JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2025
·
IF 6
Guo-Cui Mao,Jin-Peng Wang,Hui-Lin Jiang,Bao-Xia Dong,Yun-Lei Teng
We found that the activated LiBH 4 or Ni/LiBH 4 can effectively assist CO 2 hydrogenation into C1 and C2 products at low temperature (100–300 ℃). After CO 2 hydrogenation over the activated LiBH 4 or Ni/LiBH 4 , CH 4 with approximately 100 % selectivity was formed in the gas phase products. CH 3 OH, HCOO − , and high-value CH 3 CH 2 OH were observed in aqueous solution of spent LiBH 4 or Ni/LiBH 4 after CO 2 hydrogenation. CO 2 conversion and CH 4 production are able to be further improved by doping 5–20 wt% Ni into the activated LiBH 4 . The LiBH 4 sample shows a 61.34 % CO 2 conversion at 200 ℃, while the 20 %Ni/LiBH 4 composite displays an 80.14 % CO 2 conversion under the same conditions. The experimental and theoretical results suggest that the synergistic effect from Ni and LiBH 4 results in high CO 2 conversion at low temperature. This new method for CO 2 conversion to C1, C2 products using the activated Ni/LiBH 4 composite may enlighten the materials design for CO 2 utilization.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2017
·
IF 3.133
Dandan Peng,Yuan Li,Yang Liu,Lu Zhang,Hongming Zhang,Zhenmin Ding,Shumin Han
In this paper, a magnesium hydride-carbon composite (MgH 2 @CS) was successfully synthesized by hydrogenation, employing magnesium powder and carbonized-starch (CS) as the raw material. The as-prepared MgH 2 @CS was ball-milled with LiBH 4 to constitute a novel Li–Mg–B–H system (2LiBH 4 –MgH 2 @CS). Compared with the primary 2LiBH 4 –MgH 2 , the 2LiBH 4 –MgH 2 @CS composite showed a significant improvement in hydrogen storage performance. Temperature programmed desorption (TPD) analyses show that the 2LiBH 4 –MgH 2 @CS composite starts to slowly release hydrogen at about 150 °C, which is 245 °C lower than that of the pure 2LiBH 4 –MgH 2 ; the final hydrogen desorption capacity reaches 9.3 wt% (LiBH 4 with a weight loss of 7.0 wt%). In particular, the capacity retention rate of 2LiBH 4 –MgH 2 @CS reaches 80.5% after five reversible de/hydrogenation cycles at 400 °C. Microstructure analyses reveal that the CS with lamellar structure could not only serve as a support for anchoring well-dispersed MgH 2 nanoparticles , but could also effectively prevent the aggregation and growth of Mg and magnesium hydrides during de/hydrogenation. Furthermore, the homogeneous nanosized Mg that is generated from decomposition of MgH 2 @CS has high reactivity, which could accelerate the decomposition of LiBH 4 and meanwhile shorten the incubation period of MgB 2 , thereby greatly enhancing the kinetics of dehydrogenation . These studies provide us with fundamental insights into the design of the Li–Mg–B–H system.
研究领域:
材料科学
·
能源储存与转换
✓ 已验证
DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2020
·Vol. 22
·期 7
·4096-4105
·
IF 3.43
Zhixiang Liu,Mengyuan Xiang,Yao Zhang,Huaiyu Shao,Yunfeng Zhu,Xinli Guo,Liquan Li,Hui Wang,Wanqiang Liu
LiBH4 is one of the most promising solid electrolyte materials for use in solid-state batteries because its hexagonal phase above 110 °C offers Li-ion conductivity of almost 10−3 S cm−1. However, near room temperature, its orthorhombic phase delivers Li-ion conductivity of only 10−8 S cm−1, which considerably hampers its further applications. In the present study, a highly disordered interface between LiBH4 and two-dimensional MoS2 in the composite material was formed, yielding ionic conductivity of 10−4 S cm−1 at room temperature. LiBH4 and MoS2 are found to be in close contact without the formation of any intermediate phase at the interface. First-principles calculations employing density functional theory (DFT) and the nudged elastic band (NEB) method reveal that the migration energy barrier on three specific pathways could be established via microstructure analyses. It was found that the interface between the two phases yields the lowest Li-ion diffusion barrier among all the possible Li-ion pathways; further, the superior conductivity of the composite could be attributed to the interface with high Li-ion conductivity. This study proposes a new strategy for designing solid electrolytes and provides certain possibilities for two-dimensional materials to serve as superior solid electrolytes.
研究领域:
材料科学
·
固态电池研究
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Xueye Zhuang,Shiman He,Long Hu,Qian Shi,Hui Wang,Renzong Hu
LiBH 4 has been considered as a promising solid electrolyte for lithium-ion batteries. However, the low ionic conductivity at room temperature has been the biggest challenge of LiBH 4 solid-state electrolyte (SSE) toward practical solid-state batteries. In this work, a ternary electrolyte is designed and prepared by milling LiBH 4 with LiNH 2 and interfacially decorated with g-C 3 N 4 . It is revealed that the soft dispersed phase of two-dimensional g-C 3 N 4 can build an effective transportation network in the composite electrolyte, thereby decreasing the interfacial impedance and reducing the energy barrier for lithium ion diffusion. The optimized SSE, LiBH 4 -2LiNH 2 -g-C 3 N 4 -10 % (LBN-CN-10 %), exhibits an ionic conductivity of 1.5×10 −3 S cm −1 , five orders of magnitude higher than that of the LiBH 4 electrolyte at 30 °C. The LiIn symmetric cell with LBN-CN-10 % electrolyte delivers a low polarization of ∼89 mV over 10,000 h. When assembling with Li 4 Ti 5 O 12 cathode, the all-solid-state battery exhibits excellent cycling over 1000 cycles at 30 ℃, achieving a breakthrough in the lifetime of solid-state batteries with LiBH 4 -based electrolyte. Moreover, the all-solid-state battery with LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode also delivers a discharge plateau at 3.0 V, revealing the high voltage withstanding of LBN-CN-10 % electrolyte. This work provides new options for the development and practical application of room-temperature hydride all-solid-state batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2017
·Vol. 7
·期 9
·1838-1847
·
IF 5.773
Yi Zhang,Zhenyun Lan,Ni Jian,Zhuanghe Ren,Jianjiang Hu,Mingxia Gao,Hongge Pan,Yunhao Lu,Yongfeng Liu
In this work, we demonstrate a first attempt at understanding the catalytic mechanism of nanosized Co in reducing the dehydrogenation temperature of the Li–B–N–H hydrogen storage system by experimental observation and theoretical calculation. A nanosized Co@C composite (Co particles <10 nm) is successfully synthesized by casting a furfuryl alcohol-filled, Co-based metal–organic framework, MOF-74(Co), at 700 °C. Adding small quantities of the prepared nanosized Co@C composite significantly reduces the dehydrogenation temperature of the LiBH4–2LiNH2 system. The 5 wt% Co@C-containing sample releases approximately 10.0 wt% hydrogen at 130–230 °C with a peak temperature of 210 °C, which is reduced by 125 °C from that of the pristine sample. During hydrogen desorption, nanosized Co remains in the metallic state and only works as a catalyst to reduce the kinetic barriers of hydrogen release from the LiBH4–2LiNH2 system. Ab initio calculations reveal that the presence of a Co catalyst induces a redistribution of charge, which not only weakens the chemical H–B bonding but also enhances the electrostatic interactions between Hδ+ in the NH2 groups and Hδ− in the BH4 groups, consequently reducing the energy barriers for the formation of H2 molecules. This explains the low-temperature dehydrogenation behaviour of the Co-catalysed Li–B–N–H systems.
研究领域:
材料科学
·
能源化学
·
催化化学
·
氢能源存储
·
纳米技术
✓ 已验证
DOI
高影响因子
RARE METALS
·
2025
·Vol. 44
·期 4
·2379-2392
·
IF 11
Na Guo-Quan,Cui Wen-Gang,Shi Hang-Yan,Li Zheng-Long,Gao Fan,Wang Xing-Qiang,Wang Ke,Gao Yong,Yang Ya-Xiong,Shen Zi-Chao,Pan Hong-Ge
High-capacity LiBH 4 is a promising solid hydrogen storage material. However, the large electron cloud density between the B-H bonds in LiBH 4 induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics. To solve the above problems, it is proposed to enhance the hydrogen storage properties of LiBH 4 through the synergistic effect of Brønsted and Lewis acid in Hβ zeolite. Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling. At a LiBH 4 -to-Hβ mass ratio of 6:4, the 6LiBH 4 -4Hβ system released hydrogen at 190 °C and achieved a hydrogen release capacity of 7.0 wt% H 2 upon heating to 400 °C. More importantly, the hydrogen release capacity of the system reached 6.02 wt% at 350 °C under isothermal conditions after 100 min and 7.2 wt% at 400 °C under isothermal conditions after 80 min, whereas the pristine LiBH 4 only achieved 2.2 wt%. The improvement in hydrogen storage performance of the system was mainly attributed to two factors: (i) Lewis acid sites with acceptable electrons in the Hβ weaken the electron density of B–H bonds in LiBH 4 , and (ii) the H + proton from the Brønsted acid sites and H − of LiBH 4 undergo a H + + H − = H 2 reaction. Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβ zeolite are conducive to the weakening of B – H bonds and that storage charge transfer occurs near the Lewis acid sites. The present work provides new insights into improving the hydrogen storage performance of LiBH 4 by weakening the B–H bonds in the LiBH 4 .
研究领域:
能源存储
·
催化
·
材料科学
·
无机化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2020
·
IF 4.939
Jiaguang Zheng,Zhendong Yao,Xuezhang Xiao,Xuancheng Wang,Jiahuan He,Man Chen,Hao Cheng,Liuting Zhang,Lixin Chen
Novel porous hollow carbon nanospheres (HCNS) have been synthesized and utilized as scaffold for LiBH 4 –Mg(BH 4 ) 2 eutectic borohydride (LMBH). Large loading amounts of LMBH (33, 50 and 67 wt%) have been melt-infiltrated into HCNS, and the significantly improved dehydrogenation properties have been discovered. The LMBH@HCNS composites not only exhibit high actual dehydrogenation amounts and fast hydrogen desorption rates, but also an increased reversible hydrogen storage capacities after three cycles without obvious degradation. Further structural tests have revealed that the over-infiltrated LMBH covering the spherical surface of HCNS could also contribute to the improved hydrogen storage behaviors, due to a strong interfacial adhesion effect that avoid LMBH from aggregation during de/rehydrogenation cycles.
研究领域:
材料科学
·
化学工程
·
能源存储
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2016
·Vol. 41
·期 39
·17462-17470
·
IF 3.205
Bing Zhai,Xuezhang Xiao,Wenping Lin,Xu Huang,Xiulin Fan,Shouquan Li,Hongwei Ge,Qidong Wang,Lixin Chen
NbF 5 and eutectic 0.68LiBH 4 –0.32Ca(BH 4 ) 2 were successively infiltrated into highly ordered mesoporous carbon (CMK-3) to obtain a LiBH 4 –Ca(BH 4 ) 2 –NbF 5 @CMK-3 composite. A synergetic effect of nanoconfinement and catalysis on hydrogen desorption properties of the composite was achieved. The onset desorption temperature of LiBH 4 –Ca(BH 4 ) 2 –NbF 5 @CMK-3 is dramatically lower than 120 °C compared with that of as-milled LiBH 4 –Ca(BH 4 ) 2 or LiBH 4 –Ca(BH 4 ) 2 @CMK-3. A hydrogen amount as high as 13.3 wt% can be released within 250 min for LiBH 4 –Ca(BH 4 ) 2 –NbF 5 @CMK-3, compared with only 10.4 wt% for pure LiBH 4 –Ca(BH 4 ) 2 , in which nanoconfinement and catalysis both make some contribution. The cycling hydrogen desorption performance of the composite becomes better likewise due to the addition of NbF 5 . Further microstructure analysis reveals that F − tended to bind with Ca 2+ to form CaF 2 , whereas Nb compound is believed to catalyze the whole system in the form of Nb-based boride (NbB 2 ).
研究领域:
材料科学
·
能源化学
·
纳米科技
·
储氢材料
·
物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yuchen Pang,Xuechun Hu,Xiaoyue Zhang,Xuebin Yu,Guanglin Xia
LiBH 4 , with its ultrahigh hydrogen capacity of 18.5 wt%, is regarded as a promising solid-state hydrogen storage material; however, its high thermodynamic stability and sluggish kinetics severely hinder practical application. In this study, two-dimensional Co-based high-entropy metal oxide nanoplates, (CoNiMnFeCr) 3 O 4 (HEO), were synthesized as catalysts to enhance the hydrogen storage performance of LiBH 4 . Benefiting from the unique multicomponent synergy and abundant oxygen vacancies generated by lattice distortions, HEO significantly lowers the dehydrogenation temperature of LiBH 4 . Specifically, in the case of LiBH 4 catalyzed by 30 wt% HEO, the onset and peak hydrogen release temperatures decrease to 100.0 °C and 364.8 °C, respectively—reductions of 175 °C and 130 °C compared with pristine LiBH 4 . The decomposition fractions of LiBH 4 before 250 °C and 400 °C increase from 2 % and 16 % (without catalyst) to 29 % and 61 %, respectively. Moreover, the catalytic effect of HEO surpasses that of mixed metal oxides and single-component Co-based oxides in reducing the dehydrogenation temperature of LiBH 4 . The dehydrogenation activation energy of LiBH 4 is reduced by 37.37 kJ mol −1 H 2 , enabling complete hydrogen desorption within 1 h at 380 °C, demonstrating excellent dehydrogenation kinetics. During the first two cycles, Co B-like high-entropy borides are formed in-situ on the surface of HEO through reaction with LiBH 4 , which effectively prevents further hydrogen capacity loss and catalyzes subsequent H 2 absorption/desorption cycles. After 10 cycles, the reversible H 2 capacity of LiBH 4 under the catalysis of HEO stabilizes at 6.38 wt%, corresponding to a capacity retention of 66.7 %.
研究领域:
储能
·
纳米材料
·
储氢材料
·
催化
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yongyang Zhu,Liming Zeng,Daifeng Wu,Renheng Tang,Qing Zhou
The lack of cost-effective regeneration techniques for LiBH 4 limits its large-scale applications for supplying hydrogen via hydrolysis. Now, we report a facile method to regenerate LiBH 4 by ball milling its real hydrolytic byproduct (LiBO 2 · x H 2 O) with cheap Al based reducing agents, instead of traditional Mg. Effective strategies are developed to promote the formation of LiBH 4 by introducing Li 2 O to enable the dense Al 2 O 3 to convert into LiAlO 2 on Al surface and break up passivation layers, and by partially replacing Al with Al-RE alloy to improve grinding and contacting efficiency of raw materials and facilitate the conversion from initial H + in LiBO 2 ·2H 2 O to final H ¯ in LiBH 4 . A yield of 10.4 % can be obtained for a relatively short ball milling time (10 h) for the Al-Al 2 Ce-Li 2 O-LiBO 2 ·2H 2 O system. Another advantage of this method is that the utilization of H + source in LiBO 2 ·2H 2 O improves energy efficiency and reduces the cost. This work broadens the species of reducing agents for borohydride regeneration and enriches its regeneration methods.
研究领域:
材料科学
·
化学工程
·
氢气储存
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2013
·
IF 2.39
Pei Pei Yuan,Bin Hong Liu,He Peng Zhu,Wei Yuan Pan,Zhou Peng Li
In this work, the composites of LiBH 4 and AlF 3 were prepared and their hydrogen storage properties were investigated. The AlF 3 addition to LiBH 4 resulted in significant decreases in dehydrogenation temperature. All the x LiBH 4 + AlF 3 ( x = 1, 2, 3, 5) composites started to release hydrogen from about 100 °C. The dehydrogenation of the composites was accomplished through several steps, depending on the molar ratio of LiBH 4 to AlF 3 . A new phase Li 3 AlF 6 was formed during the first dehydrogenation step, which further reacted with LiBH 4 . AlB 2 was formed only at temperatures higher than 300 °C. Li 2 B 12 H 12 was detected as an intermediate. The dehydrogenation reactions have significantly reduced and thus favorable enthalpy changes. However, the reversibility of the composites needs to be improved.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Yiqi Wei,Zhenglong Li,Zichong Chen,Panyu Gao,Qihang Ma,Mingxi Gao,Chenhui Yan,Jian Chen,Zhijun Wu,Yinzhu Jiang,Xuebin Yu,Xin Zhang,Yongfeng Liu,Yaxiong Yang,Mingxia Gao,Wenping Sun,Hongge Pan
LiBH4 is one of the most promising candidates for use in all-solid-state lithium batteries. However, the main challenges of LiBH4 are the poor Li-ion conductivity at room temperature, excessive dendrite formation, and the narrow voltage window, which hamper practical application. Herein, we fabricate a flexible polymeric electronic shielding layer on the particle surfaces of LiBH4. The electronic conductivity of the primary LiBH4 is reduced by 2 orders of magnitude, to 1.15 × 10–9 S cm–1 at 25 °C, due to the high electron affinity of the electronic shielding layer; this localizes the electrons around the BH4– anions, which eliminates electronic leakage from the anionic framework and leads to a 68-fold higher critical electrical bias for dendrite growth on the particle surfaces. Contrary to the previously reported work, the shielding layer also ensures fast Li-ion conduction due to the fast-rotational dynamics of the BH4– species and the high Li-ion (carrier) concentration on the particle surfaces. In addition, the flexibility of the layer guarantees its structural integrity during Li plating and stripping. Therefore, our LiBH4-based solid-state electrolyte exhibits a high critical current density (11.43 mA cm–2) and long cycling stability of 5000 h (5.70 mA cm–2) at 25 °C. More importantly, the electrolyte had a wide operational temperature window (−30–150 °C). We believe that our findings provide a perspective with which to avoid dendrite formation in hydride solid-state electrolytes and provide high-performance all-solid-state lithium batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）