CN103183312B - Li-Mg-B-N-H hydrogen storage material - Google Patents
Li-Mg-B-N-H hydrogen storage material Download PDFInfo
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Abstract
The invention relates to a Li-Mg-B-N-H hydrogen storage material taking a nano-metal oxide as a catalyst. The ingredient of the hydrogen storage material is aLiBH4-bLiNH2-cMgH2-d(MOn/2)N, wherein n is the valence state of M, a is equal to 1, b is not less than 1 and not greater than 10, c is not less than 0.5 and not greater than 5, d is not less than 0.02 and not greater than 0.2, M in MOn/2 is Co, Fe, Ti, Zr, Ce, Al or Si, and N represents the type number of the elements aforementioned, and is 1 to 7; when N is equal to 1, MOn/2 represents any one single oxide in the elements aforementioned; and when N is 2 to 7, (MOn/2)N represents the mixture of the N oxides in the seven elements aforementioned. The Li-Mg-B-N-H hydrogen storage material is obtained by ball-milling the mixture of LiNH2 and LiBH4 to prepare LixBNyHz in an inert atmosphere at first, and then mechanically mixing the nanoscale MOn/2 catalyst, MgH2 and LixBNyHz. The hydrogen storage capacity of the Li-Mg-B-N-H hydrogen storage material disclosed by the invention is 7 to 8 wt.%, the hydrogen discharge temperature is low, the initial hydrogen discharge temperature can achieve about 50 DEG C, and more than 5.4% of hydrogen can be discharged in the condition of 140 DEG C without side reaction products. The Li-Mg-B-N-H hydrogen storage material is a hydrogen storage material which is excellent in performance.
Description
Technical field
The present invention relates to hydrogen storage material field, be specially a kind of Li-Mg-B-N-H hydrogen storage material by nano-metal-oxide catalyst.
Technical background
Realize the application of hydrogen energy source on automobile and be faced with some technical difficulties, find a kind of safety, efficient and the hydrogen storage material that can be applied to mobile equipment is the key of dealing with problems.According to the goal in research that USDOE (Department of Energy, DOE) sets, by 2015, hydrogen storage system should reach reversible hydrogen storage capacity 9.0wt.% and reversible hydrogen storage density 81kg H
2m
-3target, the expectation of this target relatively automobile industry.
In order to meet the requirement of these harshnesses, the complex hydrides be made up of light element in recent years or complicated hydride are widely studied.As alanate system, hydroborate system and amino-imino-system etc.They are generally formed with IIIA element (as B, Al) or non-metallic element (as N) by basic metal (as Li, Na, K) or alkaline-earth metal (as Mg, Ca).This kind of material, compared with traditional metal hydride, has higher hydrogen-storage amount, and the meaning of commercial applications is also larger.But this kind of material is generally through two steps or multistep hydrogen discharge reaction, and the condition often walking hydrogen discharge reaction is different, often there is larger difference with theoretical value in the actual hydrogen storage capability reached, and also therefore becomes complicated to the accurate control of putting hydrogen process.Low hydrogen desorption kinetics performance is also the bottleneck problem that such material of restriction moves towards practical application.
Li-Mg-B-N-H system is by LiBH
4, LiNH
2and MgH
2the composite hydrogen storage material of three kinds of material compositions.Not only have very high theoretical hydrogen-storage amount (8-10wt.%), and hydrogen discharge reaction by product is few, more simple hydroborate system hydrogen discharging temperature obviously reduces, and has part reversibility, is that in current compound system, performance is a kind of preferably.Although present stage has some preliminary study to Li-Mg-B-N-H system in preparation method and reaction process, this system still exists that to inhale hydrogen desorption kinetics slow, the problem of the higher and cyclicity difference of hydrogen discharging temperature.Catalyzer is added in this system, by the interaction between material, can the improvement hydrogen desorption kinetics of high degree and thermodynamic behaviour, prepare the novel hydrogen storage material that performance is more excellent, promote cheap, catalyzer and there is the development of novel light hydrogen storage material of practical value efficiently.
Summary of the invention
The object of the present invention is to provide a kind of Li-Mg-B-N-H hydrogen storage material of nano-metal-oxide catalysis, can effectively improve system hydrogen discharging performance.
The composition of this hydrogen storage material is aLiBH
4-bLiNH
2-cMgH
2-d (MO
n/2)
n, n is the valence state of M, a=1,1≤b≤10,0.5≤c≤5,0.02≤d≤0.2, wherein MO
n/2in M be Co, Fe, Ti, Zr, Ce, Al or Si, N represents the kind of above-mentioned element, is 1-7; When N is 1, MO
n/2represent any one single oxide in above-mentioned element; When N is 2-7, (MO
n/2)
nrepresent the N kind hopcalite in above-mentioned seven kinds of elements.
When N is 2-7, (MO
n/2)
nrepresent the N kind hopcalite in above-mentioned seven kinds of elements, such as, when N is 2, (MO
n/2)
2represent the mixture of the two oxides in above-mentioned seven kinds of elements, e.g., M is the valence state n of Fe and Co, Fe is 3 valencys, and the valence state n of Co is 8/3 valency; Like this, (MO
n/2)
2just represent Fe
2o
3-Co
3o
4mixture, namely represents Fe
2o
3and Co
3o
4mixture.
Described MO
n/2granularity is 10-100nm, MgH
2granularity is-200 orders.Wherein, described MO
n/2granularity is the oxide compound of Co, Fe, Ti, Zr, Ce, Al or Si or the granularity of above-mentioned hopcalite.
Described Li-Mg-B-N-H hydrogen storage material is under an inert atmosphere, is obtained by mechanically mixing mode.The pressure range of rare gas element is 0.1-5.0Mpa, and Ball-milling Time is 2-50 hour, and ball material weight ratio is 1: 1-50: 1.
Li-Mg-B-N-H hydrogen storage material of the present invention, hydrogen storage capability is at 7-8wt.%, and initial hydrogen discharging temperature can reach 50 DEG C, can release the hydrogen of more than 5.4% under 140 DEG C of conditions, without side reaction product, is a kind of hydrogen storage material of excellent property.
Accompanying drawing explanation
Fig. 1 is LiBH
4-2LiNH
2-MgH
2-0.1Co
3o
4material, LiBH
4-2LiNH
2-MgH
2-0.1SiO
2material, LiBH
4-2LiNH
2-MgH
2-0.1TiO
2material and LiBH
4-2LiNH
2-MgH
2the temperature programmed control desorption comparison curves of material;
Fig. 2 is LiBH
4-2LiNH
2-MgH
2-0.05Fe
2o
3material and LiBH
4-2LiNH
2-MgH
2-0.1Fe
2o
3the temperature programmed control desorption comparison curves of material;
Fig. 3 is LiBH
4-2LiNH
2-MgH
2-0.05Fe
2o
3material, LiBH
4-2LiNH
2-MgH
2-0.05Co
3o
4material and LiBH
4-2LiNH
2-MgH
2material at 140 DEG C, under 0MPa condition hydrogen desorption kinetics comparison curves;
Fig. 4 is LiBH
4-2LiNH
2-MgH
2-0.05 (Co
3o
4-Fe
2o
3) sample at 200 DEG C, the hydrogen desorption kinetics curve under 0MPa condition.
Embodiment
First, by LiNH
2and LiBH
4according to certain mol proportion mixing, then mixture is carried out ball milling mixing under inert atmosphere protection, inert gas pressure scope is 0.1-5.0MPa, and Ball-milling Time is 2-50 hour, and ball material weight ratio is 10: 1-50: 1, prepares Li
xbN
yh
z.Then, by obtained Li
xbN
yh
z, MgH
2with MO
n/2or its mixture adopts aforesaid method mechanically mixing equally, obtain final Li-Mg-B-N-H hydrogen storage material, and test the hydrogen discharging performance of sample.Because the oxygen G&W of sample easily and in air reacts, sample weighing and transfer are all carried out in the glove box being filled with high-purity argon gas or nitrogen, and in glove box, the content of oxygen and water is less than 1ppm.
Embodiment 1
Under Ar gas atmosphere, mol ratio is respectively the LiBH of 1: 2,1: 3 and 1: 4
4and LiNH
2mixing, loads in the stainless cylinder of steel of sealing, ball milling mixing on high energy ball mill, and ratio of grinding media to material is 20: 1, and Ball-milling Time is 10 hours, obtained Li
xbN
yh
z.Then mol ratio is respectively the Li of 1: 1: 0.1,1: 1.5: 0.1 and 1: 2: 0.1
xbN
yh
z, MgH
2and SiO
220nm (or TiO
210nm or ZrO
220nm or Al
2o
320nm or CeO
220nm or Co
3o
450nm etc.) mixing, adopt Ar gas shielded, ball milling mixing on high energy ball mill, ratio of grinding media to material is 30: 1, and Ball-milling Time is 10 hours.After ball milling, sample carries out temperature programmed control detachment assays, and temperature rise rate is 2 DEG C/min, and experimental result shows, hydrogen desorption capacity is all at more than 7wt.% at 350 DEG C for above-mentioned sample, and initial hydrogen discharging temperature is all lower than 90 DEG C.
Comparing embodiment 1
Under Ar gas atmosphere, be the LiBH of 1: 2 by mol ratio
4and LiNH
2mixing, loads in the stainless cylinder of steel of sealing, ball milling mixing on high energy ball mill, and ratio of grinding media to material is 20: 1, and Ball-milling Time is 5 hours, obtained Li
xbN
yh
z.Then be the Li of 1: 1 by mol ratio
xbN
yh
zand MgH
2mixing, adopts Ar gas shielded, and ball milling mixing on high energy ball mill, ratio of grinding media to material is 25: 1, and Ball-milling Time is 5 hours.
Figure 1 shows that various LiBH
4-2LiNH
2-MgH
2-0.1MO
n/2sample and LiBH
4-2LiNH
2-MgH
2the temperature programmed control desorption comparison curves of sample.As can be seen from the figure, LiBH
4-2LiNH
2-MgH
2-0.1TiO
2, LiBH
4-2LiNH
2-MgH
2-0.1SiO
2and LiBH
4-2LiNH
2-MgH
2-0.1Co
3o
4sample put hydrogen starting temperature between 50-70 DEG C, comparatively LiBH
4-LiNH
2-MgH
2the hydrogen starting temperature of putting of sample reduces about 80 DEG C.
Embodiment 2
Under Ar gas atmosphere, be the LiBH of 1: 2 by mol ratio
4and LiNH
2mixing, loads in the stainless cylinder of steel of sealing, ball milling mixing on high energy ball mill, and ratio of grinding media to material is 20: 1, and Ball-milling Time is 5 hours, obtained Li
xbN
yh
z.Change the mol ratio adding metal oxide, mol ratio is respectively the Li of 1: 1: 0.05 and 1: 1: 0.1
xbN
yh
z, MgH
2and Fe
2o
320nm mixes, and adopts Ar gas shielded, and ball milling mixing on high energy ball mill, ratio of grinding media to material is 30: 1, and Ball-milling Time is 5 hours.By sample LiBH after ball milling
4-2LiNH
2-MgH
2-0.05Fe
2o
3and LiBH
4-2LiNH
2-MgH
2-0.1Fe
2o
3carry out temperature programmed control detachment assays, temperature rise rate is 5 DEG C/min, and experimental result shows, increases Fe
2o
3content, the change of initial hydrogen discharging temperature is little, but the hydrogen peak temperature of putting of more than 200 DEG C reduces obviously, hydrogen desorption kinetics quickening.
Embodiment 3
Under Ar gas atmosphere, be the LiBH of 1: 2 by mol ratio
4and LiNH
2mixing, loads in the stainless cylinder of steel of sealing, ball milling mixing on high energy ball mill, and ratio of grinding media to material is 20: 1, and Ball-milling Time is 5 hours, obtained Li
xbN
yh
z.Then be the Li of 1: 1: 0.05 by mol ratio
4bN
3h
10, MgH
2and Co
3o
4mixing, adopts Ar gas shielded, and ball milling mixing on high energy ball mill, ratio of grinding media to material is 30: 1, and Ball-milling Time is 5 hours.By the LiBH in sample after ball milling and example 2
4-2LiNH
2-MgH
2-0.05Fe
2o
3sample carries out hydrogen storage property test.At 140 DEG C, relatively more visible to 0MPa hydrogen desorption kinetics curve, LiBH
4-2LiNH
2-MgH
2-0.05Co
3o
4and LiBH
4-2LiNH
2-MgH
2-0.05Fe
2o
3the hydrogen desorption capacity of sample and hydrogen discharging rate comparatively LiBH
4-2LiNH
2-MgH
2sample improves obviously.In time sufficiently long situation, LiBH
4-2LiNH
2-MgH
2-0.05Co
3o
4and LiBH
4-2LiNH
2-MgH
2-0.05Fe
2o
3sample can release the hydrogen of about 5.3wt.% at 140 DEG C.
Embodiment 4
Under Ar gas atmosphere, be the LiBH of 1: 2 by mol ratio
4and LiNH
2mixing, loads in the stainless cylinder of steel of sealing, ball milling mixing on high energy ball mill, and ratio of grinding media to material is 20: 1, and Ball-milling Time is 5 hours, obtained Li
xbN
yh
z.Then be the Li of 1: 1: 0.05 by mol ratio
4bN
3h
10, MgH
2and Fe
2o
3-Co
3o
4mixture mixes, and adopts Ar gas shielded, and ball milling mixing on high energy ball mill, ratio of grinding media to material is 30: 1, and Ball-milling Time is 5 hours.Sample after ball milling is carried out hydrogen storage property test.At 200 DEG C, visible to 0MPa hydrogen desorption kinetics curve, LiBH
4-2LiNH
2-MgH
2-0.05 (Co
3o
4-Fe
2o
3) sample can release the hydrogen of 7.0wt.% in 60min.
Claims (3)
1. a Li-Mg-B-N-H hydrogen storage material, is characterized in that: composition is aLiBH
4-bLiNH
2-cMgH
2-d (MO
n/2)
n, n is the valence state of M, a=1,1≤b≤2,0.5≤c≤1,0.02≤d≤0.2, wherein MO
n/2in M be Co, Fe, Ti, Zr, Ce, Al or Si, N represents the kind of above-mentioned element, be 1 ?7; When N is 1, MO
n/2represent any one single oxide in above-mentioned element; When N be 2 ?7 time, (MO
n/2)
nrepresent the N kind hopcalite in above-mentioned seven kinds of elements.
2. a kind of Li-Mg-B-N-H hydrogen storage material according to claim 1, is characterized in that: described MO
n/2granularity is 10-100nm, MgH
2granularity is-200 orders.
3. a kind of Li-Mg-B-N-H hydrogen storage material according to claim 1, is characterized in that: described aLiBH
4-bLiNH
2-cMgH
2-d (MO
n/2)
nbe under an inert atmosphere, obtained by mechanically mixing mode;
The pressure range of rare gas element is 0.1-5.0MPa, and Ball-milling Time is 2-50 hour, and ball material weight ratio is 1:1-50:1.
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Inventor after: Yuan Huiping Inventor after: Li Zhinian Inventor after: Ye Jianhua Inventor after: Guo Xiumei Inventor after: Liu Xiaopeng Inventor after: Wang Shumao Inventor after: Jiang Lijun Inventor before: Li Zhinian Inventor before: Zhang Xugang Inventor before: Lv Fang Inventor before: Mi Jing Inventor before: Liu Xiaopeng Inventor before: Hao Lei Inventor before: Wang Shumao Inventor before: Jiang Lijun |
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Free format text: CORRECT: INVENTOR; FROM: LI ZHINIAN ZHANG XUGANG LV FANG MI JING LIU XIAOPENG HAO LEI WANG SHUMAO JIANG LIJUN TO: YUAN HUIPING LI ZHINIAN YE JIANHUA GUO XIUMEI LIU XIAOPENG WANG SHUMAO JIANG LIJUN |
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Effective date of registration: 20190621 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: No. 2, Xinjie street, Xicheng District, Beijing, Beijing Patentee before: General Research Institute for Nonferrous Metals |