CN102431968B - Reversible composite hydrogen storage material containing rare earth element Y, and preparation method thereof - Google Patents

Reversible composite hydrogen storage material containing rare earth element Y, and preparation method thereof Download PDF

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Publication number
CN102431968B
CN102431968B CN2011102493476A CN201110249347A CN102431968B CN 102431968 B CN102431968 B CN 102431968B CN 2011102493476 A CN2011102493476 A CN 2011102493476A CN 201110249347 A CN201110249347 A CN 201110249347A CN 102431968 B CN102431968 B CN 102431968B
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hydrogen storage
storage material
composite hydrogen
hydrogen
reversible composite
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CN102431968A (en
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邹建新
李龙津
曾小勤
丁文江
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Shanghai Jiaotong University
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Shanghai Jiaotong 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 discloses a reversible composite hydrogen storage material containing a rare earth element Y, and a preparation method thereof. The reversible composite hydrogen storage material comprises components of YF3 and NaBH4. With the material provided by the invention, the dynamic performance of the hydrogen storage material is improved. With the added YF3 rare earth compound, the hydrogen storage material has a better dynamic performance than traditional pure-NaBH4 materials. The material provided by the invention has lower hydrogen discharging temperature (which is reduced by 80DEG C), and reversibility. The material provided by the invention has a higher hydrogen storage capacity. Under a temperature of 300 DEG C, the hydrogen absorption of the material is approximately 1.5%. The total content of impurity elements in the material is lower than 0.01% by mass.

Description

A kind of reversible composite hydrogen storage material containing rare earth element y and preparation method thereof
Technical field
The present invention relates to a kind of hydrogen storage material that belongs to the non-metallic material class, be specifically related to a kind of hydrogen storage material containing rare earth element y.
Background technology
Hydrogen is a kind of energy carrier of high-efficiency cleaning.Hydrogen can obtain from multiple channel, in use by fuel cell, hydrogen can be converted into to electricity and heat, can realize zero release simultaneously.Along with the intensification of energy dilemma, the effect of hydrogen energy source more and more is taken seriously, and is considered to connect the bridge of fossil energy to the renewable energy source transition, realizes one of important carrier of energy sustainable supply and circulation.But the application of hydrogen fuel cell also has a lot of difficulties, is mainly there is no convenient and swift, direct hydrogen supply mode and lack hydrogen storage technology safely and effectively.Therefore the main key that develops hydrogen energy automobile and portable power supplies is exactly to develop hydrogen supply and hydrogen storage technology safely and effectively.
At present, the hydrogen storage mode that most common technique is the most ripe is to utilize high-pressure cylinder to store, but this method is not only dangerous, and the superelevation weight of bomb self has greatly restricted its application as portable energy source.The solid-state hydrogen storage material storage is by chemical reaction or physical adsorption, hydrogen to be stored in solid-state material, and its energy density is high and security good, is considered to the most promising a kind of storage hydrogen mode.The lightweight high power capacity storage hydrogen material theoretical capacity be comprised of protium all reaches more than 5%, for the breakthrough of solid-state hydrogen storage material and technology has brought hope.Sodium borohydride (NaBH4) is one of research object the most popular in the lightweight high power capacity storage hydrogen material.
Sodium borohydride is the crystalline powder of a kind of white, and theoretical hydrogen storage capability is 10.8% (massfraction).Sodium borohydride is a kind of strong reductant, under room temperature and catalyst action, can produce hydrogen with the water reaction.But also there are many difficulties in preparing hydrogen by sodium borohydride hydrolysis, and do not there is reversibility.But another kind method utilization heating sodium borohydride decomposes also hydrogen manufacturing, but equally also has a lot of shortcomings, as high as decomposition temperature, pure NaBH 4need ability decomposing hydrogen more than 500 ℃ in 1atmAr, and almost there is no reversibility, so also be difficult to be applied in reality.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, provide a kind of containing YF 3the compound reversible hydrogen storage material of rare earth of (yttrium fluoride) and preparation method thereof, simple for process, the hydrogen storage material made has than pure NaBH 4with other NaBH 4the performances such as the superior hydrogen discharging temperature of composite hydrogen storage material, reversibility keep higher hydrogen-storage amount simultaneously.
For achieving the above object, the present invention is by the following technical solutions:
A kind of reversible composite hydrogen storage material containing rare earth element y, comprise following component: YF 3and NaBH 4; Described constituent mass percentage composition is: YF 3be 10%～56.26%, NaBH 4be 43.74%～90%.
The invention still further relates to a kind of method for preparing above-mentioned reversible composite hydrogen storage material, comprise the following steps:
A. by NaBH 4and YF 3be configured to mixed powder;
B. above-mentioned mixed powder is placed in to ball mill and carries out ball milling under protection of inert gas;
C. after above-mentioned mixed powder fully reacts, stop ball milling, products therefrom is the reversible composite hydrogen storage material that the present invention contains rare earth element y.
YF in described step a 3be 10%～56.26% (quality), NaBH 4be 43.74%～90% (quality); In described step b, rare gas element is argon gas, steel ball: the mass ratio of mixed powder is 30: 1, big steel ball: the mass ratio of small ball is 1: 2; Described drum's speed of rotation is set to 400r/min, and in 10～50 cycles of ball milling, each cycle turns 6～50 minutes and stops 6～12 minutes.
Advantage of the present invention is:
(1) improved the dynamic performance of hydrogen storage material, by adding YF 3the rare earth compound hydrogen storage material has the purer NaBH than in the past 4better dynamic performance, i.e. lower hydrogen discharging temperature (having reduced by 80 ℃).
(2) make containing NaBH 4hydrogen storage material reversibility appears, and than existing added catalyzer containing NaBH 4hydrogen storage material will have better reversibility, and under 300 ℃ of conditions, material is still inhaled hydrogen approximately 1.5%.
(3) system has the hydrogen-storage amount that maximum can reach 4.5wt%, and the total amount of impurities element is less than 0.01% (quality).
The accompanying drawing explanation
Fig. 1 inhales the PCT curve (P-C-T curve) of putting after hydrogen circulates under 300 ℃;
Fig. 2 inhales the PCT curve (P-C-T curve) of putting after hydrogen circulates under 350 ℃;
Fig. 3 repeatedly inhales the PCT curve (P-C-T curve) of putting after hydrogen circulates under 380 ℃;
Fig. 4 repeatedly inhales the PCT curve (P-C-T curve) of putting after hydrogen circulates under 380 ℃;
The DSC curve that Fig. 5 is reversible composite hydrogen storage material of the present invention (differential scanning calorimetric analysis curve);
The XRD spectra that Fig. 6 is reversible composite hydrogen storage material of the present invention (X-ray diffraction spectrum).
Embodiment
Embodiment 1
(1) take 3.402gNaBH 4powder and 4.377gYF 3powder, then mix;
(2) mixed powder is joined to ball grinder, and add steel ball with the ball material mass ratio of 30: 1 and the sizes of balls mass ratio of 1: 2;
(3) ball milling under argon shield, rotational speed of ball-mill is set to 400r/min, and in 25 cycles of ball milling, each cycle turns 48 minutes and stops 12 minutes;
(4) after ball milling completes, take out sample, obtain the reversible composite hydrogen storage material of product of the present invention containing rare earth element y, contained YF 3be 56.26% (quality), NaBH 4be 43.74% (quality).
Above-mentioned prepared product reversible composite hydrogen storage material of the present invention is carried out to DSC (differential scanning calorimetric analysis) and XRD (X-ray diffraction spectrum) test: the PCT curve (P-C-T curve) of putting after hydrogen circulates is inhaled for product reversible composite hydrogen storage material of the present invention in Fig. 1～4; Fig. 1 shows that, under the low temperature of 300 ℃, described reversible composite hydrogen storage material still has the reversible hydrogen storage capacity up to 1.5%, has excellent low temperature hydrogen storage property.Fig. 1～3 show that increasing reversible hydrogen－sucking amount with temperature increases; Fig. 3～4 show that the reversible hydrogen storage capacity of described reversible composite hydrogen storage material has stability preferably; The DSC curve that Fig. 5 is product reversible composite hydrogen storage material of the present invention (differential scanning calorimetric analysis curve), comprise weight-loss curve and endothermic curve, and X-coordinate is temperature, and left ordinate zou is caloric value, and right ordinate zou is mass percent.The DSC result shows that hydrogen desorption capacity is 4.16 (wt) %, 425 ℃ of hydrogen discharging temperatures.Illustrate that described reversible composite hydrogen storage material hydrogen discharging temperature reduces, dynamic performance improves; The XRD spectra that Fig. 6 is product reversible composite hydrogen storage material of the present invention, show in system to contain this technique synthetic containing YF 3composite hydrogen storage material do not generate cenotype, YF 3play catalyzer.
Embodiment 2
(1) take 3.402gNaBH 4powder and 4.377gYF 3powder, then mix;
(2) mixed powder is joined to ball grinder, and add steel ball with the ball material mass ratio of 30: 1 and the sizes of balls mass ratio of 1: 2;
(3) ball milling under the 1atm argon shield, rotational speed of ball-mill is set to 400r/min, and in 50 cycles of ball milling, each cycle turns 48 minutes and stops 12 minutes;
(4) after ball milling completes, take out sample, obtain the reversible composite hydrogen storage material of product of the present invention containing rare earth element y, contained YF 3be 56.26%, NaBH 4be 43.74%.
Product of the present invention after ball milling is carried out to DSC and XRD test.
The DSC result shows that hydrogen desorption capacity is 3.68 (wt) %, 437 ℃ of hydrogen discharging temperatures.
In XRD test chart phaneroplasm system, contain this technique synthetic containing YF 3composite hydrogen storage material do not generate cenotype, YF 3play catalyzer.
Embodiment 3
(1) take 3.402gNaBH 4powder and 0.5gYF 3powder, then mix;
(2) mixed powder is joined to ball grinder, and add steel ball with the ball material mass ratio of 30: 1 and the sizes of balls mass ratio of 1: 2;
(3) ball milling under argon shield, rotational speed of ball-mill is set to 400r/min, and in 12 cycles of ball milling, each cycle turns 48 minutes and stops 12 minutes;
(4) after ball milling completes, take out sample, obtain the reversible composite hydrogen storage material of product of the present invention containing rare earth element y, contained YF 3be 12.81%, NaBH 4be 87.19%.
Product of the present invention after ball milling is carried out to DSC and XRD test.
The DSC result shows that hydrogen desorption capacity is 3.86 (wt) %, 432 ℃ of hydrogen discharging temperatures.
In XRD test chart phaneroplasm system, contain this technique synthetic containing YF 3composite hydrogen storage material do not generate cenotype, YF 3play catalyzer.
Embodiment 4
(1) take 1.194gNaBH 4powder and 1gYF 3powder, then mix;
(2) mixed powder is joined to ball grinder, and add steel ball with the ball material mass ratio of 30: 1 and the sizes of balls mass ratio of 1: 2;
(3) ball milling under argon shield, rotational speed of ball-mill is set to 400r/min, and in 50 cycles of ball milling, each cycle turns 6 minutes and stops 6 minutes;
(4) after ball milling completes, take out sample, obtain the reversible composite hydrogen storage material of product of the present invention containing rare earth element y, contained YF 3be 45.58%, NaBH 4be 54.42%.
Product of the present invention after ball milling is carried out to DSC and XRD test.
The DSC result shows that hydrogen desorption capacity is 3.89 (wt) %, 435 ℃ of hydrogen discharging temperatures.
In XRD test chart phaneroplasm system, contain this technique synthetic containing YF 3composite hydrogen storage material do not generate cenotype, YF 3play catalyzer.
Embodiment 5
(1) take 3.402gNaBH 4powder and 1gYF 3, powder, then mix;
(2) mixed powder is joined to ball grinder, and add steel ball with the ball material mass ratio of 30: 1 and the sizes of balls mass ratio of 1: 2;
(3) ball milling under argon shield, rotational speed of ball-mill is set to 400r/min, and in 12 cycles of ball milling, each cycle turns 48 minutes and stops 12 minutes;
(4) after ball milling completes, take out sample, obtain the reversible composite hydrogen storage material of product of the present invention containing rare earth element y, contained YF 3be 22.72%, NaBH 4be 77.28%.
Product of the present invention after ball milling is carried out to DSC and XRD test.
The DSC result shows that hydrogen desorption capacity is 4.05%, 440 ℃ of hydrogen discharging temperatures.
In XRD test chart phaneroplasm system, contain this technique synthetic containing YF 3composite hydrogen storage material do not generate cenotype, YF 3play catalyzer.

Claims (6)

1. the reversible composite hydrogen storage material containing rare earth element y, is characterized in that being comprised of the component of following quality percentage composition: 10%～56.26% YF 3with 43.74%～90% NaBH 4.
2. a method for preparing reversible composite hydrogen storage material claimed in claim 1 is characterized in that comprising the following steps:
A. by NaBH 4and YF 3be configured to mixed powder;
B. above-mentioned mixed powder is placed in to ball mill and carries out ball milling under protection of inert gas;
C. after above-mentioned mixed powder fully reacts, stop ball milling, products therefrom is the reversible composite hydrogen storage material containing rare earth element y.
3. the method for preparing reversible composite hydrogen storage material according to claim 2, is characterized in that: YF in described step a 3be 10%～56.26%(quality), NaBH 4be 43.74%～90%(quality).
4. the method for preparing reversible composite hydrogen storage material according to claim 2, it is characterized in that: in described step b, rare gas element is argon gas.
5. the method for preparing reversible composite hydrogen storage material according to claim 2, it is characterized in that: steel ball in described step b: the mass ratio of mixed powder is 30:1, big steel ball: the mass ratio of small ball is 1:2.
6. the method for preparing reversible composite hydrogen storage material according to claim 2, it is characterized in that: described drum's speed of rotation is set to 400r/min, and in 10～50 cycles of ball milling, each cycle turns 6～50 minutes and stops 6～12 minutes.
CN2011102493476A 2011-08-26 2011-08-26 Reversible composite hydrogen storage material containing rare earth element Y, and preparation method thereof Expired - Fee Related CN102431968B (en)

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