CN107934913B - Preparation of transition metal fluoride doped composite hydrogen storage material and application thereof in hydrogen storage material - Google Patents
Preparation of transition metal fluoride doped composite hydrogen storage material and application thereof in hydrogen storage material Download PDFInfo
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Abstract
The invention discloses a transition metal fluoride doped composite hydrogen storage material, which is prepared from LiBH4、LiNH2、MgH2The composite hydrogen storage material is prepared by mixing the transition metal fluoride and mechanical ball milling, wherein the initial hydrogen releasing temperature of hydrogen releasing is ~ 100 ℃ at 90 ℃, the second hydrogen releasing temperature is about 150 ℃, the main hydrogen releasing is completed within the range of ~ 200 ℃ at 180 ℃, and the composite hydrogen storage material releases ~ 7.0.0 wt% of hydrogen when heated to 200 ℃.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials of new energy materials, in particular to a preparation method of a transition metal fluoride doped composite hydrogen storage material and application of the transition metal fluoride doped composite hydrogen storage material in the hydrogen storage material.
Background
The hydrogen energy is known as a new energy source in 21 century because of its characteristics of high efficiency, cleanness, renewability and the like, and is well paid attention by people in the world. The development and utilization of hydrogen energy relate to four key technologies such as preparation, storage, transportation and application of hydrogen gas, and the storage technology of hydrogen gas becomes a bottleneck of utilization of hydrogen energy towards practicality and scale due to the problems of flammability, explosiveness, easiness in diffusion, low volume energy density at normal temperature and normal pressure and the like of hydrogen gas. Therefore, the development of hydrogen storage technology with high energy density, high efficiency and safety is a key problem to be solved urgently today.
Among the numerous hydrogen storage materials, light metal borohydrides are considered to be one of the most promising systems of hydrogen storage materials. Wherein, LiBH4Has high hydrogen storage capacity of 18.3 wt percent and is a hydrogen storage material with great potential. But the high thermodynamic stability and slow hydrogen absorption and desorption kinetics can not meet the requirements of practical application.
In recent years, continuous research shows that the combination of amino compound and borohydride can effectively improve the dehydrogenation thermodynamic and kinetic properties. Pinkerton et al [ F.E. Pinkerton, C.P. Meisner, M.S. Meyer, M.P.Balough and M.D. Kundrate. Hydrogen desorption emission ten Li3BN2H8.Journal of Physical Chemistry B,2005, 109: 6-8.]LiBH is mixed according to a molar ratio of 1:24And LiNH2Compounding to prepare the novel Li-B-N-H system hydrogen storage material, wherein when the temperature is heated to ~ 350 ℃ to about 10 wt%, the hydrogen release capacity of the Li-B-N-H system is about 10 wt%, and the hydrogen release performance of the Li-B-N-H system is equal to that of LiBH4And LiNH2The ratio is remarkably improved, and the method attracts people's attention. Because of high kinetic barrier, the hydrogen release temperature is still high, and NH exists in the process of heating decomposition3Is discharged. Tang et al [ W.S. Tang, G.T. Wu, T.Liu, A.T.S. Wee, C.K. Yong, Z.T. Xiong, A.T. S.Hor, P.Chen.cobalt-catalyst hydrogen desorption from the LiNH2-LiBH4system. Dalton Trans. 2008:2395-2399.]The hydrogen release temperature of the Li-B-N-H system is obviously reduced by adding transition metal as a catalyst. To improve the hydrogen storage properties of the composite system, Yang [ J. Yang, A. Sudik, D.J. Siegel, D.Halliday, A.Drews, R.O. Carter, C.Wolferton, C.J.Lewis, J.W.A. Sachtler, J.J.Low, S.A.Faheem, D.A. Lesch and V Ozolins.A.Self-Catalyzing Hydrogen-StorageMaterial.Angewandte Chemie International Edition,2008, 47: 882-887.]Etc. have developed the reaction with LiBH4、LiNH2And MgH2A complex multi-component system hydrogen storage system. The system is an autocatalytic system and has better hydrogen storage performance: the initial hydrogen release temperature is about 150 ℃, and the kinetic and thermodynamic properties are improved to a certain extent; simultaneous NH3The release of (a) is suppressed. Meanwhile, the cycle performance of the modified material is also improved. However, it also has the following technical problems:
1. the initial hydrogen release temperature is still higher than 150 ℃;
2. two steps of hydrogen release are needed, the hydrogen release amount in the first step is small, the hydrogen release temperature in the second step is high, namely, the hydrogen release is started at 250 ℃, and the complete hydrogen release can be realized at 320 ℃.
Disclosure of Invention
The invention aims to provide a transition metal fluoride doped composite hydrogen storage material, a preparation method thereof and application thereof in the hydrogen storage material.
By doping transition metal fluoride, promoting the decomposition of intermediate products in the reaction process by using transition metal ions, and controlling the hydrogen release process, on one hand, the initial hydrogen release temperature of the whole hydrogen release process is reduced, on the other hand, the induction period of the second hydrogen release process which is used as a speed control step is greatly reduced, the hydrogen release temperature of the second hydrogen release is reduced, the two-step hydrogen release process is coordinated, finally, the hydrogen release process of a large amount is realized below 200 ℃, and the hydrogen storage material can release 7.0wt% hydrogen at 200 ℃.
The specific technical scheme for realizing the purpose of the invention is as follows:
transition metal fluoride doped composite hydrogen storage materials made from LiBH4、LiNH2、MgH2The composite hydrogen storage material is prepared by mixing and mechanically ball-milling transition metal fluoride which is nickel fluoride or cobalt fluoride, the composite hydrogen storage material discharges hydrogen in two steps, the initial hydrogen discharge temperature is 90 ℃ ~ 100 ℃, the second hydrogen discharge temperature is about 150 ℃, the main hydrogen discharge is completed within the range of 180 ℃ ~ 200 ℃, and when the composite hydrogen storage material is heated to 200 ℃, the composite hydrogen storage material discharges 6.5 wt% of ~ 7.0.0 wt% of hydrogen.
The preparation method of the transition metal fluoride doped composite hydrogen storage material comprises the following steps:
step 1) weighing raw materials according to LiBH4、LiNH2、MgH2The mass ratio of the LiBH to the transition metal fluoride is 1:2 (0 ~ 2) to (0 ~ 0.1.1), and LiBH is weighed4、LiNH2、MgH2And transition metal fluoride, mixing;
and 2) preparing the composite hydrogen storage material by a ball milling method, namely, putting the milling balls and the weighed raw materials in the step 1) into a ball milling tank according to a ball-to-material ratio of (100 ~ 200): 1, sealing, putting the ball milling tank into a ball mill, setting the ball milling time to be 1 ~ 3 h, and the ball milling rotation speed to be 100 ~ 300 r/min, and performing ball milling to obtain the transition metal fluoride-doped composite hydrogen storage material, wherein all the preparation steps are performed under the condition of inert gas.
The initial dehydrogenation temperature of the composite hydrogen storage material is 90 ℃ compared with LiBH (lithium borohydride) as detected by a temperature rise dehydrogenation experiment4-2LiNH2-MgH2The hydrogen storage material is reduced by 60 ℃; the hydrogen release rate is obviously accelerated, and LiBH is achieved at 200 DEG C4-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2The hydrogen storage material is capable of storing 6.8 wt% and 7.0wt% hydrogen, respectively, and LiBH4-2LiNH2-MgH2The hydrogen storage material only releases 3.3 wt% of hydrogen; the total hydrogen release at 300 ℃ reaches 8.3wt% and 8.5 wt%.
The detection of isothermal dehydrogenation experiment shows that the LiBH is prepared at 200 DEG C4-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2The hydrogen storage material can release 6.8 wt% and 7.0wt% hydrogen gas respectively in 20 min, and LiBH4-2LiNH2-MgH2The hydrogen storage material is only capable of evolving 3.3 wt% hydrogen.
Therefore, compared with the prior art, the invention has the following advantages:
1. the composite hydrogen storage material has lower hydrogen release temperature, and starts to release hydrogen at 90-100 ℃;
2. the composite material greatly reduces the induction period of the second hydrogen discharging process as a speed control step, and reduces the hydrogen discharging temperature of the second hydrogen discharging, namely, the hydrogen discharging is started when the original temperature is reduced from about 250 ℃ to about 150 ℃;
3. when the composite hydrogen storage material is heated to 200 ℃, a large amount of hydrogen is discharged, the hydrogen discharge amount can reach about 7.0wt%, and the composite hydrogen storage material has good dehydrogenation dynamic performance;
4. the composite hydrogen storage material has the advantages of low cost, wide source, simple synthesis method and process and easy large-scale production.
Therefore, the invention has certain application prospect in hydrogen storage materials.
Description of the drawings:
FIG. 1 is a LiBH prepared in examples 1 and 24-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2Temperature programmed dehydrogenation profile of the hydrogen storage material;
FIG. 2 is a LiBH prepared in examples 1 and 24-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2Constant temperature dehydrogenation curve at 200 ℃ for hydrogen storage materials.
Detailed Description
The invention is further described by the embodiments and the accompanying drawings in the specification, but the invention is not limited thereto.
Example 1
A transition metal fluoride doped composite hydrogen storage material, LiBH4-2LiNH2-MgH2-0.05NiF2The preparation method of the hydrogen storage material comprises the following steps:
step 1) weighing raw materials: weighing 0.088 g of LiBH in the presence of argon4、0.1856 g LiNH2、0.1064 g MgH2And 0.02 g of NiF2Powder, total 0.4 g;
step 2) preparing the composite hydrogen storage material by a ball milling method: under the protection of argon, the reaction kettle is,putting grinding balls and the raw materials weighed in the step 1) into a ball-milling tank and sealing according to the ball-material ratio of 200: 1; then putting the ball milling tank into a ball mill, setting the ball milling rotation speed to be 200 rpm, and setting the ball milling time to be 2 h to obtain LiBH4-2LiNH2-MgH2-0.05NiF2A hydrogen storage material.
Example 2
A transition metal fluoride doped composite hydrogen storage material, LiBH4-2LiNH2-MgH2-0.05CoF2The preparation method of the hydrogen storage material comprises the following steps:
step 1) weighing raw materials: weighing 0.088 g of LiBH in the presence of argon4、0.1856 g LiNH2、0.1064 g MgH2And 0.02 g CoF2Powder, total 0.4 g;
step 2) preparing the composite hydrogen storage material by a ball milling method: under the protection of argon, putting grinding balls and the weighed raw materials in the step 1) into a ball-milling tank and sealing according to the ball-material ratio of 200: 1; then putting the ball milling tank into a ball mill, setting the ball milling rotation speed to be 200 rpm, and setting the ball milling time to be 2 h to obtain LiBH4-2LiNH2-MgH2-0.05CoF2A hydrogen storage material.
In order to study the influence of different transition metal fluorides on the hydrogen storage performance of the composite hydrogen storage material, the LiBH of the composite hydrogen storage material doped with 2 different transition metal fluorides prepared in examples 1 and 2 was prepared4-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2The hydrogen storage material is tested by a temperature rise dehydrogenation experiment, and the temperature rise rate is 2 ℃/min.
The experimental result is shown in fig. 1, and it can be seen from the dehydrogenation curve that the hydrogen release performance of the transition metal fluoride doped composite hydrogen storage material is effectively improved. The initial dehydrogenation temperature is 90 ℃ in comparison with LiBH4-2LiNH2-MgH2The initial dehydrogenation temperature of the hydrogen storage material is reduced by 60 ℃; after heating to 200 deg.C, the large quantity of hydrogen is discharged, LiBH4-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2The hydrogen release amount of the hydrogen storage material reaches 7.0wt% and 6.8 wt% respectively; the hydrogen release amounts reached 8.5 wt% and 8.3wt%, respectively, at 300 ℃.
Isothermal dehydrogenation experiments of transition metal fluoride doped composite hydrogen storage materials.
The transition metal fluoride doped composite hydrogen storage material was subjected to isothermal dehydrogenation experiments at 200 ℃. The results are shown in FIG. 2, LiBH at 200 ℃ C4-2LiNH2-MgH2-0.05NiF2Hydrogen storage material and LiBH4-2LiNH2-MgH2-0.05CoF2The hydrogen storage material can respectively release 6.8 wt% and 7.0wt% of hydrogen in 20 min, and LiBH4-2LiNH2-MgH2The hydrogen storage material evolved only 3.3 wt% hydrogen.
Claims (2)
1. A transition metal fluoride doped composite hydrogen storage material, characterized in that: the material is prepared from LiBH4、LiNH2、MgH2The composite hydrogen storage material is prepared by mixing the transition metal fluoride and mechanically milling, wherein the transition metal fluoride is cobalt fluoride, the composite hydrogen storage material discharges hydrogen in two steps, the initial hydrogen discharging temperature is ~ 100 ℃ at 90 ℃, the second hydrogen discharging temperature is about 150 ℃, the main hydrogen discharging is completed within the range of 180 ℃ to ~ 200 ℃ and 35200 ℃, and the composite hydrogen storage material can discharge 6.5 wt% of ~ 7.0.0 wt% of hydrogen when heated to 200 ℃.
2. The method for preparing a composite hydrogen storage material according to claim 1, characterized by comprising the steps of:
step 1) weighing raw materials, namely weighing LiBH according to a certain mass ratio4、LiNH2、MgH2And transition metal fluoride mixed powder, said step 1) LiBH4、LiNH2、MgH2And a transition metal fluoride in an amount of LiBH4：LiNH2：MgH2Transition metal fluorides = 1:2 (0 ~ 2) (0 ~ 0.1.1);
step 2) preparing a composite hydrogen storage material by a ball milling method, putting milling balls and the weighed raw materials in the step 1) into a ball milling tank according to a certain ball-to-material ratio, sealing, putting the ball milling tank into a ball mill, and performing ball milling under certain ball milling conditions to obtain the transition metal fluoride doped composite hydrogen storage material, wherein the ball-to-material ratio in the step 2) is (100 ~ 200): 1, the ball milling time is 1 ~ 3 h, and the ball milling speed is 100 ~ 300 r/min;
all the preparation steps are carried out under inert gas conditions.
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| CN109081383B (en) * | 2018-07-10 | 2023-08-25 | 扬州大学 | Process for preparing transition metal fluorides |
| CN112110426B (en) * | 2020-08-20 | 2022-06-03 | 浙江工业大学 | Method for synthesizing amino lithium potassium by mechanical ball milling |
| CN112110427A (en) * | 2020-08-20 | 2020-12-22 | 浙江工业大学 | Synthesis method of lithium potassium amino fluoride |
| CN112110428A (en) * | 2020-08-25 | 2020-12-22 | 浙江工业大学 | Method for synthesizing amino lithium potassium by solid-solid reaction |
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| CN103183312A (en) * | 2011-12-26 | 2013-07-03 | 北京有色金属研究总院 | Li-Mg-B-N-H hydrogen storage material |
| CN103539066A (en) * | 2012-07-13 | 2014-01-29 | 中国科学院大连化学物理研究所 | NiF2-dopped LiBH4-LiNH2-CaH2 composite hydrogen storage material and preparation method thereof |
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| CN103183312A (en) * | 2011-12-26 | 2013-07-03 | 北京有色金属研究总院 | Li-Mg-B-N-H hydrogen storage material |
| CN103539066A (en) * | 2012-07-13 | 2014-01-29 | 中国科学院大连化学物理研究所 | NiF2-dopped LiBH4-LiNH2-CaH2 composite hydrogen storage material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Effects of nano additives on hydrogen storage behavior of the multinary complex hydride LiBH4/LiNH2/MgH2;Sesha S. Srinivasan et al.;《International Journal of Hydrogen Energy》;20100731;第35卷;摘要及第9648页左栏第1段 * |
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