CN103145098A - Solid hydrogen storage material and preparation method thereof - Google Patents

Solid hydrogen storage material and preparation method thereof Download PDF

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Publication number
CN103145098A
CN103145098A CN2013100687067A CN201310068706A CN103145098A CN 103145098 A CN103145098 A CN 103145098A CN 2013100687067 A CN2013100687067 A CN 2013100687067A CN 201310068706 A CN201310068706 A CN 201310068706A CN 103145098 A CN103145098 A CN 103145098A
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hydrogen storage
hydrogen
nabh
storage material
solid
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CN103145098B (en
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郑雪萍
刘胜林
邓娟莉
郑姣姣
冯鑫
肖果
刘敏
鲁卓睿
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Changan University
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Changan University
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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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention provides a solid hydrogen storage material and a preparation method thereof. The preparation method comprises the following steps: 1) mixing Co3B and rare earth oxide according to the Co3B:rare earth oxide mass ratio of 1:(0.5-1.5) to obtain a mixed catalyst; and 2) mixing the mixed catalyst and an NaBH4 alkaline water solution, hydrolyzing at 25-30 DEG C to carry out hydrogen desorption reaction for 10-30 minutes to obtain a hydrolysate, filtering the hydrolysate, and drying at room temperature for 12-24 hours to obtain an NaBO2-Co3B-rare earth oxide system which is the solid hydrogen storage material. The preparation method has the advantages of simple apparatuses and simple technical process, and is easy to control; the material is a sodium borohydride hydrolysate, and thus, is low in cost; and the prepared solid hydrogen storage material has the advantages of hydrogen storage reversibility, large hydrogen storage quantity, mild conditions for hydrogen absorption and desorption, and high hydrogen absorption speed, and is suitable for efficient and safe storage and transportation of hydrogen.

Description

A kind of solid-state hydrogen storage material and preparation method thereof
Technical field
The invention belongs to the hydrogen storage material field, be specifically related to a kind of novel hydrogen storage material and preparation method thereof.
Background technology
Hydrogen Energy is regarded as the most potential clean energy of 21 century, and still, due to the hydrogen storage material and the hydrogen storage technology that lack easily and effectively, the application of Hydrogen Energy has been subject to very large obstruction for a long time.The hydrogen storage material of research mainly contains hydrogen storage alloy, complex hydrides, aminocompound, organic liquid, carbon-based material and metal organic frame material (MOF) etc. at present.Compare with hydrogen storage alloy, complex hydrides has higher hydrogen-storage amount, for example, and LiBH 4Hydrogen-storage amount be 18%, head and shoulders above hydrogen storage alloy AB for example 5, AB 2, A 2B and V based solid solution hydrogen storage alloy hydrogen-storage amount, the main drawback that this class hydrogen storage material exists is synthetic difficulty and inhales the hydrogen desorption kinetics poor performance.The aminocompound hydrogen storage system has obtained broad research in recent years.This system hydrogen-storage amount is high, and working conditions is relatively gentle.But inhale the hydrogen desorption kinetics poor performance under the low temperature of this class material, to inhale hydrogen excess Temperature and reversibility poorer.Compare with traditional hydrogen storage method, organic liquid storage hydrogen is on hydrogen storage property, aspects such as hydrogen-storage amount, storage hydrogen efficiency, storage transportation, cycle life have more obvious advantage, yet show according to the result of present report, and the dehydrogenation efficient of this material is also very low.What be different from above different materials is carbon-based material and MOF material, their storage hydrogen mode belongs to the physical adsorption storing, this class material has obtained fast development because of its storage hydrogen safety, storage hydrogen efficiency advantages of higher, the main drawback that exists at present is that suction hydrogen temperature is lower, and its hydrogen－sucking amount seldom at ambient temperature.Although the hydrogen storage material of research is of a great variety now, each tool advantage, but according to USDOE (Department of Energy, DOE) hydrogen-storage amount 〉=6.5wt% that proposes, decomposition temperature are the target of 60-120 ℃, low cost and low toxicity, up to now, go back the neither one system and can satisfy all requirements.Therefore, seeking the better hydrogen storage material of performance is still the major objective of studying at present.
Summary of the invention
The object of the present invention is to provide a kind of solid-state hydrogen storage material and preparation method thereof.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of solid-state hydrogen storage material, this solid-state hydrogen storage material is by NaBO 2, Co 3B and rare earth oxide form, Co in described solid-state hydrogen storage material 3The massfraction sum of B and rare earth oxide is 20-40%.
Described Co 3B: the mass ratio of rare earth oxide is 1:0.5-1.5.The interpolation of rare earth oxide has improved the hydrogen storage property of hydrogen storage system, but rare earth oxide and Co 3After the mass ratio of B surpassed maximum ratio, the hydrogen storage property of hydrogen storage system can reduce.
Described rare earth oxide is Y 2O 3Or CeO 2
The preparation method of above-mentioned solid-state hydrogen storage material comprises the following steps:
1) with Co 3B and rare earth oxide are pressed Co 3B: the mass ratio of rare earth oxide is that 1:0.5-1.5 mixes, and gets mixed catalyst;
2) preparation NaBH4 alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With the 50-60% of mixed catalyst total mass, with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in the 25-30 ℃ of hydrolysate that was hydrolyzed hydrogen discharge reaction 10-30 minute to get, after hydrolysate is filtered under 15-30 ℃ dry 12-24 hour NaBO 2-Co 3B-rare-earth oxidation objects system, i.e. solid-state hydrogen storage material.
Described NaBH 4The preparation method of alkaline aqueous solution is: preparation pH is the NaOH aqueous solution of 12-13, then with NaBH 4Be dissolved in the NaOH aqueous solution NaBH 4Massfraction be 8-10%.
Advantage of the present invention is: in the preparation of solid-state hydrogen storage material of the present invention simple, the technological process of instrument simple, be easy to control, and material is the sodium borohydride hydrolysate, the cost of material is low; The solid-state hydrogen storage material reversible hydrogen storage capacity that the present invention prepares is large, inhale put the hydrogen condition gentleness, inhale hydrogen speed fast, be fit to the efficient accumulating of hydrogen and transport safely.
Description of drawings
Fig. 1 is NaBO 2-Co 3B-Y 2O 3Inhale hydrogen 3-5mim under the hydrogen pressure of room temperature, 3MPa, but then at vacuum, 150 ℃ of 4 inverse put hydrogen figure putting hydrogen.
Fig. 2 is the XRD analysis figure of hydrolysate.
Fig. 3 is NaBO 2-Co 3B-Y 2O 3Inhale before hydrogen (a) but, for the first time inverse put hydrogen (b) but and the SEM of the 3rd inverse put hydrogen (c) scheme.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
With 1.07g NaBH 4With 0.101g CoCl 2Add in 4g water, then reaction 2-5 minute that is hydrolyzed under 25-30 ℃ of condition filters to get filter residue, and filter residue and drying is obtained Co 3B。
Embodiment 1
A kind of preparation method of New Solid hydrogen storage material, step is as follows:
1) with Co 3B and Y 2O 3Mass ratio by 1:1 mixes in mortar, gets mixed catalyst; 2) secure ph is 12 the NaOH aqueous solution, then with NaBH 4(sodium borohydride) is dissolved in and gets NaBH in the NaOH aqueous solution 4Alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Massfraction be 9%, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With the 50%(of mixed catalyst total mass be NaBH 4The NaBH that alkaline aqueous solution contains 4With the mass ratio of mixed catalyst be 1:1); 3) with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in 30 ℃ of hydrogen discharge reactions 30 minutes of being hydrolyzed hydrolysate, after hydrolysate is filtered under 25 ℃ dry 12 hours solid-state hydrogen storage material.
As can be seen from Figure 1, the reversible hydrogen adsorption and desorption performance of this solid-state hydrogen storage material is more stable, after 4 circulations, reversible hydrogen desorption capacity is significantly decay not, in addition, can find out according to Fig. 1, this solid-state hydrogen storage material is after inhaling hydrogen 3-5min under the hydrogen pressure of room temperature, 3MPa, transfer hydrogen in vacuum, 150 ℃ again, its reversible hydrogen desorption capacity can reach 3.5wt%, illustrates that this solid-state hydrogen storage material has good reversible hydrogen storage performance under comparatively gentle condition.
Referring to Fig. 2, by the XRD analysis result as can be known, the main component of this hydrolysate is NaBO 2-Co 3B-Y 2O 3Wherein, Co 3B-Y 2O 3Account for NaBO 2-Co 3B-Y 2O 336% of quality.
As seen from Figure 3, this solid-state hydrogen storage material is a kind of cotton-shaped vesicular structure, and according to after circulation with circulation before SEM figure can find out, through suction put the hydrogen circulation after, the microtexture of material does not significantly change, and this structure that this kind material is described is highly stable.
Embodiment 2
1) with Co 3B and Y 2O 3Mass ratio by 1:1.5 mixes in mortar, gets mixed catalyst; 2) secure ph is 12.5 the NaOH aqueous solution, then with NaBH 4Be dissolved in and get NaBH in the NaOH aqueous solution 4Alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Massfraction be 9%, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With 55% of mixed catalyst total mass; 3) with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in 30 ℃ of hydrogen discharge reactions 20 minutes of being hydrolyzed hydrolysate, after hydrolysate is filtered under 25 ℃ dry 16 hours solid-state hydrogen storage material.
This solid-state hydrogen storage material is through after XRD analysis, and phase forms identical with Fig. 2, wherein, and Co 3B-Y 2O 3Account for NaBO 2-Co 3B-Y 2O 332% of quality.And the microtexture of material does not have considerable change through after sem analysis yet, its structure is the same with Fig. 3 is a kind of cotton-shaped vesicular structure, after its hydrogen storage property is tested through PCT, its reversible hydrogen adsorption and desorption curve is similar to Fig. 1, through after 4 reversible cycle, the reversible hydrogen desorption capacity of solid-state hydrogen storage material does not descend, but compares with the solid-state hydrogen storage material in Fig. 1, its total hydrogen desorption capacity descends a little to some extent, and its hydrogen desorption capacity is 3.3wt%.
Embodiment 3
1) with Co 3B and Y 2O 3Mass ratio by 1:0.5 mixes in mortar, gets mixed catalyst; 2) secure ph is 13 the NaOH aqueous solution, then with NaBH 4Be dissolved in and get NaBH in the NaOH aqueous solution 4Alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Massfraction be 9%, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With 58% of mixed catalyst total mass; 3) with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in 25 ℃ of hydrogen discharge reactions 15 minutes of being hydrolyzed hydrolysate, after hydrolysate is filtered under 25 ℃ dry 20 hours solid-state hydrogen storage material.
This solid-state hydrogen storage material is through after XRD analysis, and phase forms identical with Fig. 2, wherein, and Co 3B-Y 2O 3Account for NaBO 2-Co 3B-Y 2 O 330% of quality.And the microtexture of material does not have considerable change through after sem analysis yet, its structure is the same with Fig. 3 is a kind of cotton-shaped vesicular structure, after its hydrogen storage property is tested through PCT, its reversible hydrogen adsorption and desorption curve is similar to Fig. 1, through after 4 reversible cycle, reversible hydrogen desorption capacity does not descend, but compares with the solid-state hydrogen storage material in Fig. 1, its total hydrogen desorption capacity descends a little to some extent, and its hydrogen desorption capacity is 3.4wt%.
Embodiment 4
1) with Co 3B and CeO 2Mass ratio by 1:1 mixes in mortar, gets mixed catalyst; 2) secure ph is 13 the NaOH aqueous solution, then with NaBH 4Be dissolved in and get NaBH in the NaOH aqueous solution 4Alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Massfraction be 9%, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With 60% of mixed catalyst total mass; 3) with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in 25 ℃ of hydrogen discharge reactions 10 minutes of being hydrolyzed hydrolysate, after hydrolysate is filtered under 25 ℃ dry 24 hours solid-state hydrogen storage material.
This solid-state hydrogen storage material is through after XRD analysis, and phase forms similar to Fig. 2, wherein, and Co 3B-CeO 2Account for NaBO 2-Co 3B-CeO 228% of quality.And the microtexture of material is the same with Fig. 3 is a kind of cotton-shaped vesicular structure, and different is that after its hydrogen storage property is tested through PCT, its reversible hydrogen adsorption and desorption amount has reached 5.8wt%.This illustrates CeO 2To NaBO 2-Co 3B-CeO 2The raising of reversible hydrogen desorption capacity is more obvious.
The above is only to of the present invention further illustrating and non-limiting; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvement or retouching, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (5)

1. solid-state hydrogen storage material, it is characterized in that: this solid-state hydrogen storage material is by NaBO 2, Co 3B and rare earth oxide form, Co in described solid-state hydrogen storage material 3The massfraction sum of B and rare earth oxide is 20-40%.
2. a kind of solid-state hydrogen storage material according to claim 1, is characterized in that: described Co 3B: the mass ratio of rare earth oxide is 1:0.5-1.5.
3. a kind of solid-state hydrogen storage material according to claim 1, it is characterized in that: described rare earth oxide is Y 2O 3Or CeO 2
4. preparation method of solid-state hydrogen storage material as claimed in claim 1 is characterized in that: comprise the following steps:
1) with Co 3B and rare earth oxide are pressed Co 3B: the mass ratio of rare earth oxide is that 1:0.5-1.5 mixes, and gets mixed catalyst;
2) preparation NaBH 4Alkaline aqueous solution, NaBH 4NaBH in alkaline aqueous solution 4Content be NaBH 4With the 50-60% of mixed catalyst total mass, with mixed catalyst and NaBH 4After alkaline aqueous solution mixes in the 25-30 ℃ of hydrolysate that was hydrolyzed hydrogen discharge reaction 10-30 minute to get, after hydrolysate is filtered under 15-30 ℃ dry 12-24 hour solid-state hydrogen storage material.
5. a kind of preparation method of solid-state hydrogen storage material according to claim 4, is characterized in that: described NaBH 4The preparation method of alkaline aqueous solution is: preparation pH is the NaOH aqueous solution of 12-13, then with NaBH 4Be dissolved in the NaOH aqueous solution NaBH 4Massfraction be 8-10%.
CN201310068706.7A 2013-03-04 2013-03-04 Solid hydrogen storage material and preparation method thereof Expired - Fee Related CN103145098B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922277A (en) * 2014-04-04 2014-07-16 长安大学 Porous hydrogen storage material and preparation method thereof
CN103922276A (en) * 2014-04-04 2014-07-16 长安大学 Preparation method of hydrogen storage material with high reversible hydrogen storage capacity
CN113735057A (en) * 2021-08-31 2021-12-03 苏州睿分电子科技有限公司 Activation-free hydrogen storage material and preparation method and device thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
CN102431968A (en) * 2011-08-26 2012-05-02 上海交通大学 Reversible composite hydrogen storage material containing rare earth element Y, and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
CN102431968A (en) * 2011-08-26 2012-05-02 上海交通大学 Reversible composite hydrogen storage material containing rare earth element Y, and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YI-CHUN LU ET AL.: "Hydrogen generation by sodium borohydride hydrolysis on nanosized CoB catalysts supported on TiO2 , Al2O3 and CeO2", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 37, 21 December 2011 (2011-12-21), pages 4254 - 4258 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922277A (en) * 2014-04-04 2014-07-16 长安大学 Porous hydrogen storage material and preparation method thereof
CN103922276A (en) * 2014-04-04 2014-07-16 长安大学 Preparation method of hydrogen storage material with high reversible hydrogen storage capacity
CN103922276B (en) * 2014-04-04 2015-12-02 长安大学 A kind of preparation method of high reversible hydrogen storage capacity hydrogen storage material
CN113735057A (en) * 2021-08-31 2021-12-03 苏州睿分电子科技有限公司 Activation-free hydrogen storage material and preparation method and device thereof

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