CN107381501A - The application of cerium and compound in amide hydride systems hydrogen storage property is improved - Google Patents
The application of cerium and compound in amide hydride systems hydrogen storage property is improved Download PDFInfo
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- CN107381501A CN107381501A CN201710613093.9A CN201710613093A CN107381501A CN 107381501 A CN107381501 A CN 107381501A CN 201710613093 A CN201710613093 A CN 201710613093A CN 107381501 A CN107381501 A CN 107381501A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention discloses the application of metallic cerium and cerium compound in Metal Substrate amide hydride composite system hydrogen storage property is improved, described cerium compound includes CeO2、CeF3And CeF4.In use, being to be doped to metallic cerium and/or cerium compound in Metal Substrate amide-hydride composite system by the method for mechanical ball mill, addition is 1 10%wt.Metallic cerium and cerium compound can completely inhibit ammonolysis craft of the Metal Substrate amide hydride composite system during hydrogen is put, and significantly reduce its hydrogen discharging temperature, improve hydrogen discharging rate；And after hydrogen circulation is put by repeatedly suction, metallic cerium and cerium compound still have excellent catalytic effect for Metal Substrate amide hydride composite system.
Description
Technical field
The invention belongs to hydrogen storage material and its catalytic modification field, more particularly to metallic cerium and cerium compound is improving metal
Application in base amide-hydride compound system hydrogen storage property.
Background technology
Metal Substrate amide-hydride compound system, such as LiNH2- LiH and Mg (NH2)2- 2LiH systems, it is developed recently
One of high power capacity storage hydrogen material of several most application potentials to get up, its have appropriate suction put hydrogen thermodynamic property, compared with
High reversible hydrogen storage capacity and preferably suction puts hydrogen cyclical stability.However, the suction of Metal Substrate amide-hydride compound system
Put hydrogen activation it excessive can be caused to inhale hydrogen desorption kineticses performance is too slow, and hydrogen operation temperature is put in suction need to be of about 200 DEG C, and put hydrogen process
Ammonia can be discharged, cycle performance is poor, therefore is not suitable as the hydrogen source of on-vehicle fuel.
It is that an improvement Metal Substrate amide-hydride is answered that being adulterated by catalyst, which reduces suction hydrogen discharge reaction kinetic barrier,
The effective way of zoarium system hydrogen storage property.Research shows, TiCl3Mg (NH can be significantly increased2)2The dehydrogenation of -2LiH systems
Can, but TiCl3Catalytic action experience twice inhale put hydrogen circulation after just disappear.In addition, KH, KOH, single-walled carbon nanotube,
V、V2O5、VCl3、TiN、TaN、NaH、Li3N、LaH3And Li3AlH6It can improve Metal Substrate ammonification to a certain extent etc. compound
The suction of thing-hydride composite system, hydrogen desorption kineticses performance, but improvement is still extremely limited, Metal Substrate amide-hydride
Compound system still has a small amount of ammonia to discharge in certain embodiments.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the invention to provide metallic cerium and cerium compound to improve
Application in Metal Substrate amide-hydride compound system hydrogen storage property.
The purpose of the present invention is achieved through the following technical solutions：
The application of metallic cerium and cerium compound in Metal Substrate amide-hydride compound system hydrogen storage property is improved；
Described cerium compound includes CeO2、CeF3And CeF4；
The described preferred LiNH of Metal Substrate amide-hydride compound system2- LiH or Mg (NH2)2-2LiH；
In use, be by metallic cerium and/or cerium compound by the method for mechanical ball mill be doped to Metal Substrate amide-
In hydride composite system；The addition of metallic cerium and/or cerium compound is 1-10%wt (with metallic cerium and/or cerium compound
With the quality of Metal Substrate amide-hydride compound system and be calculating benchmark)；
Preferably, it is under inert gas shielding, by metallic cerium and/or cerium compound, Metal Substrate amide and Metal Substrate
Hydride mixes, ball milling；
Preferable Ball-milling Time is 1-20h, and ratio of grinding media to material is (30-100):1, ball mill revolution speed is 300-500rpm.
The present invention is had the following advantages relative to prior art and effect：
The metallic cerium and cerium compound of the present invention is used to improve Metal Substrate amide-hydride compound system hydrogen storage property,
Doping process is simple, and there is the Metal Substrate amide-hydride compound system after overdoping the hydrogen of putting for being suitable to FC work to work
The characteristics such as temperature, high hydrogen discharging rate.
The metallic cerium and cerium compound for adulterating 1-10wt% can completely inhibit Metal Substrate amide-hydride complex
Tie up to and put ammonolysis craft during hydrogen, significantly reduce its hydrogen discharging temperature, improve hydrogen discharging rate；And followed putting hydrogen by repeatedly suction
After ring, metallic cerium and cerium compound still have excellent catalytic effect for Metal Substrate amide-hydride compound system.
Brief description of the drawings
Fig. 1 is LiNH2- LiH compounds and the LiNH being doped with after metallic cerium and cerium compound2The XRD of-LiH compounds
Spectrum；Wherein, a-LiNH2- LiH compounds, b- adulterate 10wt.% Ce, and c- adulterates 10wt.% CeO2, d- doping 10wt.%
CeF3, e- doping 10wt.% CeF4。
Fig. 2 is LiNH2- LiH compounds and the LiNH being doped with after metallic cerium and cerium compound2- thermogravimetric of LiH compounds-
Gaseous mass spectrum curve.
Fig. 3 is LiNH2- LiH compounds and the LiNH being doped with after metallic cerium and cerium compound2- LiH compounds are in difference
At a temperature of isothermal Hydrogen desorption isotherms.
Fig. 4 is LiNH2- LiH compounds and it is doped with CeF4LiNH2The gaseous mass spectrum curve of-LiH compounds.
Fig. 5 is to be doped with CeF4LiNH2Thermogravimetric-gaseous mass spectrum curve of-LiH the compounds after circulating twice.
Fig. 6 is Mg (NH2)2- 2LiH compounds and it is doped with CeF4Mg (NH2)2The gaseous mass spectrum of -2LiH compounds is bent
Line.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
In the glove box full of argon gas, by mol ratio 1:1 LiNH2With LiH mix, then be separately added into 10wt% (with
The quality of metallic cerium and/or cerium compound and Metal Substrate amide-hydride compound system and be calculating benchmark) Ce, CeO2,
CeF3And CeF4It is sufficiently mixed, is fitted into the ball grinder with controlled valve, after ball grinder forvacuum, in planet gear type ball
Ball milling mixing on grinding machine, ratio of grinding media to material 60:1, rotating speed 400rpm, Ball-milling Time are 2 hours.
LiNH2Purity is 95%；LiH purity is 99.9%；Ce, CeO2, CeF3And CeF4Purity is 99%.
Fig. 1 is to be doped with Ce, CeO respectively2、CeF3Or CeF4LiNH2The X-ray diffraction curve of-LiH samples, shows
LiNH2, LiH and metallic cerium and cerium compound be mechanical mixture, both and reactionless generation during ball milling.
The hydrogen storage property of test sample：In the glove box full of argon gas, after sample taking-up weighing prepared by ball milling,
Carry out thermogravimetric-gaseous mass spectrum test.As a result from Figure 2 it can be seen that LiNH2- LiH samples are being doped with Ce, CeO2, CeF3Or CeF4Afterwards
Desorption temperature decrease, and do not produce ammonolysis craft phenomenon in certain embodiments.
Fig. 3 is the LiNH after ball milling2- LiH compounds (do not add cerium compound), and are doped with Ce, CeO respectively2、
CeF3Or CeF4LiNH2The isothermal dehydrogenation kinetic curve of-LiH compounds at different temperatures, shows metallic cerium and cerium chemical combination
The addition of thing significantly increases LiNH2The dehydrogenation dynamic performance of-LiH compounds, after adding metallic cerium and cerium compound
LiNH2The isothermal dehydrogenation speed of-LiH compounds at 180 DEG C, 200 DEG C and 220 DEG C improves about 3 times.
Embodiment 2
In the glove box full of argon gas, by mol ratio 1:1 LiNH2With LiH mix, then be separately added into 1wt%,
3wt% or 10wt% are (by metallic cerium and/or cerium compound with the quality of Metal Substrate amide-hydride compound system and in terms of
Calculate benchmark) CeF4It is sufficiently mixed, is fitted into the ball grinder with controlled valve, after ball grinder forvacuum, in planetary gear
Ball milling mixing on formula ball mill, ratio of grinding media to material 50:1, rotating speed 400rpm, Ball-milling Time are 4 hours.
LiNH2Purity is 95%；LiH purity is 99.9%；CeF4Purity is 99%.
The hydrogen storage property of test sample：In the glove box full of argon gas, after sample taking-up weighing prepared by ball milling,
Carry out thermogravimetric-gaseous mass spectrum test.From fig. 4, it can be seen that LiNH2- LiH samples are being doped with 1wt%, 3wt% or 10wt% CeF4
Ammonolysis craft phenomenon is not produced in certain embodiments afterwards.
Embodiment 3
In the glove box full of argon gas, by mol ratio 1:1 LiNH2Mixed with LiH, add 10wt% (with metal
The quality of cerium and/or cerium compound and Metal Substrate amide-hydride compound system and be calculating benchmark) CeF4It is fully mixed
Close, be fitted into the ball grinder with controlled valve, after ball grinder forvacuum, the ball milling mixing on planet gear type ball mill,
Ratio of grinding media to material is 80:1, rotating speed 400rpm, Ball-milling Time are 5 hours.Sample after ball milling is anti-using Sievert type gas-solids
Answer test equipment to carry out suction at 150 DEG C and put hydrogen circulation twice, suction hydrogen pressure is 5MPa, and the suction hydrogen time is 4h, and dehydrogenation pressure is
0.01MPa, dehydrogenation time 4h.
LiNH2Purity is 95%；LiH purity is 99.9%；CeF4Purity is 99%.
The dehydrogenation of test sample：In the glove box full of argon gas, the sample inhaled after putting hydrogen circulation is taken out and weighed
Afterwards, thermogravimetric-gaseous mass spectrum test is carried out.As seen from Figure 5, after 2 times are inhaled and put hydrogen circulation, LiNH2- LiH samples are being doped with
10wt% CeF4Certain embodiments in do not produce ammonolysis craft phenomenon.
Embodiment 4
In the glove box full of argon gas, by mol ratio 1:2 Mg (NH2)2With LiH mix, then be separately added into 1wt%,
3wt% or 10wt% are (by metallic cerium and/or cerium compound with the quality of Metal Substrate amide-hydride compound system and in terms of
Calculate benchmark) CeF4It is sufficiently mixed, is fitted into the ball grinder with controlled valve, after ball grinder forvacuum, in planetary gear
Ball milling mixing on formula ball mill, ratio of grinding media to material 40:1, rotating speed 400rpm, Ball-milling Time are 2 hours.
Mg(NH2)2Purity is 95%；LiH purity is 99.9%；CeF4Purity is 99%.
The hydrogen storage property of test sample：In the glove box full of argon gas, after sample taking-up weighing prepared by ball milling,
Carry out thermogravimetric-gaseous mass spectrum test.As seen from Figure 6, Mg (NH2)2- 2LiH samples are being doped with 1wt%, 3wt% or 10wt%
CeF4Ammonolysis craft phenomenon is not produced in certain embodiments afterwards.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
1. the application of metallic cerium and cerium compound in Metal Substrate amide-hydride compound system hydrogen storage property is improved.
2. metallic cerium according to claim 1 and cerium compound are improving the storage of Metal Substrate amide-hydride compound system
Application in hydrogen performance, it is characterised in that：Described cerium compound includes CeO2、CeF3And CeF4。
3. metallic cerium according to claim 1 and cerium compound are improving the storage of Metal Substrate amide-hydride compound system
Application in hydrogen performance, it is characterised in that：Described Metal Substrate amide-hydride compound system is LiNH2- LiH or Mg
(NH2)2-2LiH。
4. metallic cerium according to claim 1 and cerium compound are improving the storage of Metal Substrate amide-hydride compound system
Application in hydrogen performance, it is characterised in that：In use, it is to mix metallic cerium and/or cerium compound by the method for mechanical ball mill
It is miscellaneous to arrive in Metal Substrate amide-hydride composite system；The addition of metallic cerium and/or cerium compound is 1-10%wt.
5. metallic cerium according to claim 1 and cerium compound are improving the storage of Metal Substrate amide-hydride compound system
Application in hydrogen performance, it is characterised in that：Under inert gas shielding, by metallic cerium and/or cerium compound, Metal Substrate amide
Mixed with metal base hydride, ball milling；The addition of metallic cerium and/or cerium compound is 1-10%wt.
6. the metallic cerium and cerium compound according to claim 4 or 5 are improving Metal Substrate amide-hydride compound system
Application in hydrogen storage property, it is characterised in that：Ball-milling Time is 1-20h, and ratio of grinding media to material is (30-100):1, ball mill revolution speed
For 300-500rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710613093.9A CN107381501B (en) | 2017-07-25 | 2017-07-25 | Application of cerium and compound in improving hydrogen storage performance of amide-hydride system |
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| CN201710613093.9A CN107381501B (en) | 2017-07-25 | 2017-07-25 | Application of cerium and compound in improving hydrogen storage performance of amide-hydride system |
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| CN107381501B CN107381501B (en) | 2020-01-17 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020146624A1 (en) * | 2001-02-23 | 2002-10-10 | Hajime Goto | Hydrogen-storage material |
| US20050191235A1 (en) * | 2004-02-26 | 2005-09-01 | Vajo John J. | Regeneration of hydrogen storage system materials and methods including hydrides and hydroxides |
| CN1842489A (en) * | 2003-08-26 | 2006-10-04 | 通用汽车公司 | Combinations of hydrogen storage materials including amide/imide |
| CN1852860A (en) * | 2003-06-25 | 2006-10-25 | 通用汽车公司 | Imede/amide hydrogen storage materials and methods |
| CN106542497A (en) * | 2015-09-16 | 2017-03-29 | 现代自动车株式会社 | Hydrogen storage material and preparation method thereof |
| CN108930166A (en) * | 2018-07-29 | 2018-12-04 | 宁波革创新材料科技有限公司 | The method of hydrogen storage material is formed on spinning fibre layer |
-
2017
- 2017-07-25 CN CN201710613093.9A patent/CN107381501B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020146624A1 (en) * | 2001-02-23 | 2002-10-10 | Hajime Goto | Hydrogen-storage material |
| CN1852860A (en) * | 2003-06-25 | 2006-10-25 | 通用汽车公司 | Imede/amide hydrogen storage materials and methods |
| CN1842489A (en) * | 2003-08-26 | 2006-10-04 | 通用汽车公司 | Combinations of hydrogen storage materials including amide/imide |
| US20050191235A1 (en) * | 2004-02-26 | 2005-09-01 | Vajo John J. | Regeneration of hydrogen storage system materials and methods including hydrides and hydroxides |
| CN106542497A (en) * | 2015-09-16 | 2017-03-29 | 现代自动车株式会社 | Hydrogen storage material and preparation method thereof |
| CN108930166A (en) * | 2018-07-29 | 2018-12-04 | 宁波革创新材料科技有限公司 | The method of hydrogen storage material is formed on spinning fibre layer |
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