International Journal of Minerals Metallurgy and Materials
·
2023
·Vol. 30
·期 11
·2270-2279
·
IF 4.8
Zhong Tao,Zhang Haoyu,Song Mengchen,Jiang Yiqun,Shang Danhong,Wu Fuying,Zhang Liuting
The catalytic effect of FeCoNiCrMo high entropy alloy nanosheets on the hydrogen storage performance of magnesium hydride (MgH 2 ) was investigated for the first time in this paper. Experimental results demonstrated that 9wt% FeCoNiCrMo doped MgH 2 started to de-hydrogenate at 200°C and discharged up to 5.89wt% hydrogen within 60 min at 325°C. The fully dehydrogenated composite could absorb 3.23wt% hydrogen in 50 min at a temperature as low as 100°C. The calculated de/hydrogenation activation energy values decreased by 44.21%/55.22% compared with MgH 2 , respectively. Moreover, the composite’s hydrogen capacity dropped only 0.28wt% after 20 cycles, demonstrating remarkable cycling stability. The microstructure analysis verified that the five elements, Fe, Co, Ni, Cr, and Mo, remained stable in the form of high entropy alloy during the cycling process, and synergistically serving as a catalytic union to boost the de/hydrogenation reactions of MgH 2 . Besides, the FeCoNiCrMo nanosheets had close contact with MgH 2 , providing numerous non-homogeneous activation sites and diffusion channels for the rapid transfer of hydrogen, thus obtaining a superior catalytic effect.
研究领域:
材料科学
·
能源存储
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DOI
高影响因子
CHINESE CHEMICAL LETTERS
·
2024
·
IF 9.4
Shuai Li,Liuting Zhang,Fuying Wu,Yiqun Jiang,Xuebin Yu
Hydrogen, as a cheap, clean, and cost-effective secondary energy source, performs an essential role in optimizing today's energy structure. Magnesium hydride (MgH 2 ) represents an attractive hydrogen carrier for storage and transportation, however, the kinetic behavior and operating temperature remain undesirable. In this work, a dual-phase multi-site alloy (MsA) anchored on carbon substrates was designed, and its superior catalytic effects on the hydrogen storage properties of MgH 2 were reported. Mechanism analysis identified that multi-site FeNi 3 /NiCu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH 2 -MsA systems. Concretely, the unique multi-metallic site structure attached to the surface of MgH 2 provided substantial reversible channels and accessible active sites conducive to the adsorption, activation, and nucleation of H atoms. In addition, the coupling system formed by FeNi 3 and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH 2 and H atoms. Hence, the onset dehydrogenation temperature of MgH 2 + 5 wt% MsA was reduced to 195°C and the hydrogen desorption apparent activation energy was reduced to 83.6 kJ/mol. 5.08 wt% H 2 could be released at 250°C in 20 min, reaching a high dehydrogenation rate of 0.254 wt% H 2 /min, yet that for MgH 2 at a higher temperature of 335°C was only 0.145 wt% H 2 /min. Then, the dehydrogenated MgH 2 -MsA sample could absorb hydrogen from room temperature (30°C) and charge 3.93 wt% H 2 at 100°C within 20 min under 3.0 MPa H 2 pressure. Benefiting from carbon substrates, the 5 wt% MsA doped-MgH 2 could still maintain 6.36 wt% hydrogen capacity after 20 cycles. In conclusion, this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
研究领域:
材料科学
·
能源存储
·
催化
·
氢能技术
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Dongqiang Gao,Liuting Zhang,Mengchen Song,Fuying Wu,Jiao Wang,Hu Zhao,Hong Li
As a high-density solid-state hydrogen storage material, magnesium hydride (MgH 2 ) is promising for hydrogen transportation and storage. Yet, its stable thermodynamics and sluggish kinetics are unfavorable for that required for commercial application. Herein, nickel/vanadium trioxide (Ni/V 2 O 3 ) nanoparticles with heterostructures were successfully prepared via hydrogenating the NiV-based two-dimensional layered double hydroxide (NiV-LDH). MgH 2 + 7 wt% Ni/V 2 O 3 presented more superior hydrogen absorption and desorption performances than pure MgH 2 and MgH 2 + 7 wt% NiV-LDH. The initial discharging temperature of MgH 2 was significantly reduced to 190 °C after adding 7 wt% Ni/V 2 O 3 , which was 22 and 128 °C lower than that of 7 wt% NiV-LDH modified MgH 2 and additive-free MgH 2 , respectively. The completely dehydrogenated MgH 2 + 7 wt% Ni/V 2 O 3 charged 5.25 wt% H 2 in 20 min at 125 °C, while the hydrogen absorption capacity of pure MgH 2 only amounted to 4.82 wt% H 2 at a higher temperature of 200 °C for a longer time of 60 min. Moreover, compared with MgH 2 + 7 wt% NiV-LDH, MgH 2 + 7 wt% Ni/V 2 O 3 shows better cycling performance. The microstructure analysis indicated the heterostructural Ni/V 2 O 3 nanoparticles were uniformly distributed. Mg 2 Ni/Mg 2 NiH 4 and metallic V were formed in-situ during cycling, which synergistically tuned the hydrogen storage process in MgH 2 . Our work presents a facile interfacial engineering method to enhance the catalytic activity by constructing a heterostructure, which may provide the mentality of designing efficient catalysts for hydrogen storage.
研究领域:
材料科学
·
能源存储
·
纳米技术
·
化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Ruihan Li,Feng Hu,Ran Wu,Jianyi Xu,Jin Xu,Zhonghui Hou,Min Zhou,Junyu Bai,Yanghuan Zhang
In the present study, the synthesis of NdMg 12 + x wt%Ni( x = 0, 5, 10, 15) alloy was effectively accomplished through the technique of ball milling , and the profound impact of Ni on the microstructural attributes, as well as the hydrogen absorption and desorption characteristics of NdMg 12 alloy, was meticulously examined. The microstructural analysis reveals that Ni can notably facilitate the development of nanocrystalline and amorphous structural configurations. Subsequent investigations uncovered that a portion of Ni was transformed into the Mg 2 Ni phase on the surface of the NdMg 12 alloy, thereby increasing the number of hydrogen absorption active sites and subsequently enhancing the hydrogen absorption and desorption capabilities of the NdMg 12 +Ni alloy. A thermodynamic analysis reveals that the incorporation of Ni exerts a substantial elevating effect on the hydrogen desorption plateau pressure of NdMg 12 +Ni alloy. As the Ni content escalates from 0 wt% to 5 wt%, the enthalpy of the hydrogen desorption process plummets significantly, from 89.1888 kJ/mol H 2 to 80.2806 kJ/mol H 2 . Concurrently, the addition of Ni markedly diminishes the hysteresis coefficient during hydrogen absorption and desorption, thereby enhancing the overall hydrogen absorption and desorption efficiency of NdMg 12 +Ni alloy. Moreover, the inclusion of Ni not only expedites the hydrogen absorption rate within the NdMg 12 +Ni alloy but also substantially diminishes the activation energy for hydrogen desorption, effectively lowering the minimal hydrogen desorption temperature from 261℃ to 199℃. Notably, the NdMg 12 + 10 wt%Ni alloy exhibited the lowest activation energy (Ea = 114.4995 kJ/mol) and demonstrated superior hydrogen desorption kinetics.
研究领域:
材料科学
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金属氢化物
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储能材料
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固态储氢
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物理化学
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合金设计
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纳米材料
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
He Zhang,Yong Liu,Guodong Miao,Zhihui Ma,Feng Sun,Aimin Ju,Xuanhui Qu,Ping Li
TiFe hydrogen storage alloys possess the merits of abundance on earth and availability at ambient temperature in ever-growing applications but suffer from the challenge of complicated activation. Herein, FeCl 3 , which has synergistic effects of deoxygenation and pore formation, is reported to address this issue. For one thing, the production of oxygen vacancies and weakened Ti O interactions in TiFe alloys accelerate hydrogen absorption. For another, tailored defects fabricated by FeCl 3 , such as pores and cracks, harmoniously facilitate hydrogen transportation. Consequently, it enables the oxygen content of the sintered TiFe alloy to be as low as 0.29 wt%, which delivers a marvelous hydrogen absorption capacity of 1.67 wt% at 25 °C almost without incubation. The deoxygenation mechanism and influence of the pore-forming effect on microstructure and hydrogen storage performance are unambiguously elucidated by atomic-scale characterizations and theoretical calculations. This work proposes deep insights into the hydrogenation kinetics mechanism of the up-to-date TiFe alloys and provides promising prospects to synthesize the high-performance and low-cost solid-state hydrogen storage materials.
研究领域:
材料科学
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金属功能材料
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固态储氢
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表面与界面化学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
RARE METALS
·
2025
·
IF 11
Ya-Ke Wu,Kai Jia,Fu-Ying Wu,Bei-Bei Xiao,Ting Bian,Hu Liu,Hong Li,Liu-Ting Zhang
en Weakening the electrostatic attraction between Mg 2+ ions and H − ions in MgH 2 is vital for improving the kinetic performance of MgH 2 for hydrogen storage. Herein, a multivalent microenvironment is synergistically created by Mn and Mg 2 Ni to break the stable structure of MgH 2 , enabling rapid and stable de/hydrogenation performance. Specifically, the catalyzed MgH 2 system rapidly emits 5.98 wt% H 2 at 265°C within just 20 min and swiftly absorbs 6.24 wt% H 2 at 150°C in a mere 10 min. Microscopic characterization shows that a tight interface is formed between Ni and Mn 2 O 3 , which provides a stable anchor point for the formation of hydrogen pumps. Additionally, the multivalency of Mn and abundant oxygen vacancies accelerate the electron transfer and provide the shortest path for H dissociation. Moreover, density functional theory (DFT) indicates that Mg-H is extracted from 0.173 to 0.204 nm after modification, achieving a reduced decomposition energy of MgH 2 . Besides, 97.8% reversible hydrogen storage capacity was maintained after 30 cycles, presenting prominent potential for practical applications. 摘要 zh 削弱MgH 2 中Mg 2+ 离子与H − 离子之间的静电吸引力对于提升MgH 2 作为氢储存材料的动力学性能至关重要。在此,通过Mn与Mg 2 Ni的协同作用,构建了多价微环境,打破了MgH 2 的稳定结构,从而实现了快速且稳定的脱氢和加氢性能。具体而言,催化后的MgH 2 体系在265°C下仅需20分钟即可快速释放5.98 wt%的H 2 ,并在150°C下仅需10分钟即可迅速吸收6.24 wt%的H 2 。微观表征显示,Ni与Mn 2 O 3 之间形成紧密界面,为氢泵的形成提供了稳定的锚定点。并且,锰的多价性和丰富的氧空位加速了电子转移,并为氢的解离提供了最短路径。此外,DFT表明,经过改性后,Mg-H键键长从0.173 nm增加至0.204 nm,从而降低了MgH 2 的结合能。此外,经过30个循环后,可逆氢储存容量仍保持在97.8%,展现出显著的实际应用潜力。
研究领域:
材料科学
·
能源化学
·
固态储氢
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纳米催化
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Yi Liu,Weiqi Sun,Zhicheng Yang,Ruoyang Zhang,Bin Li,Lixian Sun,Fen Xu,Wenwei Guo,Conglong Shi,Ting Yu,Zhengyi Liang,Qingjie He
Magnesium hydride (MgH 2 ), recognized as a promising alternative energy material to replace fossil fuels, possesses distinct advantages, including higher stability and hydrogen storage capacity. Nevertheless, its widespread application remains limits due to intrinsic drawbacks such as high thermodynamic stability and sluggish hydrogen adsorption-desorption kinetics. Coral-like NiO/NiFe 2 O 4 heterojunction catalysts were efficaciously synthesized through a conventional hydrothermal-calcination method in our work. These catalysts were subsequently ball-milled with MgH 2 to obtain the MgH 2 –NiO/NiFe 2 O 4 composite. A comprehensive series of hydrogen storage performance (HSP) evaluations demonstrated that the composite exhibits markedly enhanced hydrogen adsorption-desorption characteristics. Specifically, MgH 2 –NiO/NiFe 2 O 4 initiated hydrogen release at 188 °C, which represents a 133 °C decrease compared with ball-milled MgH 2 . At 275 °C, its composite released 6.2 wt% H 2 within 20 min, while at a hydrogen absorption temperature of 100 °C, it absorbed 4.4 wt% H 2 within 30 min. Besides, the composite dehydrogenation activation energy was declined to 86.97 kJ/mol, a decrease of 62.17 kJ/mol relative to ball-milled MgH 2 . Mechanistic investigations revealed that NiO/NiFe 2 O 4 underwent in situ transformation into Mg 2 Ni and FeO during hydrogen adsorption-desorption process. Simultaneously, the reversible “Mg 2 NiH 4 /Mg 2 Ni” phase functioned as hydrogen pump, thereby accelerating the kinetics. First-principles calculations further demonstrated that Fe atoms in the in situ-generated FeO acquired electrons from the MgH 2 interface, which weakened the Mg–H bonds and facilitated hydrogen desorption. This electronic modulation of MgH 2 effectively enhanced its hydrogen adsorption-desorption dynamics and substantially lowered hydrogen desorption activation energy. To sum up, our study reports successful preparation of a binary transition-metal heterojunction catalyst, NiO/NiFe 2 O 4 , derived from Ni and Fe. The outcomes offer new thoughts into design and classification of transition-metal-based catalysts for hydrogen storage applications.
研究领域:
材料科学
·
能源化学
·
纳米催化
·
氢储能
·
固态储氢
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Tian Tian,Xuansheng Wang,Keke Shi,Fang Liu,Jiali Wang,Xiaoying Zhang,Shengting Li,Wei Chen,Yufei Song,Jinping Li,Guang Liu
Magnesium hydride (MgH₂) is deemed to a prospective high-capacity solid-state hydrogen storage material. However, slow kinetics and high desorption temperature severely limit its practical application. In this study, V₂O₃/C nanospheres composed of two-dimensional nanosheets were especially synthesized and employed as catalysts to enhance the hydrogen storage performance of MgH₂. The initial dehydrogenation temperature of the MgH₂-V₂O₃/C system was reduced to 200.4°C, with a dehydrogenation capacity of 6.69 wt%. At 300°C, the MgH₂ with 10 wt% V₂O₃/C catalyst could release 6.3 wt% H₂ in just 7 min and could start hydrogen absorption reaction at room temperature. The dehydrogenation activation energy (Ea) of the MgH₂-10 wt% V₂O₃/C system was calculated to be 88.96 ± 4.66 kJ/mol, representing an approximate 34.8 % reduction compared to the 136.43 ± 4.32 kJ/mol of ball-milled (BM) MgH₂. Moreover, the sample demonstrated exceptional cyclic stability, remaining the hydrogen storage capacity of 99.5 % after 30 cycles. In this system, in-situ elemental vanadium serves as the catalytic active site and plays a crucial catalytic role. Additionally, the carbon material helps prevent the agglomeration of MgH₂. The combined effect of these two components significantly improves the kinetic property for the MgH₂ system.
研究领域:
材料科学
·
能源化学
·
纳米催化
·
固态储氢
·
物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2018
·
IF 3.779
Zan Jiang,Jianguang Yuan,Huanqing Han,Ying Wu
As an important member of complex hydrides , Mg(BH 4 ) 2 has a high gravimetric capacity (14.9 wt%). In this study, the Mg(BH 4 ) 2 was synthesized by the ion exchange method. Afterwards, the Mg(BH 4 ) 2 composites with different amounts (2, 5, 10, 25 and 50 wt%) of carbon nanotubes (CNTs) were prepared by mechanical milling. Effects of the CNTs on the microstructural evolution and hydrogen storage properties were investigated. The onset desorption temperature of the Mg(BH 4 ) 2 -5 wt% CNTs is decreased to lower temperature around 120 °C from 275 °C. The desorption plateau of Mg(BH 4 ) 2 -5 wt% CNTs is the highest, which ascribes that CNTs causes the reaction pathway change. Additionally, the Mg(BH 4 ) 2 -5 wt% CNTs shows the best dehydriding kinetics properties, and can desorb 6.04 wt% hydrogen within 2000 s at 300 °C. The dehydrogenation activation energy of the Mg(BH 4 ) 2 -5 wt% CNTs is decreased to 130.2 kJ/mol H 2 , which is much lower than that of pure Mg(BH 4 ) 2 .
研究领域:
材料科学
·
无机化学
·
能源材料
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纳米材料
·
固态储氢
✓ 已验证
DOI
高影响因子
Materials Today Energy
·
2020
·
IF 5.604
T. Huang,X. Huang,C. Hu,J. Wang,H. Liu,Z. Ma,J. Zou,W. Ding
In this work, one-dimensional NiMoO 4 and CoMoO 4 nanorods are prepared and introduced into MgH 2 to improve its hydrogen storage properties. It is observed that the MgH 2 –NiMoO 4 system exhibits lower dehydrogenation temperature and faster kinetics than the MgH 2 –CoMoO 4 system and pure MgH 2 , indicating the superior promoting effect of NiMoO 4 over CoMoO 4 . Concretely, NiMoO 4 reacts with MgH 2 during the first dehydrogenation to in situ form Mg 2 Ni and Mo 0 , both of which are crucial factors for the following hydrogen cycling process. The ‘Mg 2 Ni/Mg 2 NiH 4 ’ mutual transformation upon hydrogen release/uptake is the well-known ‘hydrogen pump’ effect which boosts the hydrogen storage performance of MgH 2 . Moreover, theoretical calculations reveal the dual roles of Mo 0 played for the hydrogen storage in MgH 2 : i) it accelerates the hydrogen de/absorption of MgH 2 through weakening the Mg–H bonding; ii) it facilitates the mutual ‘Mg 2 Ni/Mg 2 NiH 4 ’ transformation as the formation energy of Mg 2 NiH 4 decreases under the influence of Mo 0 , which we call ‘facilitated hydrogen pump’ effect in this work. Ascribing to the collaborative action between Ni- and Mo- containing species, the hydrogen storage kinetics of MgH 2 has been accelerated.
研究领域:
材料科学
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纳米材料
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能源化学
·
固态储氢
·
金属氢化物
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催化材料
·
理论计算
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2013
·
IF 2.39
H. Wang,J. Zhang,J.W. Liu,L.Z. Ouyang,M. Zhu
The addition of NaH by ball milling is shown to greatly improve the hydrogen storage properties and the hydrolysis properties of MgH 2 , which is related to the formation of ternary hydride NaMgH 3 with specific perovskite structure. The MgH 2 –10%NaH mixture exhibits better hydriding and dehydriding kinetics than the MgH 2 –10%LiH mixture, in which the LiMgH 3 with perovskite structure could not be formed. The catalytic role of NaMgH 3 is attributed to fast hydrogen mobility in the perovskite structure, which provides fast hydrogen diffusion pathways for the hydriding and dehydriding of MgH 2 . The NaMgH 3 also shows fast hydrolysis reaction kinetics without any passivation. Our work shows that such perovskite-type hydride demonstrates great potential as efficient catalysts for the high-capacity hydrides for whether reversible or irreversible hydrogen storage.
研究领域:
材料化学
·
无机化学
·
能源材料
·
氢储能
·
固态储氢
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2013
·Vol. 38
·期 25
·10932-10938
·
IF 3.548
H. Wang,J. Zhang,J.W. Liu,L.Z. Ouyang,M. Zhu
In this study, alkali hydroxides (NaOH, LiOH, KOH) were attempted as new-type catalytic additives to improve the hydrogen storage properties of MgH 2 by ball milling . It is shown that the additives readily react with the MgH 2 to form perovskite-structured NaMgH 3 and KMgH 3 , but not the LiMgH 3 . Although the in-situ formed perovskite hydrides remain stable during hydriding/dehydriding cycles, both NaMgH 3 and KMgH 3 show predominant catalytic role on the hydriding and dehydriding of MgH 2 . In contrast, the LiOH modified MgH 2 presents much inferior sorption kinetics because of the absence of LiMgH 3 . The catalytic mechanism of perovskite hydrides can be explained by the high hydrogen mobility in the perovskite structure . This study shows that such cheap hydroxides could be used as efficient catalysts to improve the hydrogen storage properties of high-capacity metal hydrides and complex hydrides .
研究领域:
材料科学
·
无机化学
·
能源化学
·
氢能存储
·
金属氢化物
·
固态储氢
·
催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）