CN104030239A - High-capacity light metal composite hydrogen storage material and preparation method thereof - Google Patents
High-capacity light metal composite hydrogen storage material and preparation method thereof Download PDFInfo
- Publication number
- CN104030239A CN104030239A CN201410230333.3A CN201410230333A CN104030239A CN 104030239 A CN104030239 A CN 104030239A CN 201410230333 A CN201410230333 A CN 201410230333A CN 104030239 A CN104030239 A CN 104030239A
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- CN
- China
- Prior art keywords
- hydrogen storage
- storage material
- boron hydride
- urea
- earth metal
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Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000011232 storage material Substances 0.000 title claims abstract description 30
- 239000002905 metal composite material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- -1 alkali metal boron hydride Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical group B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000011575 calcium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010389 TiMn Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a high-capacity light metal composite hydrogen storage material and a preparation method thereof. The hydrogen storage material mainly comprises alkali metal boron hydride or alkali earth metal boron hydride bonded with at least one urea molecule group. The method comprises the following steps: mixing alkali metal boron hydride or alkali earth metal boron hydride with urea at a molar ratio of (10:1)-(1:10), and performing ball-milling reaction in an inert atmosphere for 1-10 hours. According to the novel composite hydrogen storage material disclosed by the invention, high-purity hydrogen can be released at 100-250 DEG C.
Description
Technical field
The present invention relates to Material Field, be specifically related to a kind of heavy body light-weight metal composite hydrogen storage material and preparation method.
Background technology
Hydrogen, because its aboundresources, efficiency of combustion are high, pollution-free etc., is considered to the secondary energy of desirable alternative fossil resource, has now become the emphasis direction of whole world research.But a key factor that realizes " hydrogen economy " is the research and development of efficient, reversible solid hydrogen storage material, its technical indicator is more than hydrogen storage capability reaches 6wt%.In current all kinds of hydrogen storage alloy, AB
5(with LaNi
5for representative) and AB
2(with TiMn
2for representative) research and development ripe, but its hydrogen-storage amount is less than the practical application that 2wt% has limited them.Magnuminium has larger hydrogen storage capability (MgH
2hydrogen storage capability reach 7.6wt%), but the application requiring that hydrogen condition (temperature is more than 300 ℃) is difficult to meet fuel cell is equally put in the suction of its harshness.
At present, metal borohydride is as hydrogen storage material, and its hydrogen discharging temperature is higher, and it is poor that reversible hydrogen is put in suction.
2005, the people such as Pinkerton [1] prepared novel hydrogen storage material Li
3bN
2h
8.This material is heated to the 250-350 ℃ of hydrogen that can discharge higher than 10wt%.
The people such as Soloveichik [2] have prepared complex compound Mg (BH
4)
26NH
3, the initial hydrogen discharging temperature of this complex compound is reduced to 150 ℃, and reaches maximum hydrogen discharging rate at 205 ℃, finally can at 400 ℃, discharge 13.6wt%H
2.
Reference:
[1]Pinkerton?F?E,Meisner?G?P,Meyer?M?S,Balogh?M?P?and?Kundrat?M?D,J.Phys.Chem.B,2004,109:6-8.
[2]Soloveichik?G,Her?J-H,Stephens?P?W,Gao?Y,Rijssenbeek?J,Andrus?M?and?Zhao?J?C,Inorg.Chem.,2008,47:4290-4298.
Summary of the invention
In view of its hydrogen discharging temperature of current hydrogen storage material is still higher, the invention provides a kind of heavy body light-weight metal composite hydrogen storage material and preparation method, described material can discharge high-purity hydrogen at 100-250 ℃, is a kind of NEW TYPE OF COMPOSITE hydrogen storage material.
A heavy body light-weight metal composite hydrogen storage material, described hydrogen storage material mainly contains alkali metal borohydride or alkaline-earth metal boron hydride, described alkali metal borohydride or alkaline-earth metal boron hydride have at least been gone back a bonding urea molecule group.
Described alkali metal borohydride is LiBH
4or NaBH
4or KBH
4; Described alkaline-earth metal boron hydride is Mg (BH
4)
2or Ca (BH
4)
2.
Described hydrogen storage material is LiBH
4cO (NH
2)
2, Mg (BH
4)
2cO (NH
2)
2, Mg (BH
4)
22CO (NH
2)
2or Ca (BH
4)
24CO (NH
2)
2.
A kind of preparation method of heavy body light-weight metal composite hydrogen storage material, described method comprises: by alkali metal borohydride or alkaline-earth metal boron hydride and urea in molar ratio the ratio of 10:1～1:10 mix, and in inert atmosphere ball-milling reaction, the time of ball-milling reaction is 1-10 hour.
Accompanying drawing explanation
Fig. 1 is CO (NH
2)
2(in figure a), Ca (BH
4)
24CO (NH
2)
2(b in figure) and Ca (BH
4)
2the X ray diffracting spectrum of (c in figure).
Fig. 2 is Mg (BH
4)
2cO (NH
2)
2(in figure a) and Mg (BH
4)
22CO (NH
2)
2the X ray diffracting spectrum of (b in figure).
Fig. 3 is Ca (BH
4)
24CO (NH
2)
2the mass spectrum of matrix material thermal degradation.
Fig. 4 is Ca (BH
4)
24CO (NH
2)
2the temperature programming Hydrogen desorption isotherms figure of matrix material.
Embodiment
Below by embodiment, the present invention is described in further detail.
Embodiment 1:
Take respectively 0.4754 gram of calcium borohydride and 1.6299 grams of urea (mol ratio 1:4) in stainless steel jar mill, argon shield, on planetary ball mill, ball milling mixes, and Ball-milling Time is 2 hours, obtains powdered product after taking-up.The X ray diffracting spectrum of product as shown in Figure 1, as can be seen from the figure, the Ca (BH obtaining
4)
24CO (NH
2)
2matrix material is a kind of new compound.Its temperature programming dehydrogenation behavior as shown in Figure 3, Figure 4, is warming up to the speed of 2 ℃/min the hydrogen that 250 ℃ and constant temperature can discharge 5.2wt% for 1 hour, is one of more promising hydrogen storage material.
Embodiment 2:
Take respectively 0.9800 gram of magnesium borohydride and 1.1253 grams of urea (mol ratio 1:1) and 0.6533 gram of magnesium borohydride and 1.4663 grams of urea (mol ratio 1:2) in stainless steel jar mill; argon shield; on planetary ball mill, ball milling mixes; Ball-milling Time is 2 hours, obtains powdered product after taking-up.The X ray diffracting spectrum of product as shown in Figure 2.This matrix material can at least discharge the hydrogen of 6.4wt% at 250 ℃.
Embodiment 3:
Take respectively 0.5648 gram of lithium borohydride and 1.5404 grams of urea (mol ratio 1:1) in stainless steel jar mill, argon shield, on planetary ball mill, ball milling mixes, and Ball-milling Time is 5 hours, obtains powdered product after taking-up.The compound L iBH obtaining
4cO (NH
2)
2through X-ray diffractogram spectrum analysis, it is a kind of new composite hydrogen storage material.This matrix material constant temperature at 150 ℃ can discharge the hydrogen of 4.2wt% for 5 hours, continues to be heated to the hydrogen that 250 ℃ and constant temperature can discharge 8.2wt% for 6 hours, is one of more promising hydrogen storage material.
Embodiment 4:
Take respectively 0.8163 gram of sodium borohydride and 1.2889 grams of urea (mol ratio 1:1) in stainless steel jar mill, argon shield, on planetary ball mill, ball milling mixes, and Ball-milling Time is 2 hours, obtains powdered product after taking-up.The product obtaining, through X-ray diffractogram spectrum analysis, is a kind of new composite hydrogen storage material.
Embodiment 5:
Take respectively 0.9972 gram of POTASSIUM BOROHYDRIDE and 1.1080 grams of urea (mol ratio 1:1) in stainless steel jar mill; argon shield; on planetary ball mill, ball milling mixes; Ball-milling Time is 3 hours; after taking-up, obtain powdered product; the product obtaining, through X-ray diffractogram spectrum analysis, is a kind of new composite hydrogen storage material.
Embodiment 6:
Take respectively 1.8180 grams of sodium borohydrides and 0.2870 gram of urea (mol ratio 10:1) in stainless steel jar mill; argon shield; on planetary ball mill, ball milling mixes; Ball-milling Time is 3 hours; after taking-up, obtain powdered product; the product obtaining, through X-ray diffractogram spectrum analysis, is a kind of new composite hydrogen storage material.
Embodiment 7:
Take respectively 0.1254 gram of sodium borohydride and 1.9798 grams of urea (mol ratio 1:10) in stainless steel jar mill; argon shield; on planetary ball mill, ball milling mixes; Ball-milling Time is 3 hours; after taking-up, obtain powdered product; the product obtaining, through X-ray diffractogram spectrum analysis, is a kind of new composite hydrogen storage material.
Claims (5)
1. a heavy body light-weight metal composite hydrogen storage material, described hydrogen storage material mainly contains alkali metal borohydride or alkaline-earth metal boron hydride, described alkali metal borohydride or alkaline-earth metal boron hydride have at least been gone back a bonding urea molecule group.
2. hydrogen storage material according to claim 1, wherein said alkali metal borohydride is LiBH
4or NaBH
4or KBH
4.
3. hydrogen storage material according to claim 1, wherein said alkaline-earth metal boron hydride is Mg (BH
4)
2or Ca (BH
4)
2.
4. hydrogen storage material according to claim 1, described hydrogen storage material is LiBH
4cO (NH
2)
2, Mg (BH
4)
2cO (NH
2)
2, Mg (BH
4)
22CO (NH
2)
2or Ca (BH
4)
24CO (NH
2)
2.
5. the preparation method of a heavy body light-weight metal composite hydrogen storage material, described method comprises: by alkali metal borohydride or alkaline-earth metal boron hydride and urea in molar ratio the ratio of 10:1～1:10 mix, and in inert atmosphere ball-milling reaction, the time of ball-milling reaction is 1-10 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410230333.3A CN104030239B (en) | 2014-05-28 | 2014-05-28 | A kind of heavy body light-weight metal composite hydrogen storage material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410230333.3A CN104030239B (en) | 2014-05-28 | 2014-05-28 | A kind of heavy body light-weight metal composite hydrogen storage material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104030239A true CN104030239A (en) | 2014-09-10 |
| CN104030239B CN104030239B (en) | 2016-04-06 |
Family
ID=51461272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410230333.3A Expired - Fee Related CN104030239B (en) | 2014-05-28 | 2014-05-28 | A kind of heavy body light-weight metal composite hydrogen storage material and preparation method |
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| Country | Link |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198933A (en) * | 2011-04-20 | 2011-09-28 | 复旦大学 | Method for preparing high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine |
| CN102515101A (en) * | 2011-11-29 | 2012-06-27 | 复旦大学 | Method for preparing titanium-containing boron hydride amide of high-efficiency hydrogen storage system |
| CN102730639A (en) * | 2011-04-13 | 2012-10-17 | 浙江大学 | Solid-phase synthesis method of Mg(BH4)2 hydrogen storage material |
| CN102951608A (en) * | 2011-08-19 | 2013-03-06 | 中国科学院大连化学物理研究所 | High-volume composite hydrogen storage material, and synthetic method and hydrogen desorption method thereof |
| CN103159171A (en) * | 2013-03-08 | 2013-06-19 | 燕山大学 | LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof |
| CN103420334A (en) * | 2012-05-14 | 2013-12-04 | 中国科学院大连化学物理研究所 | LiBH4-Fe2O3-TiF3 composite hydrogen storage material and preparation thereof |
-
2014
- 2014-05-28 CN CN201410230333.3A patent/CN104030239B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730639A (en) * | 2011-04-13 | 2012-10-17 | 浙江大学 | Solid-phase synthesis method of Mg(BH4)2 hydrogen storage material |
| CN102198933A (en) * | 2011-04-20 | 2011-09-28 | 复旦大学 | Method for preparing high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine |
| CN102951608A (en) * | 2011-08-19 | 2013-03-06 | 中国科学院大连化学物理研究所 | High-volume composite hydrogen storage material, and synthetic method and hydrogen desorption method thereof |
| CN102515101A (en) * | 2011-11-29 | 2012-06-27 | 复旦大学 | Method for preparing titanium-containing boron hydride amide of high-efficiency hydrogen storage system |
| CN103420334A (en) * | 2012-05-14 | 2013-12-04 | 中国科学院大连化学物理研究所 | LiBH4-Fe2O3-TiF3 composite hydrogen storage material and preparation thereof |
| CN103159171A (en) * | 2013-03-08 | 2013-06-19 | 燕山大学 | LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAILIANG CHU, ET AL.: ""Improved Dehydrogenation Properties of Calcium Borohydride Combined with Alkaline-Earth Metal Amides"", 《THE JOURNAL OF PHSICAL CHEMISTRY C》, vol. 115, 20 July 2011 (2011-07-20), pages 18035 - 18041 * |
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| Publication number | Publication date |
|---|---|
| CN104030239B (en) | 2016-04-06 |
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Granted publication date: 20160406 |