of LiBH4. This work provides insight into developing non-noble metals supported on functional graphene as additives to improve the hydrogen storage properties of LiBH4.
研究领域:
材料科学
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能源科学
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DOI
高影响因子
Journal of Physical Chemistry C
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2015
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IF 4.772
Yi Zhang,Yongfeng Liu,Xin Zhang,You Li,Mingxia Gao,Hongge Pan
A nanosized Ni@C composite (Ni particles: < 10 nm) was successfully synthesized by casting a Ni-based metal–organic framework MOF-74(Ni) filled with furfuryl alcohol at 700 °C. The resulting Ni@C composite exhibits remarkable catalytic activity for reducing the operating temperature of hydrogen release from the LiBH4–2LiNH2 system. The LiBH4–2LiNH2–10 wt % Ni@C sample releases approximately 10 wt % of hydrogen at 135–250 °C, and the end temperature for hydrogen release is reduced by 110 °C in comparison to that of the pristine sample. During dehydrogenation, nanosized Ni remains almost unchanged and only works as a catalyst to reduce kinetic barriers of hydrogen release from the LiBH4–2LiNH2 system, which is responsible for lowered dehydrogenation temperatures of the Ni@C-containing sample. More importantly, the dehydrogenated Ni@C-containing sample presents a loose porous morphology that slightly improves its rehydrogenation properties.
研究领域:
材料科学
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催化化学
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氢气储存
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纳米技术
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能源材料
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Xingyu Liu,Shaoyang Shen,Yunqi Jia,Lin Jiang,Liuzhang Ouyang
Hydrogen is a clean, sustainable, and efficient energy carrier. However, achieving safe and controllable storage for practical applications remains a challenge. The practical applications of lithium borohydride remain challenging due to its violent hydrolysis reaction. Herein, we report the synthesis of bimetallic hydrogen storage materials based on LiK(BH4)2 (LKBH-x-1) through ball-milling various ratios of potassium borohydride and lithium borohydride, which demonstrate excellent stability in aqueous solutions and extremely high hydrogen storage capacity. Optimizing reaction conditions indicated that the LKBH-4-1 produced from a 4:1 ratio exhibited an exceptionally high theoretical hydrogen storage capacity of 14.3 wt % while retaining excellent stability in aqueous solutions at ambient conditions. Further density functional theory (DFT) calculations revealed that the stability of LKBH-x-1 in aqueous solution is attributed to the robustness of B–H bonds in the differing phases. Furthermore, we clarify the feasibility of the LKBH-x-1 regeneration cycle by ball milling MgH2 and the hydrolysis products of LKBH-x-1. This work provides a new perspective for regulating borohydride hydrolysis for hydrogen production.
研究领域:
材料科学
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化学工程
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能源科学
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DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Kang Chen,Mili Liu,Zhuoyin Peng,Hao Zhong,Lang Gan,Jincheng Huang,Jing Zhao,Hui Wang,Jiangwen Liu,Huaiyu Shao,Liuzhang Ouyang
LiBH 4 (LB in short) with a hydrogen capacity as high as 18.5 wt% and a low molecular weight (21.78 g mol −1 ) is among the most promising candidates for the hydrogen-based economy. However, current major technologies in (re)generation of LB rely heavily on energy-intensive processes, which greatly prohibits practical scaling-up of applications. Here we report a sustainable and effective approach to (re)generate LB via converting renewable H + in crystalline water into H - , achieving a desirable yield of ∼50%. This one-step synthesis method relies on the reaction between spent fuels, specifically LiBO 2 · x H 2 O, and Mg-based alloys to form LB under ambient atmosphere. Notably, our approach surpasses the efficiency of other conventional method, such as LiH-B-H 2 and MgH 2 -LiBO 2 systems, which not only bypasses the energy-intensive dehydration procedure of LiBO 2 · x H 2 O (∼470 ℃) but also eliminates the use of costly hydrides or high-pressure H 2 . Our findings indicate that Mg participated in the regeneration process prior to Al in Mg-Al alloys and [BH 4 ] - is gradually evolved from other intermediate species [BH x (OH) 4- x ] - ( x = 0, 1, 2, 3). By combining hydrogen release and efficient storage of hydrogen-rich substrate in a closed materials cycle, this study may shed light on a promising step toward application of renewable hydrogen in a fuel cell-based hydrogen economy.
研究领域:
材料科学
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能源科学
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化学工程
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产品关联
DOI
高影响因子
ACS Applied Energy Materials
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2025
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IF 5.5
Guoquan Na,Wen-Gang Cui,Hangyan Shi,Zhenglong Li,Fan Gao,Xingqiang Wang,Ke Wang,Yong Gao,Yaxiong Yang,Zichao Shen,Yanxia Liu,Jian Miao,Hongge Pan
LiBH4 has attracted significant interest due to its high-hydrogen storage capacity (18.5 wt % H2). However, its practical application is severely impeded by the high dehydrogenation temperature, sluggish hydrogen release kinetics, and poor reversibility. In this work, a graphene-supported rodlike FeF2/FeOX additive (FeF2/FeOX@G) is prepared and introduced into LiHB4 by a simple ball-milling. With an optimized LiBH4-to-FeF2/FeOX@G weight ratio of 7:3, the 7LiBH4-3(FeF2/FeOX@G) system starts dehydrogenation at a low temperature of 100 °C below and 8.7 wt % H2 is released upon heating to 400 °C, while 1.1 wt % H2 is released for pristine LiBH4. Moreover, the system releases rapidly 7.0 wt % H2 at 350 °C within 80 min, and a dehydrogenation capacity of 5.5 wt % is reached after 10 reversible hydrogen absorption and desorption cycles. The in situ formed FeB, Li3BO3, and Fe2B during the first dehydrogenation process acted as a synergistic catalysis, effectively improving the reversible hydrogen storage of LiBH4. This work provides insights into the design of unique additives to introduce multiple catalyst synergies to enhance the hydrogen storage performance of LiBH4.
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高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Zhenglong Li,Shun Wang,Mingxia Gao,Kaicheng Xian,Yi Shen,Yaxiong Yang,Panyu Gao,Wenping Sun,Yongfeng Liu,Hongge Pan
LiBH4 as a promising candidate material for solid-state hydrogen storage still suffers from high dehydrogenation temperature and poor reversibility. A catalyzed LiBH4-based system with in situ introduced Li3BO3 and V is synthesized by adding NH4VO3 into LiBH4 followed by a heat treatment and a hydrogenation process. The optimized LiBH4 system introduced with 0.06 molar fraction of Li3BO3 + V, which is denoted as LiBH4–0.06LiBOV, shows excellent hydrogen storage kinetics and high reversible stability. The system starts to release hydrogen at 220 °C, and a capacity of 5.8 wt % H2 is obtained at 350 °C within 90 min. Furthermore, full rehydrogenation can be achieved at 500 °C and 50 bar of H2 for 50 min, and a capacity retention as high as 87.5% is obtained after five cycles. In situ introduced Li3BO3 and V lower the activation energy of LiBH4 and inhibit the generation of Li2B12H12 during the hydrogenation of LiBH4, which contribute to the synergistic catalytic effects on hydrogen desorption and absorption. In addition, the restraining of the particle size growth during dehydrogenation/hydrogenation is critical to inhibiting the generation of Li2B12H12 and thus improves the hydrogenation property of LiBH4. The catalyzed LiBH4 system provides new insights on LiBH4 as a high-density hydrogen storage material.
研究领域:
材料科学
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氢气储存
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固态化学
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能量存储
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）