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
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2020
·
IF 4.473
Jiuyi Zhu,Yuchen Mao,Hui Wang,Jiangwen Liu,Liuzhang Ouyang,Min Zhu
LiBH4 (lithium borohydride) is a promising high capacity hydrogen storage material but suffering from its high dehydrogenation temperature and poor reversibility. To solve this problem, surface-modified AlN (aluminum nitride) was prepared by the alcoholysis process of LiBH4 and composited with LiBH4. By controlling the temperature of the drying process, it can tune the sorts and quantities of the functional groups on AlN. The de/rehydrogenation of LiBH4 is greatly improved by compositing it with surface-modified AlN because oxygen atoms in functional groups promote the decomposition of intermediates of LiBH4 and Hδ+ (positive hydrogen atom) reacting with Hδ− (negative hydrogen atom) in LiBH4. Besides, AlN provides the pathway of H and Li atoms to improve the kinetics of the de/rehydrogenation of LiBH4. Freeze-dried AlN containing O–H and C–H groups shows the best catalytic effect on the hydrogen storage reaction of LiBH4. The optimized composite could release a stable capacity of more than 6.1 wt % after cycling, which has potential applications in high-temperature environment hydrogen storage.
研究领域:
材料科学
·
能源存储
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2011
·Vol. 36
·期 23
·15266-15272
·
IF 4.057
Pei Pei Yuan,Bin Hong Liu,Zhou Peng Li
A comparative study was performed on four LiBH 4 -based hydrogen storage composites 2LiBH 4 + MgX 2 and 6LiBH 4 + CaX 2 (X = H and F). The composites with fluorides and those with corresponding hydrides exhibited similar hydrogen storage properties. The dehydrogenation of 2LiBH 4 + MgF 2 demonstrated a strong dependence on the hydrogen back pressure , similar to that of 2LiBH 4 + MgH 2 . The reversible hydrogen storage of 2LiBH 4 + MgF 2 was achieved under a back pressure of 5 bar at 450 °C. Dehydrogenation under lower H 2 pressures resulted in the production of Mg and thus a partial reversibility. In contrast, both 6LiBH 4 + CaH 2 and 6LiBH 4 + CaF 2 revealed reversible hydrogen storage properties regardless of the hydrogen back pressure. The structural difference between MgB 2 and CaB 6 may account for the observed differences in hydrogen storage properties of the Mg- and Ca-containing LiBH 4 reactive composites.
研究领域:
材料科学
·
能源化学
·
固态储氢
·
无机化学
·
功能材料
✓ 已验证
DOI
高影响因子
Journal of Energy Storage
·
2025
·
IF 9.8
Yongyang Zhu,Shun Wang,Yanwu Chen,Feng Liu,Libing Guo,Yingxi Wei,Guijing Xiao,Qing Zhou,Longwen Chen
The hydrolysis of lithium borohydride (LiBH 4 ) is very promising for on-site hydrogen generation to supply hydrogen since it has appealing features such as a high hydrogen capacity (13.9 wt%, water included), fast hydrogen evolution rate, and mild reaction conditions. The large-scale application of LiBH 4 , however, is restricted by its difficult regeneration from stable hydrolytic products (LiBO 2 · x H 2 O), which requires expensive reducing agents such as MgH 2 , high energy-consuming dehydration process for LiBO 2 ·2H 2 O, and additional hydrogen input. Herein, we develop a facile method to directly regenerate LiBH 4 from LiBO 2 ·2H 2 O by ball milling with low-cost Al-rich alloys as reductants and Li 2 O as additives, balancing efficiency and economy well. Introducing Mg (or Ca) into Al to form Al-rich alloys optimizes the mechanical brittleness and chemical reducibility, which facilitate the crushing, collision, and reaction of reactants and the conversion of H + to H − . The specific mechanism study illustrates that Mg in Al 3 Mg 2 preferentially reacts and the in-situ derived Al with fresh surface and fine size is highly active for reductive regeneration of LiBH 4 . Besides, a little addition of Li 2 O suppresses the formation of “boron sink”, [B 12 H 12 ] − , further increasing the yield of LiBH 4 . This work evidences the regeneration potential of Al-based reducing agents on metal borohydrides.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2023
·
IF 10.9
Shaoyang Shen,Wenfang Liao,Zhijie Cao,Jiangwen Liu,Hui Wang,Liuzhang Ouyang
MgH 2 , as one of the typical solid-state hydrogen storage materials, has attracted extensive attention. However, the slow kinetics and poor cycle stability limit its application. In this work, LiBH 4 and YNi 5 alloy were co-added as additives to MgH 2 via ball milling, thereby realizing an excellent dehydrogenation performance and good cycle stability at 300 °C. The MgH 2 -0.04LiBH 4 -0.01YNi 5 composite can release 7 wt.% of hydrogen in around 10 min at 300 °C and still have a reversible hydrogen storage capacity of 6.42 wt.% after 110 cycles, with a capacity retention rate as high as 90.3 % based on the second dehydrogenation capacity. The FTIR results show that LiBH 4 can reversibly absorb and desorb hydrogen throughout the hydrogen ab/desorption process, which contributes a portion of the reversible hydrogen storage capacity to the MgH 2 -0.04LiBH 4 -0.01YNi 5 composite. Due to the small amount of LiBH 4 and YNi 5 , the dehydrogenation activation energy of MgH 2 did not decrease significantly, nor did the dehydrogenation enthalpy (∆ H ) change. However, the MgNi 3 B 2 and in-situ formed YH 3 during the hydrogen absorption/desorption cycles is not only beneficial to the improvement of the kinetics performance for MgH 2 but also improves its cycle stability. This work provides a straightforward method for developing high reversible hydrogen capacity on Mg-based hydrogen storage materials with moderate kinetic performance.
研究领域:
材料科学
·
氢气储存
·
能量存储
·
固态化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2026
·
IF 6.7
Jinting Chen,Lei Wang,Ming Yao,Yue Pan,Zeyu Zhang,Yawei Li,Haixiang Huang,Bogu Liu,Jianguang Yuan,Bao Zhang,Ying Wu
To address the sluggish dehydrogenation kinetics and high operating temperatures of LiBH 4 , Ti 2 VC 2 MXene was incorporated with LiBH 4 to modify its dehydrogenation performance. With 40 wt% Ti 2 VC 2 MXene additive, the onset dehydrogenation temperature of LiBH 4 is reduced to 98.31 °C, while the peak hydrogen release occurs at 332.86 °C. Isothermal dehydrogenation measurements demonstrate that the composite rapidly desorbs 9.50 wt% H 2 within 40 min at 325 °C, 10.67 times faster than that of LiBH 4 . Furthermore, the addition of 40 wt% Ti 2 VC 2 MXene effectively lowers the activation energies for the dehydrogenation to 104.76 and 112.99 kJ mol⁻ 1 , respectively. Mechanism studies reveal that the enhanced dehydrogenation performance originates from the in-situ formation of catalytic active species, including Ti 0 , V 0 and Li 3 BO 3 , promoting the cleavage of ionic and covalent bonds in LiBH 4 . Simultaneously, the multiphase Ti/V/Li 3 BO 3 hetero-ensembles create abundant interfacial boundaries, serving as efficient pathways for hydrogen diffusion and accelerating the dehydrogenation kinetics.
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2020
·
IF 6.274
Kang Chen,Liuzhang Ouyang,Hui Wang,Jiangwen Liu,Huaiyu Shao,Min Zhu
Lithium borohydride (LiBH 4 ) has received much attention due to its high hydrogen density of 18.5 wt%. However, in the hydrolytic process for hydrogen supply, the sluggish kinetics of LiBH 4 and the agglomeration of by-product greatly limit its wide utilization. In this work, transition-metal chlorides (CoCl 2 , NiCl 2 , FeCl 3 ) are firstly adopted to explore the hydrogen liberation behaviors of LiBH 4 . The hydrolysis kinetics can be well-controlled by tuning the concentration of chlorides. Among the above chlorides, CoCl 2 displays much faster reaction kinetics, delivering a hydrogen generation rate ranging from 421 to 41701 mL min −1 g −1 with a maximum conversion of 95.3%, much higher than the value of 225 mL min −1 g −1 H 2 with Pt–LiCoO 2 . The maximum gravimetric hydrogen density may reach 8.7 wt% at H 2 O/LiBH 4 = 2–6 mol/mol. Furthermore, NH 3 is introduced to solve the issue of uncontrollable kinetics of LiBH 4 by forming its ammoniates, where LiBH 4 ·NH 3 catalyzed by CoCl 2 could stably release over 4350 mL g −1 H 2 per unit weight of LiBH 4 within 30 min at 40 °C, with a hydrogen density of ∼7.1 wt% and a hydrogen yield of 97.0%. Our approaches adopting non-noble metal chlorides are efficient and affordable for hydrogen supply to PEMFCs via hydrolysis of LiBH 4 -based materials.
研究领域:
材料科学
·
化学工程
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2015
·
IF 3.313
Qian Wen Bao,Wei Yuan Pan,Hao Liu,Bin Hong Liu,Zhou Peng Li
In this study, hydrogen release and uptake properties for composites of LiBH 4 with the conjugated polymer poly( p -phenylene) (PPP) were investigated. The incorporation of LiBH 4 with PPP led to a significant destabilization effect, decreasing the dehydrogenation temperature of LiBH 4 by 100 °C. Moreover, LiBH 4 could be regenerated at 450 °C under 9.0 MPa H 2 . By thorough analyses using XRD , HRTEM , FTIR , Raman, XPS as well as 11 B MAS NMR, the dehydrogenation product of LiBH 4 +PPP and the regeneration mechanism of LiBH 4 are elucidated. Also the reason of capacity degradation is discussed based on the analysis results. The formation condition of LiBH 4 was significantly moderated due to the presence of a simultaneously formed amorphous mixture of boron and carbon, which sheds light on the improvement of LiBH 4 reversibility .
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Kang Chen,Mili Liu,Liuzhang Ouyang,Hui Wang,Jiangwen Liu,Min Zhu
Hydrolysis of LiBH 4 (LB in short) is considered as a potential means of releasing the hydrogen stored in the hydride and the water. However, the hydrolysis of LB occurs only above 0 °C and efficient catalysts are required to accelerate the hydrogen kinetics. Here, we demonstrate an efficient non-catalytical hydrogen generation system that enables H 2 production of LB over a wide range of temperatures with methanol (referred to MeOH), ethylene glycol, and MeOH/water mixtures as reaction solvents. The results indicate that the hydrogen kinetics of LB is controllable by MeOH dose, MeOH species, reaction temperature, and solution components. For instance, the hydrogen evolution rate could be accelerated from 266 to 515 mL H2 min −1 g −1 (per unit weight of LB) with a H 2 yield up to 93% by tailoring the dose of methanol at 25 °C. Notably, the glycolysis kinetics is much faster than that for the methanolysis of LB, delivering a hydrogen rate varying from 523 to 10,125 mL H2 min −1 g −1 . By optimizing reaction conditions, a gravimetric hydrogen density of ~4.6 wt% H 2 was realized in the LB-MeOH system. Interestingly, the methanolysis/glycolysis products of LB can spontaneously convert into MeOH and hydrated byproduct (LiBO 2 ‧2H 2 O) by reacting with water, and MeOH may be separated and reused as an intermediate. Here, LiBO 2 ‧2H 2 O can be easily regenerated back to LB by ball milling with Mg under ambient conditions. Thus, a hydrogen cycle combining hydrogen generation and storage in a closed material cycle is achieved, which may lay the foundation for developing practical hydrogen sources for mobile/portable applications.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2015
·
IF 3.313
Liuting Zhang,Jiaguang Zheng,Lixin Chen,Xuezhang Xiao,Teng Qin,Yiqun Jiang,Shouquan Li,Hongwei Ge,Qidong Wang
Mg(BH 4 ) 2 is considered as one of the most promising light metal complex hydrides because of its high volumetric and gravimetric hydrogen capacities and world-wide abundance. However, its higher major desorption temperatures (above 300 °C) and poor reaction kinetics have to be improved for the practical application. Herein, Mg(BH 4 ) 2 was successfully synthesized via wet-chemical technique and a significant enhancement in dehydrogenation performance of Mg(BH 4 ) 2 is achieved by the synergetic effect of fluorographite (FGi) and LiBH 4 . Under the effect of FGi, the hydrogen desorption of 6 Mg(BH 4 ) 2 -4FGi composite could be completed below 170 °C in seconds. However, the hydrogen released from 6 Mg(BH 4 ) 2 -4FGi suffers from impurities of B 2 H 6 and HF. More importantly, it is demonstrated that almost all the B 2 H 6 and HF impurities can be suppressed by synergetic modifying Mg(BH 4 ) 2 with FGi and LiBH 4 . The 3 Mg(BH 4 ) 2 –3LiBH 4 -4FGi composite exhibits a capacity over 8.0 wt% H 2 and starts to release hydrogen at 125.7 °C, which is 143.8 °C and 254.3 °C lower than that of pure Mg(BH 4 ) 2 and LiBH 4 , respectively. These significant improvements could be attributed to both the novel morphology that numerous nano-scale borohydride spots formed on the surface of FGi, and the formations of stable fluorides (MgF 2 and LiF) from the interaction between borohydrides and FGi.
研究领域:
材料科学
·
能源化学
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2018
·
IF 4.484
Yiwen Zhang,Xuezhang Xiao,Bosang Luo,Xu Huang,Meijia Liu,Lixin Chen
A significant improvement in reversible de/rehydrogenation properties of MgH2 doped with 2.5 wt % LiAlH4 and 2.5 wt % LiBH4 additives is achieved by reactive ball milling. Careful comparison studies show that a small amount (total mass ratio of ≤5 wt %) of LiBH4 and/or LiAlH4 can improve the hydrogen desorption performance of MgH2 in terms of reducing hydrogen desorption temperature, enhancing hydrogen desorption kinetics, and increasing hydrogen capacity. In particular, the MgH2 co-doped with LiAlH4–LiBH4 exhibits the best dehydrogenation properties, which starts to release hydrogen at about 280 °C and releases a high hydrogen capacity of 7.62 wt % with superior reaction kinetics. The activation energy of hydrogen desorption is decreased from 187.8 kJ/mol (ball-milled MgH2) to 155.8 kJ/mol. It can also uptake 7.7 wt % H2 within 15 min at 300 °C with a stable hydrogen absorption kinetics in the first 10 cycles. This synergistic effect of LiBH4 and LiAlH4 additives on improved hydrogen absorption/desorption properties is attributed to the in situ formation of Li3Mg7, Mg17Al12, and MgAlB4 new phases acting as the “catalytic active sites” to facilitate the diffusion of hydrogen through the reaction barriers in the de/hydrogenation cycles of MgH2. Moreover, these new phases can be rehydrogenated into MgH2, LiBH4, and Li3AlH6 hydrides, which further enhance the hydrogen capacity of co-doped sample more than the theoretical capacity of primitive MgH2.
研究领域:
材料科学
·
氢能
·
固态化学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2015
·Vol. 40
·期 33
·10527-10535
·
IF 3.313
Guoping Tu,Xuezhang Xiao,Yiqun Jiang,Teng Qin,Shouquan Li,Hongwei Ge,Qidong Wang,Lixin Chen
LiBH 4 is an attractive material for hydrogen storage owing to its high hydrogen capacity of 13.8 wt% capacities. However, its high thermodynamic stability and sluggish kinetics limit its practical application as an onboard hydrogen storage medium. In this work, a synergetic effect of NbCl 5 and hexagonal BN (h-BN) on notably improving the dehydrogenation properties of LiBH 4 was investigated. It is found that the addition of NbCl 5 and h-BN co-dopants can significantly enhance the dehydrogenation kinetics of LiBH 4 , and the catalytic effect of co-dopant is better than that of NbCl 5 or h-BN dopant separately. The NbCl 5 /h-BN co-doped LiBH 4 can release 10.78 wt% hydrogen, which is about 13 times and 5 times more than that of the NbCl 5 doped LiBH 4 and h-BN doped LiBH 4 within 10 min at 400 °C, respectively. The major dehydrogenation temperature of NbCl 5 /h-BN co-doped LiBH 4 is reduced to 377 °C, much lower than that of ball-milled LiBH 4 (464 °C). The apparent activation energy ( E a ) of hydrogen desorption is reduced from 195.81 kJ/mol of LiBH 4 to 122.75 kJ/mol of NbCl 5 /h-BN co-doped LiBH 4 . The microstructural results reveal that the catalytic effect of NbCl 5 /h-BN co-dopant on improving the dehydrogenation kinetics of LiBH 4 could be ascribed to the in situ formed nano NbH@h-BN, which serves as the heterogeneous nucleation site to reduce the decomposition activation energy barrier of LiBH 4 and shortens the distance of the solid–liquid phase boundary movement of LiBH 4 decomposition.
研究领域:
材料科学
·
氢气储存
·
能源材料
·
固态化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）