CN103159171A - LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof - Google Patents
LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof Download PDFInfo
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- CN103159171A CN103159171A CN2013100756902A CN201310075690A CN103159171A CN 103159171 A CN103159171 A CN 103159171A CN 2013100756902 A CN2013100756902 A CN 2013100756902A CN 201310075690 A CN201310075690 A CN 201310075690A CN 103159171 A CN103159171 A CN 103159171A
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- libh
- hydrogen
- libh4
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Abstract
The invention discloses a LiBH4-doped metal sulfide hydrogen-storage composite material and a preparation method thereof. The LiBH4-doped metal sulfide hydrogen-storage composite material comprises LiBH4 and 10 to 30wt% of one or more metal sulfides, wherein the one or more metal sulfides are selected from MnS, MoS2 and WS2. The preparation method comprises that LiBH4 and the one or more metal sulfides are subjected to intermittent ball-milling treatment in the argon protective atmosphere to form the LiBH4-doped metal sulfide hydrogen-storage composite material. The LiBH4-doped metal sulfide hydrogen-storage composite material can obviously reduce a LiBH4 initial dehydrogenation temperature and improve a hydrogen absorption/discharge capacity and performances of LiBH4. Through utilization of the cheap and easily-acquired metal sulfides, the LiBH4-doped metal sulfide hydrogen-storage composite material can be prepared by the simple preparation method and is conducive to industrial volume production.
Description
Technical field the present invention relates to a kind of LiBH
4Composite for hydrogen storage and preparation method thereof.
The advantages such as the background technology Hydrogen Energy is high due to its wide material sources, cleanliness without any pollution, energy density, reusable edible more and more are subject to people's favor.Yet how efficient storage of hydrogen is one of key factor that restricts at present the Hydrogen Energy utilization.Existing hydrogen storage material comprises: organic liquid hydrogen storage material, metal hydrogen storage material and coordinate hydride hydrogen-storing material etc., and in view of LiBH
4Have significant advantage in volume hydrogen-storage density and quality hydrogen-storage density (18.3%), developed in recent years a kind of novel hydrogen storage material that is expected to obtain practical application, this has been carried out large quantity research both at home and abroad.But LiBH
4The bond energy of middle B-H key is large, makes its initial dehydrogenated temperature higher, decomposes in addition the B simple substance that produces and causes its reversibility poor, and these shortcomings have limited LiBH greatly
4Practical application in productive life.Therefore, prepare LiBH by admixed with additives
4Composite for hydrogen storage reduces LiBH
4Thermodynamic stability and improve its reaction reversibility, become and improved LiBH
4A kind of effective ways of hydrogen storage property.Chinese patent (patent application number: 201110006077.6) disclose a kind of CaF
2Li doped BH
4High hydrogen storage reversible hydrogen storage material and preparation method thereof, the catalyzer that this patent relates to is TiF
3, CeF
3, NbCl
5, first by mechanical ball milling, then be evacuated to 1Pa in the preparation, be filled with at last the high-purity hydrogen of 90atm, thereby obtain CaF
2The LiBH of doping
4Hydrogen storage material, this patent has obviously been improved LiBH
4Suction/put reversible hydrogen, but that hydrogen pressure fills in institute is excessive, needs simultaneously pressurize 10～24h, the dwell time is long, easily cause danger; In addition, this patent catalyzer price used is higher, is unsuitable for dropping among large batch of industrial production.
Summary of the invention the object of the present invention is to provide and a kind ofly can significantly reduce LiBH
4The initial dehydrogenated temperature, improve LiBH
4Inhale/put capacity and the performance of hydrogen, and the metallic sulfide cost that uses is cheap, raw material is easy to get, and the composite manufacture method is simple, is suitable for the LiBH of industrialized mass production
4Composite for hydrogen storage of doping metals sulfide and preparation method thereof.The present invention is mainly with LiBH
4Powder and metallic sulfide powder are processed by mechanical ball milling, obtain a kind of LiBH
4The matrix material that the hydrogen storage property of doping metals sulfide is good.
Composite for hydrogen storage of the present invention is by LiBH
4Form with metallic sulfide, wherein metallic sulfide content accounts for 10～30wt.% of matrix material quality, and described metallic sulfide is MnS, MoS
2And WS
2In one or more.
Above-mentioned LiBH
4The preparation method of the composite for hydrogen storage of doping metals sulfide is with LiBH
4Carry out mechanical ball milling with metallic sulfide under the argon gas atmosphere protection, Ball-milling Time is 5～30h, and every ball milling 15min is 15min intermittently, ratio of grinding media to material 35～40:1, rotating speed 500～600r/min.Naturally cool to room temperature after ball milling, encapsulate under argon gas atmosphere, obtain the composite for hydrogen storage of doping metals sulfide.
The present invention compared with prior art has the following advantages:
1. can significantly reduce LiBH by doping metals sulfide
4The initial dehydrogenated temperature, improve LiBH
4Inhale/put capacity and the performance of hydrogen.
2. the metallic sulfide cost of the present invention's use is cheap, and raw material is easy to get, and the composite manufacture method is simple, is conducive to industrialized mass production.
Description of drawings
Fig. 1 is that the embodiment of the present invention 1 makes LiBH
4After+10wt.%MnS ball milling and fully put Fourier's infrared spectrum after hydrogen.
Fig. 2 is that the embodiment of the present invention 2 makes LiBH
4+ 20wt.%MoS
2And LiBH
4At 550 ℃ of lower hydrogen-absorption speed correlation curve figure.
Fig. 3 is that the embodiment of the present invention 3 makes LiBH
4+ 20wt.%MoS
2After ball milling and put XRD figure spectrum after hydrogen.
Fig. 4 is that the embodiment of the present invention 4 makes LiBH
4+ 25wt.%MnS and LiBH
4TPD correlation curve figure.
Fig. 5 is that the embodiment of the present invention 5 makes LiBH
4+ 15wt.%MnS+15wt.%WS
2And LiBH
4TPD correlation curve figure.
Fig. 6 is that the embodiment of the present invention 6 makes LiBH
4+ 30wt.%WS
2And LiBH
4At 400 ℃ of lower hydrogen discharging rate correlation curve figure.
Fig. 7 is that the embodiment of the present invention 7 makes LiBH
4The 1st time and the 2nd hydrogen-absorption speed correlation curve figure under 550 ℃.
Fig. 8 is that the embodiment of the present invention 7 makes LiBH
4+ 20wt.%MoS
2The 1st time and the 2nd hydrogen-absorption speed correlation curve figure under 550 ℃.
Embodiment
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the MnS of 10wt.%, rotating speed 600r/min, and ratio of grinding media to material is 40:1, Ball-milling Time is 10h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cool to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
After the pressure sheet, the sample sample tube of packing into, vacuumize 3h under 550 ℃ of constant temperature, makes it fully put hydrogen, and then naturally cooling, treat that sample tube is cooled to room temperature, and sample is taken out under argon gas atmosphere, and it is carried out Fourier's infrared test.Its test result is as shown in Figure 1: after ball milling, sample is 1134cm in wave number
-1, 2225cm
-1, 2292cm
-1Stronger B-H key characteristic peak all appears in the place, illustrates that ball milling does not destroy LiBH fully
4In [BH
4]
-Group; After putting hydrogen fully, the corresponding characteristic peak of B-H key all do not occur in above-mentioned three positions, illustrate that the B-H key ruptures fully, sample is fully put hydrogen.
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the MoS of 20wt.%
2, rotating speed 500r/min, ratio of grinding media to material is 38:1, and Ball-milling Time is 15h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
After the pressure sheet, the sample sample tube of packing into, vacuumize 3h under 550 ℃ of constant temperature, makes it fully put hydrogen, then inhales the hydrogen kinetic test under the condition of 4MPa hydrogen pressure.Its test result is as shown in Figure 2: in 2790s, and the LiBH of the sulfide that do not adulterate
4Hydrogen－sucking amount is 6.00wt.%, has added MoS
2Matrix material hydrogen－sucking amount within the identical time be 8.07wt.%, and hydrogen-absorption speed is than LiBH
4Compare and be significantly improved.This shows MoS
2Can effectively improve LiBH
4Hydrogen-absorption speed.
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the MoS of 20wt.%
2, rotating speed 550r/min, ratio of grinding media to material is that the 38:1 Ball-milling Time is 20h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
The sample after ball milling that takes a morsel, the sample tube of packing into after compressing tablet vacuumizes 3h under 550 ℃ of constant temperature, make it fully put hydrogen, and then naturally cooling, treat that sample tube is cooled to room temperature, and sample is taken out under argon gas atmosphere, obtains putting sample after hydrogen.After can finding out ball milling, the XRD figure spectrum of Fig. 3 generates a small amount of Li
2S and MoB
2Phase is fully put Li after hydrogen
2S and MoB
2Increase mutually.
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the MnS of 25wt.%, rotating speed 500r/min, and ratio of grinding media to material is that the 35:1 Ball-milling Time is 25h, ball milling method is just/counter-rotating ball milling at intermittence, every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
The sample that takes a morsel after the compressing tablet sample tube of packing into carries out the temperature programmed desorption(TPD) test, and Elevated Temperature Conditions is: temperature rise rate is 5 ℃/min, and the intensification scope is room temperature～650 ℃, and holding temperature is 650 ℃.By the TPD curve of Fig. 4 as can be known: the initial dehydrogenated temperature of the matrix material of doped with Mn S is 235 ℃, than the LiBH that does not add MnS
4Initial dehydrogenated temperature (315 ℃) has reduced by 80 ℃.Hence one can see that, and the doping of sulfide can reduce LiBH
4The initial dehydrogenated temperature.
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the MnS of 15wt.% and the WS of 15wt.%
2, rotating speed 600r/min, ratio of grinding media to material is that the 35:1 Ball-milling Time is 30h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
The sample that takes a morsel after the compressing tablet sample tube of packing into carries out the temperature programmed desorption(TPD) test, and Elevated Temperature Conditions is: temperature rise rate is 5 ℃/min, and the intensification scope is room temperature～650 ℃, and holding temperature is 650 ℃.From the TPD curve of Fig. 5 as can be known: doped with Mn S and WS
2Its initial dehydrogenated temperature of matrix material be 230 ℃, compare LiBH
4Initial dehydrogenated temperature (315 ℃) reduced by 85 ℃.Hence one can see that, and the doping of sulfide can reduce LiBH
4The initial dehydrogenated temperature.
Under the argon gas atmosphere protection, to LiBH
4Middle interpolation massfraction is the WS of 30wt.%
2, rotating speed 600r/min, ratio of grinding media to material is that the 40:1 Ball-milling Time is 5h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
The sample that takes a morsel after the compressing tablet sample tube of packing into carries out the hydrogen desorption kinetics test.The hydrogen pressure that gives 1MPa during intensification was put hydrogen to suppress sample before 400 ℃.From the TPD curve of Fig. 6 as can be known: WS has adulterated under 400 ℃
2The matrix material hydrogen discharging rate obviously accelerate, hydrogen desorption capacity can reach 2.12wt.% when 2766s, and LiBH
4Hydrogen desorption capacity only has 1.74wt.% in same time, than doping WS
2The few 0.38wt.% of matrix material.Hence one can see that: WS
2The matrix material of doping, its hydrogen discharging performance is better than LiBH
4
Under the argon gas atmosphere protection, to LiBH
4Middle doping massfraction is the MoS of 20wt.%
2, rotating speed 500r/min, ratio of grinding media to material is 36:1, and Ball-milling Time is 10h, and ball milling method is just/counter-rotating ball milling at intermittence, and every ball milling 15min is 15min intermittently, naturally cools to room temperature after ball milling is complete, carries out the compressing tablet encapsulation under argon gas atmosphere.
The sample that takes a morsel after the compressing tablet sample tube of packing into carries out the suction hydrogen kinetic test under 550 ℃.From the suction hydrogen curve of Fig. 7 as can be known: LiBH
4In 3762s, the 2nd hydrogen－sucking amount is than the 1st 1.37wt.% that decayed; From the suction hydrogen curve of Fig. 8 as can be known: MoS has adulterated
2Matrix material in 2778s, the hydrogen－sucking amount of the 2nd time and the 1st time basic identical.By Fig. 7, Fig. 8 MoS more as can be known
2Doping to LiBH
4Reversibility larger improvement is arranged.
Claims (2)
1. LiBH
4The composite for hydrogen storage of doping metals sulfide is characterized in that: this matrix material is by LiBH
4Form with metallic sulfide, wherein metallic sulfide accounts for 10～30wt.% of matrix material quality, and described metallic sulfide is MnS, MoS
2And WS
2In one or more.
2. LiBH claimed in claim 1
4The preparation method of the composite for hydrogen storage of doping metals sulfide is characterized in that: with LiBH
4Carry out mechanical ball milling with metallic sulfide under the argon gas atmosphere protection; Ball-milling Time is 5～30h; every ball milling 15min is 15min intermittently; ratio of grinding media to material 35～40:1; rotating speed 500～600r/min; naturally cool to room temperature after ball milling, encapsulate under argon gas atmosphere, obtain the composite for hydrogen storage of doping metals sulfide.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030239A (en) * | 2014-05-28 | 2014-09-10 | 桂林电子科技大学 | High-capacity light metal composite hydrogen storage material and preparation method thereof |
| CN105016298A (en) * | 2015-07-08 | 2015-11-04 | 燕山大学 | Hydrogen storage composite material of lithium borate-doped lithium borohydride and preparation method of hydrogen storage composite material |
| CN109225284A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院理化技术研究所 | Hydrogen storage material decomposition and desorption system |
| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7951747B1 (en) * | 2009-04-03 | 2011-05-31 | Sandia Corporation | Single-layer transition metal sulfide catalysts |
| CN102586660A (en) * | 2012-02-27 | 2012-07-18 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material with metal sulfide added |
-
2013
- 2013-03-08 CN CN2013100756902A patent/CN103159171A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7951747B1 (en) * | 2009-04-03 | 2011-05-31 | Sandia Corporation | Single-layer transition metal sulfide catalysts |
| CN102586660A (en) * | 2012-02-27 | 2012-07-18 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material with metal sulfide added |
Non-Patent Citations (2)
| Title |
|---|
| WEITONG CAI等: "Remarkable irreversible and reversible dehydrogenation of LiBH4 by doping with nanosized cobalt metalloid compounds", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| YANHONG JIA等: "Hydrogen absorption and desorption kinetics of MgH 2 catalyzed by MoS2 and MoO2", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030239A (en) * | 2014-05-28 | 2014-09-10 | 桂林电子科技大学 | High-capacity light metal composite hydrogen storage material and preparation method thereof |
| CN105016298A (en) * | 2015-07-08 | 2015-11-04 | 燕山大学 | Hydrogen storage composite material of lithium borate-doped lithium borohydride and preparation method of hydrogen storage composite material |
| CN109225284A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院理化技术研究所 | Hydrogen storage material decomposition and desorption system |
| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
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Application publication date: 20130619 |