CN102910581A - Me-RGO (Reduced Graphene Oxide)/LiBH4 hydrogen storage material with high hydrogen storage capacity and preparation methods of Me-RGO/LiBH4 hydrogen storage material - Google Patents

Me-RGO (Reduced Graphene Oxide)/LiBH4 hydrogen storage material with high hydrogen storage capacity and preparation methods of Me-RGO/LiBH4 hydrogen storage material Download PDF

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CN102910581A
CN102910581A CN2012104054656A CN201210405465A CN102910581A CN 102910581 A CN102910581 A CN 102910581A CN 2012104054656 A CN2012104054656 A CN 2012104054656A CN 201210405465 A CN201210405465 A CN 201210405465A CN 102910581 A CN102910581 A CN 102910581A
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rgo
hydrogen storage
libh
storage material
hydrogen
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许娟
孟蓉蓉
曹剑瑜
陈智栋
王文昌
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CHANGZHOU JIANGGONG KUOZHI ELECTRONIC TECHNOLOGY CO LTD
Changzhou University
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CHANGZHOU JIANGGONG KUOZHI ELECTRONIC TECHNOLOGY CO LTD
Changzhou 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

Abstract

The invention provides a Me-RGO (Reduced Graphene Oxide) modified LiBH4 hydrogen storage material with high hydrogen storage capacity and preparation methods of the Me-RGO modified LiBH4 hydrogen storage material. A uniformly-dispersed Me-RGO catalyst with a high special surface is compounded on the surface of the hydrogen storage material LiBH4 at the inert gas shielding atmosphere by respectively using a solid-phase high-speed ball-milling method, a melt infiltration method and a liquid-phase dispersion method to prepare the hydrogen storage material with high hydrogen storage capacity. The preparation methods of the Me-RGO catalyst with high dispensability include an aqueous phase complex reduction method, a vapour phase reduction method, an ion exchange method, a sol-gel method, a hydrothermal method, a vacuum sputtering method and a gas evaporation method. Even if the content of the used Me-RGO catalyst is as low as 3wt.%, the hydrogen discharging temperature of LiBH4 can also be greatly reduced, and meanwhile, the low-temperature hydrogen discharging capacity and the circulated hydrogen absorption and discharging properties of LiBH4 can be improved.

Description

Me-RGO/LiBH 4High hydrogen storage composite hydrogen storage material and preparation method thereof
Technical field
The present invention relates to hydrogen storage material modification field, provide a kind of heavy body, low temperature to put hydrogen and the reversible Me-RGO/LiBH that charges and discharge the hydrogen superior performance 4High hydrogen storage composite hydrogen storage material and preparation method thereof.
Background technology
Hydrogen Energy has occurred a large amount of example use owing to thermo-efficiency in the combustion processes high (combustion value is 3 times of gasoline), non-exhaust emission and product are that the advantages such as water become a kind of new cleaning fuel that 21 century has development potentiality at numerous areas (especially aspect the electromobile take hydrogen-oxygen fuel cell as power).Solid-state material storage hydrogen need not because having that high pressure and heat-insulated container, security are good, low cost and other advantages plays an important role in the development and utilization of Hydrogen Energy.
In all kinds of solid-state hydrogen storage material, with AlH 4 -, BH 4 -And NH 2 -, the advantages such as degree of safety high, convenient transport large because of its storage hydrogen specific storage in light metal (such as Li, the Na etc.) hydride that is base become the important confession hydrogen source of fuel cell.In these light metal hydride, LiBH 4Have very high theoretical hydrogen storage capability (up to 18.5wt.%), can satisfy in theory the requirement (the USDOE requirement reached 9.0wt.% in 2015) of vehicle-mounted power hydrogen source fully.But pure LiBH 4Initial hydrogen discharging temperature up to 400 ° of C, even temperature is elevated to the capacity that 600 ° of C also only can emit 8wt.%, and the condition of reversible suction hydrogen is extremely harsh, need to inhale hydrogen under 600 ° of C and 350atm hydrogen pressure condition, this has just greatly limited LiBH 4Practical application as hydrogen storage material.How optimizing it, to store hydrogen condition be current LiBH 4The hydrogen storage material exploitation needs the matter of utmost importance of research.
In recent years, existing scholar confirms that the method that nanocatalyst is modified can effectively reduce LiBH 4Initial hydrogen discharging temperature and improve it and put hydrogen capacity.2003, Zuttel seminar at first reported (the LiBH with mass ratio 1:3 4: SiO 2) ratio in LiBH4, add nanometer SiO 2, so that LiBH 4Initial hydrogen discharging temperature be reduced to about 240 ° of C, approximately have the hydrogen of 9wt.% to be released when temperature is elevated to 400 ° of C.The people such as Zhang further add the tertiary mixture (LiBH that TiF3 forms 4+ 0.2SiO 2+ 0.3TiF 3) can put hydrogen since 70 ° of C, 500 ° of following hydrogen capacities of putting of C reach approximately 8.3wt.%.The people such as Jurgensen report TiO 2, V 2O 5Can make LiBH Deng metal oxide 4Temperature of initial decomposition be reduced to approximately 200 ° of C, and degradation production can the reversible suction hydrogen of part under the condition of 600 ° of C and 80atm.According to the literature, mix LiBH with the 1:4 ratio 4And MgH 2, mix LiBH with the 1:1 ratio 4Mix LiBH with carbon material and with the 1:2 ratio 4And LiNH 2All can greatly reduce LiBH 4Initial hydrogen discharging temperature.But LiBH in these researchs 4The mass ratio of catalyst system therefor is all very high, have in addition reach LiBH 4Four times of amount, this just greatly reduces the available hydrogen total amount of putting.
Graphene is a kind of carbonaceous novel material of the tightly packed one-tenth individual layer of carbon atom bi-dimensional cellular shape crystalline network, is the elementary cell that makes up other dimension carbonaceous material (such as zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).Graphene has that quality is light, the advantage of high chemical stability and high-specific surface area, makes it become the good hydrogen storage material with physisorption storage hydrogen.The researchers of Greece university have designed novel 3D Graphene post, and its hydrogen-storage amount can reach 6.1wt.%.The calculated results shows that the hydrogen-storage amount of the Graphene that calcium atom (Ca) mixes can reach 8.4wt.%.
We have been reported in LiBH 4In mix the activated carbon supported nanometer metal palladium of 50wt.% (Pd-C) and can increase substantially LiBH 4Low temperature put hydrogen capacity, and put the hydrogen product and under the condition of 600 ° of C and 30atm, can reversibly inhale hydrogen.But LiBH 4Suction to put hydrogen condition still harsh.In order further to reduce LiBH 4Initial hydrogen discharging temperature, and can be issued in gentleer condition circulation and inhale and to put hydrogen, the present invention proposes with graphene-supported nanometer hydrogen storage metal catalysis LiBH 4
Summary of the invention
The technical problem to be solved in the present invention is: overcome existing LiBH in the prior art 4The deficiency such as the too high and hydrogen uptake condition of hydrogen discharging temperature is harsh provides a kind of Me-RGO/LiBH 4High hydrogen storage composite hydrogen storage material and preparation method thereof.Prepared hydrogen storage material hydrogen-storage amount is high, has satisfied the targets (5.5wt%) in 2015 that USDOE proposes, and can be widely used in the fields such as mass-producing transportation of hydrogen-oxygen fuel cell, hydrogen power cell and hydrogen.
The technical solution adopted for the present invention to solve the technical problems is: a kind of Me-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises LiBH 4Material and Me-RGO material, RGO material have high surface area and intensive duct, and Me is dispersed in surface, interlayer and the duct of RGO material, the Me-RGO of low levels and LiBH 4Material evenly mixes.
As preferably, the general formula of described composite hydrogen storage material is (100-x) LiBH 4+ x Me-RGO, Me is the nanometer hydrogen storage metal in the formula, and the mass percent of x is 3 ~ 70wt.%, and Me accounts for 3 ~ 60wt.% in the Me-RGO material.
As preferably, the aperture of described RGO is at 2 ~ 12nm, and pore volume is at 0.08～1.2cm 3/ g, specific surface area is 800 ~ 2540m 2/ g.
As preferably, the described nanometer hydrogen storage metal of described Me-RGO Me comprises in Pt, Pd, Ni, Co, Fe, Ce, Al, Mg, Ti, Zn, Mn, V, Cr, Cu, Sn or the Pt-Pd alloy any one, be single dispersed on the RGO surface and distribute nanometer hydrogen storage metal particle diameter 1 ~ 10nm.
Me-RGO/LiBH 4The method of high hydrogen storage composite hydrogen storage material comprises lower step: by the standby RGO of chemistry redox legal system; Adopt chemical process Me evenly to be supported on surface and the interlayer of RGO; Use solid-phase ball milling method, organic liquid phase method or melt infiltration method that Me-RGO is dispersed in LiBH 4In.
As preferably, described chemical process evenly is supported on the surface of RGO and interlayer by water complexing reduction method, gas phase reduction process, ion exchange method, sol-gel method, vacuum sputtering or gas evaporation method preparation with Me.
Used complexing agent had 1,10-phenanthroline, EDTA, dimercaprol dimercaptopropanol, Sodium Dimercapto Sulfonate, mercaptoethylamine, Thiovanic acid, thiocarbamide, ammonium fluoride, oxine, potassiumchromate, sodium sulphite, α-benzoinoxime, prussiate, methyl ethyl diketone, citric acid, tartrate, oxalic acid, sulphosalicylic acid, trolamine, EGTA, ethylenediamine tetrapropionic acid(EDTP), three second cyanogen tetramines etc. when water complexing reduction method prepared Me-RGO.
Used reductive agent had hydrazine, ethylene glycol, sodium borohydride, lithium aluminum hydride etc. when water complexing reduction method prepared Me-RGO.
Used reductive agent had CO, H when gas phase reduction process prepared Me-RGO 2Deng.
Response procedures used when ion exchange method prepares Me-RGO is: first at normal temperatures and pressures with metallic cation or complexing metal anionresin on ion exchange resin, then under the effect of potassium borohydride reduction agent, be reduced to the nano metal Me of RGO load.
Adopting metal alkoxide and RGO when sol-gel method prepares Me-RGO is raw material, and the metal oxide of synthetic RGO load restores the Me for preparing the RGO load first.
When preparing Me-RGO, adopt vacuum sputtering glow discharge sputtering method and ion beam sputtering nanometer hydrogen storage metal Me to be loaded to the RGO surface of bigger serface.
In rare gas element argon gas and helium, adopt resistive heating and beam heating method to make the hydrogen storage metal evaporation when gas evaporation method prepares Me-RGO, then uniform deposition is to the RGO surface of bigger serface.
Described high speed ball milled is with LiBH 4After the even mixing of Me-RGO, at H 2Adopt the high speed ball milled that the Me-RGO of low levels is dispersed in LiBH under protective atmosphere and the anhydrous and oxygen-free condition 4In.
Further: described high speed ball milled concrete steps are first with Me-RGO and LiBH under the anhydrous and oxygen-free condition 4Mix in the ball grinder that is placed on stainless steel sealing, then be filled with the H that initial pressure is 20 ~ 200atm 2, mechanical ball milling time 1 ~ 8h(planetary ball mill QM-1SP2 again), wherein, rotating speed is 580 ~ 1000rpm, and ratio of grinding media to material is 20:1 ~ 60:1, and the diameter of used agate ball is 5 ~ 20mm, and the mass percent of Me-RGO is 3 ~ 70wt.%.
The organic liquid phase method is with LiBH 4In the organic liquor system, evenly mix ultra-sonic dispersion with Me-RGO.
Further: described organic liquid phase method concrete steps are under Ar protective atmosphere and anhydrous and oxygen-free condition, according to the different mass ratio with Me-RGO and LiBH 4Common ultra-sonic dispersion is in organic liquid phase.
Further: described organic liquid phase is liquefied ammonia, ether, tetrahydrofuran (THF) or fatty amines.
The melt infiltration method is with LiBH 4After the even mixing of RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt the melt infiltration method with LiBH 4Be dispersed in the duct of the standby RGO of chemistry redox legal system.
Further: described melt infiltration method concrete steps are for first with Me-RGO and LiBH 4Mix and be placed in the stainless steel cauldron, then be filled with the H that initial pressure is 20 ~ 200atm 2, again biased sample is heated to 270 ~ 350 ℃ with the speed of 1 ~ 5 ℃/min, keep 5 ~ 60min, then cool to room temperature discharges H2, takes out sample.
The invention has the beneficial effects as follows: it is simple that the inventive method has technique, synthetic convenient; Technique is not high to equipment requirements, the remarkable advantage that is easy to realize; Me-RGO/LiBH of the present invention 4The initial hydrogen discharging temperature of composite hydrogen storage material is reduced to 200 ° below the C, and it puts hydrogen capacity above 10wt.%, 500 ° of following LiBH of C during 400 ° of C of temperature 4Whole hydrogen-storage amounts (18.5wt%) discharge.LiBH 4Reversible hydrogen uptake condition can be reduced to 400 ° of C and 30atm hydrogen pressure, and inhale and to put LiBH after the hydrogen circulation 30 times 4The hydrogen capacity of putting still remain on more than the 5.5wt%, satisfied the targets in 2015 that USDOE proposes.Nano metal is distributed to has bigger serface (800 ~ 2540m 2/ g) and suitable aperture (utilization ratio that the surface of 2 ~ 12nm) Graphene can the Effective Raise nano metal and the homogeneity of dispersion.
The LiBH that Me-RGO provided by the invention modifies 4Hydrogen storage material has remedied LiBH 4The shortcoming that hydrogen discharging temperature is too high and hydrogen uptake condition is too harsh can satisfy relevant production scientific research demand, will be more widely used in a plurality of fields.
Description of drawings
Fig. 1 is the N of the RGO of oxidation reduction process preparation among the embodiment 1 2(77K) adsorption desorption curve (a) and graph of pore diameter distribution (b);
Fig. 2 is among RGO (a), the embodiment 4 of oxidation reduction process preparation among the embodiment 1 and the Pd charge capacity of water complexing reduction method preparation among the embodiment 1 TEM that is respectively the Pd-RGO catalyzer of 20wt.% (b) and 60wt.% (c) schemes
Fig. 3 is embodiment 6, and the Pt charge capacity that gas phase reduction process prepares respectively among embodiment 5 and the embodiment 7 is respectively 3wt.% (a), the TEM figure of the Pt-RGO catalyzer of 20wt.% (b) and 60wt.% (c)
Fig. 4 is comparative example 1, the pure LiBH for preparing respectively among embodiment 3 and the embodiment 1 4(a), the LiBH of 3wt.% (b) and 70wt% (c) Pd-RGO catalysis 4TG figure
Fig. 5 is the pure LiBH for preparing preparation in composite hydrogen storage material (a) and the comparative example 1 among the embodiment 4 4(b) circulation is inhaled and is put hydrogen capacity
Fig. 6 is the LiBH of RGO catalysis in the comparative example 2 4TG figure after inhaling hydrogen under 400 ° of C and the 30atm hydrogen pressure
Fig. 7 comparative example 1,2 and the TG figure of the hydrogen storage material of embodiment 2 preparation
The LiBH of the Pd catalysis of Fig. 8 comparative example 3 preparations 4The TG figure of hydrogen storage material
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1
A kind of Pd-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises the LiBH of 30wt.% 4The percentage composition that the Pd-RGO material of material and 70wt.%, Pd account for the Pd-RGO material is 60wt.%, and the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Above-mentioned Pd-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) the controlled Graphene (RGO) of chemistry redox method synthetic aperture and specific surface area
Adopt the standby graphite oxide (GO) of improved Hummers legal system.At first take by weighing 0.5g graphite, 0.25g KNO 3, place the 500mL there-necked flask, add the dense H of 12mL 2SO 4, stir 30min at the environment lower magnetic force of ice bath.Then slowly add 1.5g KMnO 4, 35 ℃ of lower 24h that stir slowly splash into 150mL H again 2O stirs 12h.Again there-necked flask is moved in the oil bath pan 98 ℃ of lower reaction 24h.To be cooled to the room temperature filtering and washing, with the HCl washing, use again H first 2O is washed till neutrality, is dispersed in the water GO for subsequent use.
Adopt chemical reduction method reduction GO to make RGO.Get 50mg GO, be made into the dispersion liquid of 1mg/mL.Other takes by weighing 0.3g PVP, is made into 5% solution behind the adding 60mL water.Two kinds of solution are mixed in the there-necked flask of 250mL ultrasonic three hours of elder generation, then magnetic agitation 24h.Then there-necked flask is moved into 95 ℃ oil bath pan, slowly splash into 12mL 1% hydrazine hydrate (0.12mL hydrazine hydrate+11.8mL H simultaneously 2O) and 1mL ammoniacal liquor, make the pH ﹥ 10 of reaction system, reaction 8h.To be cooled to room temperature, suction filtration is washed to neutrality, and the RGO ultra-sonic dispersion 8h that makes is stored in the dehydrated alcohol.
Take a morsel to such an extent that RGO is N 2(77K) adsorption desorption curve and test pore size distribution, as shown in Figure 1:
In low pressure end (P/Po=0.0 ~ 0.1), curve deflection Y-axis, illustrative material and N 2Stronger reactive force is arranged, and this is because more micropore when existing, and strong adsorption potential causes in the micropore.
Intermediate voltage terminal (P/Po=0.3 ~ 0.8) is N 2Condensation is gathered in the material duct, and mesoporous analysis then derives from this segment data, has obtained the mesoporous distribution situation of material according to the BJH method.
High-pressure side (P/Po=0.9～1.0) can be found out the build-up of particles degree roughly, the cryolac number of nitrogen adsorption amount when the total pore volume that usually obtains is normally got relative pressure (P/Po) and is 0.99 left and right sides.
2) water complexing reduction method prepares Pd-RGO
The PVP solution of 40mL 1mg/mL RGO solution and 120mL 0.5% is mixed in the 500mL beaker, first ultrasonic 3h, then magnetic agitation 24h; Add 0.5g KNO 3, continue magnetic agitation 24h; With the centrifugal washing of above-mentioned reaction solution, the RGO that PVP is modified is scattered in the 100mL ethylene glycol, first ultrasonic 1h, then magnetic agitation 6h; Prepare simultaneously the Pd-EDTA complex liquid: take by weighing 99.96mg PdCl 26H 2O (being 60mgPd) adds 6.0mL 0.1mol/L EDTA solution, adds 20mL H again 2O stirs 40min(solution and becomes glassy yellow in 60 ℃ water-bath), to be cooled to room temperature, add 100mL ethylene glycol, continue to stir 6h; PVP-RGO dispersion liquid and Pd-EDTA complex liquid are mixed in the 500mL there-necked flask, continue to stir 12h; Transfer the pH ﹥ 13 of reaction system with the ethylene glycol solution of 3mol/L NaOH, then continue to stir 12h, reaction system is moved into 120 ℃ oil bath pan, reaction 24h; To be cooled to room temperature, the suction filtration water system is to neutral, and making the Pd charge capacity is the Pd-RGO catalyzer of 60wt.%.
3) LiBH of the standby Pd-RGO doping of melt infiltration legal system 4
Under argon gas atmosphere protection and anhydrous and oxygen-free condition with Pd-RGO and LiBH 4Mix according to mass ratio 70:30 and to be placed in the stainless steel cauldron, then be filled with the H that initial pressure is 100atm 2, again according to LiBH 4268 ℃ of theoretical fusing points and biased sample is heated to 300 ℃ with the speed of 3 ℃/min, record H this moment 2Pressure be 180atm, and keep 30min, then cool to room temperature discharges H 2, take out sample.
Embodiment 2
A kind of Pd-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises the LiBH of 70wt.% 4The percentage composition that the Pd-RGO material of material and 30wt.%, Pd account for the Pd-RGO material is 60wt.%, and the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Pd-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) RGO and Pd-RGO material preparation method are with embodiment 1.
2) LiBH of the standby Pd-RGO doping of melt infiltration legal system 4
Under argon gas atmosphere protection and anhydrous and oxygen-free condition with Pd-RGO and LiBH 4Mix according to mass ratio 30:70 and to be placed in the stainless steel cauldron, then be filled with the H that initial pressure is 20atm 2, again according to LiBH 4268 ℃ of theoretical fusing points and biased sample is heated to 350 ℃ with the speed of 1 ℃/min, record H this moment 2Pressure be 180atm, and keep 60min, then cool to room temperature discharges H 2, take out sample.
Embodiment 3
A kind of Pd-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises 97wt%LiBH 4Material and 3wt%Pd-RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Pd-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) RGO and Pd-RGO material preparation method are with embodiment 1.
2) LiBH of the standby Pd-RGO doping of melt infiltration legal system 4
Under argon gas atmosphere protection and anhydrous and oxygen-free condition with Pd-RGO and LiBH 4Mix according to mass ratio 3:97 and to be placed in the stainless steel cauldron, then be filled with the H that initial pressure is 200atm 2, again according to LiBH 4268 ℃ of theoretical fusing points and biased sample is heated to 270 ℃ with the speed of 5 ℃/min, record H this moment 2Pressure be 180atm, and keep 5min, then cool to room temperature discharges H 2, take out sample.
Embodiment 4
A kind of Pd-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises 30wt%LiBH 4The percentage composition that material and 70wt%Pd-RGO material, Pd account for the Pd-RGO material is 20wt.%, and the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Above-mentioned LiBH 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material:
1) preparation method of RGO is with embodiment 1.
2) water complexing reduction method prepares Pd-RGO
The PVP solution of 80mL 1mg/mL RGO solution and 120mL 0.5% is mixed in the 500mL beaker, first ultrasonic 3h, then magnetic agitation 24h; Add 0.5g KNO 3, continue magnetic agitation 24h; With the centrifugal washing of above-mentioned reaction solution, the RGO that PVP is modified is scattered in the 100mL ethylene glycol, first ultrasonic 1h, then magnetic agitation 6h; Prepare simultaneously the Pd-EDTA complex liquid: take by weighing 33.32mg PdCl 26H 2O (being 20mgPd) adds 6.0mL 0.1mol/L EDTA solution, adds 20mL H again 2O stirs 40min(solution and becomes glassy yellow in 60 ℃ water-bath), to be cooled to room temperature, add 100mL ethylene glycol, continue to stir 6h; PVP-RGO dispersion liquid and Pd-EDTA complex liquid are mixed in the 500mL there-necked flask, continue to stir 12h; Transfer the pH ﹥ 13 of reaction system with the ethylene glycol solution of 3mol/L NaOH, then continue to stir 12h, reaction system is moved into 120 ℃ oil bath pan, reaction 24h; To be cooled to room temperature, the suction filtration water system is to neutral, and namely making the Pd charge capacity is the Pd/RGO catalyzer of 20wt.%.
3) LiBH of the standby Pd-RGO doping of high speed ball milling legal system 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 70:30 with Pd-RGO and LiBH 4(the approximately amount of 0.1g) places the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under the room temperature after mixing).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of used agate ball is 10mm.
Embodiment 5
A kind of Pt-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises 30wt%LiBH 4Material and 70wt%Pt-RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Above-mentioned Pt-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) preparation method of RGO is with embodiment 1.
2) gas phase reduction process prepares Pt-RGO
Take by weighing 80mg RGO and be scattered in the 60ml ethylene glycol (EG) ultra-sonic dispersion 6h.Pipette the Na of 2.88ml 20mg/ml 2PtCl 66H 2O-EG solution joins among the above-mentioned RGO, stirs 10min, moves in the 100ml stainless steel cauldron, tightens stainless steel cauldron, passes into high-purity hydrogen, 300 ℃ of lower reaction 12h, and suction filtration, fully washing, 60 ℃ of dryings make the Pt-RGO that the Pt carrying capacity is 20wt.%.
3) ultrasonic dispersion prepares the LiBH that Pt-RGO mixes 4
Under argon gas atmosphere protection and anhydrous and oxygen-free condition according to mass ratio 70:30 with Pt-RGO and LiBH 4Common ultra-sonic dispersion is in liquefied ammonia.
Embodiment 6
A kind of Pt-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises 97wt%LiBH 4Material and 3wt%Pd-RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of Pd-RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Above-mentioned Pt-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) preparation method of RGO is with embodiment 1.
2) gas phase reduction process prepares Pt-RGO
Take by weighing 97mg RGO and be scattered in the 60ml ethylene glycol (EG) ultra-sonic dispersion 6h.Pipette the Na of 0.43ml 20mg/ml 2PtCl 66H 2O-EG solution joins among the above-mentioned RGO, stirs 10min, moves in the 100ml stainless steel cauldron, tightens stainless steel cauldron, passes into high-purity hydrogen, 300 ℃ of lower reaction 12h, and suction filtration, fully washing, 60 ℃ of dryings make the Pt-RGO that the Pt carrying capacity is 3wt.%.
3) LiBH of the standby RGO doping of high speed ball milling legal system 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 3:97 with Pt-RGO and LiBH 4(the approximately amount of 0.1g) places the ball grinder of a sealing, mechanical ball milling 1h(planetary ball mill QM-1SP2 under the room temperature after mixing).Wherein, rotating speed is 1000rpm, and ratio of grinding media to material is 20:1, and the diameter of used agate ball is 5mm.
Embodiment 7
A kind of Pt-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises 97wt%LiBH 4Material and 3wt%Pt-RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of Pt-RGO material.RGO is standby by the chemistry redox legal system.RGO has the aperture of 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g and 800 ~ 2540m 2The specific surface area of/g.
Above-mentioned Pt-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material:
1) the RGO preparation method is with embodiment 1.
2) gas phase reduction process prepares Pt-RGO
Take by weighing 30mg RGO and be scattered in the 60ml ethylene glycol (EG) ultra-sonic dispersion 6h.Pipette the Na of 6.48ml 20mg/ml 2PtCl 66H 2O-EG solution joins among the above-mentioned RGO, stirs 10min, moves in the 100ml stainless steel cauldron, tightens stainless steel cauldron, passes into high-purity hydrogen, 300 ℃ of lower reaction 12h, and suction filtration, fully washing, 60 ℃ of dryings make the Pt-RGO that the Pt carrying capacity is 60wt.%.
3) LiBH of the standby Pt-RGO doping of high speed ball milling legal system 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 3:97 with Pt-RGO and LiBH 4(the approximately amount of 0.1g) places the ball grinder of a sealing, mechanical ball milling 8h(planetary ball mill QM-1SP2 under the room temperature after mixing).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 60:1, and the diameter of used agate ball is 20mm.
The transmission electron microscope picture of Fig. 2 and the Pd-RGO that Figure 3 shows that different carrying capacity and Pt-RGO.Pd and Pt can be dispersed in the RGO surface.
Fig. 4 has reacted as Pd-RGO and LiBH 4When mixing in varing proportions, the situation that the quality of mixture raises and changes with temperature.As can be seen from Figure 4, Pd-RGO can obviously promote LiBH 4Put hydrogen capacity and its decomposition temperature of decrease, initial hydrogen discharging temperature is reduced to 200 ° below the C, it is put hydrogen capacity and surpasses 10wt.%, 600 ° of following LiBH of C during 400 ° of C of temperature 4Whole hydrogen-storage amounts (18.5wt%) discharge.Along with the increase of Pd-RGO add-on, the thermostability of mixture descends, and this also will take into full account in actual production.
Pure LiBH among Fig. 5 4The hydrogen capacity of putting be reduced to secondary 2.2wt.% from primary 10.4wt.%.And Pd-RGO can finely must promote LiBH 4Charge and discharge the hydrogen cycle performance, inhale and put LiBH after the hydrogen circulation 30 times 4The hydrogen capacity of putting still remain on more than the 5.5wt.%.
Comparative example 1: LiBH behind the high speed ball milling 4Hydrogen discharging performance
Under argon atmospher protection and anhydrous and oxygen-free condition with LiBH 4(the approximately amount of 0.1g) places the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under the room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of used agate ball is 10mm.Use thermogravimetric analyzer and mass spectrum to test LiBH behind the high speed ball milling 4The hydrogen discharging temperature of sample and hydrogen desorption capacity.Vacuumize first logical high-purity N before the thermogravimetric analysis test 2The 30min post-heating.
Comparative example 2: the LiBH of RGO catalysis behind the high speed ball milling 4Hydrogen discharging performance
Under argon atmospher protection and anhydrous and oxygen-free condition with RGO and LiBH 4Mix in the ball grinder that is placed on a sealing RGO:LiBH 4Mass ratio 70:30, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under the room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of used agate ball is 10mm.Use thermogravimetric analyzer and mass spectrum to test LiBH behind the high speed ball milling 4The hydrogen discharging temperature of sample and hydrogen desorption capacity.Vacuumize first logical high-purity N before the thermogravimetric analysis test 2The 30min post-heating.
Inhale the circulation hydrogen storage property of the composite hydrogen storage material of test comparative example 1 behind the hydrogen, comparative example 2, embodiment 4 preparations under 400 ° of C and the 30atm hydrogen pressure, acquired results is seen Fig. 5,6.
Fig. 6 has shown the LiBH of RGO catalysis 4Ten circulation hydrogen storage properties.As seen from the figure, for the first time put hydrogen capacity and only reach 11.2wt.%, and inhale under 400 ° of C and the 30atm hydrogen pressure and must put hydrogen capacity behind the hydrogen and only have 6.8wt.%, the tenth time the hydrogen capacity of putting is 3.4wt.%.Explanation is LiBH under Pd-RGO catalysis 4Hydrogen storage property greatly be better than RGO.
The LiBH of comparative example 3:Pd catalysis 4Hydrogen discharging performance
Nanometer Pd derives from U.S. Sigma-Aldrich company.Under argon atmospher protection and anhydrous and oxygen-free condition with commercialization nanometer Pd and LiBH 4Mix in the ball grinder that is placed on a sealing Pd:LiBH 4Mass ratio 50:50, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under the room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of used agate ball is 10mm.
By Fig. 7 and 8 as can be known, pure RGO and pure Pd are to LiBH 4Katalysis be significantly less than the katalysis of Pd-RGO, put hydrogen richness lower, and hydrogen discharging temperature is high.Compare with pure Pd with the RGO of physical mixed, Pd is evenly spread to the RGO surface can obtain larger hydrogen desorption capacity and lower hydrogen discharging temperature, catalyst effect is better.
Me-RGO/LiBH 4The measuring method of high hydrogen storage composite hydrogen storage material hydrogen discharging performance:
Use thermogravimetric analyzer and mass spectrum to study the LiBH that Me-RGO mixes 4The hydrogen desorption capacity of hydrogen storage material.With Me-RGO catalyzer and hydrogen storage material LiBH 4After fully mixing, in the sample pool of packing into, the usage quantity of the sample of thermogravimetric analysis is approximately 5 ~ 10mg, and rate of heating is 10 ℃/min, and the air charge rate of argon gas is 20cm 3/ min(1atm), detection signal is H 2Quality.

Claims (10)

1. Me-RGO/LiBH 4The high hydrogen storage composite hydrogen storage material comprises LiBH 4Material and Me-RGO material, RGO material have high surface area and intensive duct, and Me is dispersed in surface, interlayer and the duct of RGO material, the Me-RGO of low levels and LiBH 4Material evenly mixes.
2. Me-RGO/LiBH as claimed in claim 1 4The high hydrogen storage composite hydrogen storage material is characterized in that: the general formula of described composite hydrogen storage material is (100-x) LiBH 4+ x Me-RGO, the mass percent of x are 3 ~ 70wt.%, and Me accounts for 3 ~ 60wt.% in the Me-RGO material.
3. Me-RGO/LiBH as claimed in claim 1 4The high hydrogen storage composite hydrogen storage material is characterized in that: the aperture of described RGO is at 2 ~ 12nm, and pore volume is at 0.08 ~ 1.2cm 3/ g, specific surface area is 800 ~ 2540m 2/ g.
4. Me-RGO/LiBH as claimed in claim 1 4The high hydrogen storage composite hydrogen storage material, it is characterized in that: described nanometer hydrogen storage metal be in Pt, Pd, Ni, Co, Fe, Ce, Al, Mg, Ti, Zn, Mn, V, Cr, Cu, Sn or the Pt-Pd alloy any one, be single dispersed on the RGO surface and distribute nanometer hydrogen storage metal particle diameter 1 ~ 10nm.
5. each described Me-RGO/LiBH of claim 1 to 5 4The method of high hydrogen storage composite hydrogen storage material comprises lower step: by the standby RGO of chemistry redox legal system; Adopt chemical process Me evenly to be supported in surface, interlayer and the duct of RGO; Use solid-phase ball milling method, organic liquid phase method or melt infiltration method that Me-RGO is dispersed in LiBH 4In.
6. preparation is such as each described Me-RGO/LiBH of claim 1 to 5 4The method of high hydrogen storage composite hydrogen storage material is characterized in that: under hydrogen atmosphere, adopt the solid-phase ball milling method that the Me-RGO nanocatalyst is dispersed in LiBH 4In.
7. Me-RGO/LiBH as claimed in claim 6 4The preparation method of high hydrogen storage composite hydrogen storage material is characterized in that: described solid-phase ball milling method is with LiBH 4Place the ball grinder of a sealing by proportioning with Me-RGO, in the H of 20 ~ 200atm 2Adopt the high speed ball milled with LiBH under atmosphere and the anhydrous and oxygen-free condition 4Even with the Me-RGO dispersing and mixing, mechanical ball milling time 1 ~ 8h, rotating speed are 580 ~ 1000rpm, and ratio of grinding media to material is 20:1 ~ 60:1, and the diameter of used agate ball is 5 ~ 20mm.
8. preparation is such as each described Me-RGO/LiBH of claim 1 to 5 4The method of high hydrogen storage composite hydrogen storage material is characterized in that: under shielding gas atmosphere and anhydrous and oxygen-free condition, and graphene-supported nanometer hydrogen storage metal catalyzer and the LiBH that adopt the organic liquid phase method to synthesize 4Mix.
9. such as claim 8 a described Me-RGO/LiBH 4The preparation method of high hydrogen storage composite hydrogen storage material is characterized in that under shielding gas atmosphere and anhydrous and oxygen-free condition proportionally with Me-RGO and LiBH 4Common ultra-sonic dispersion is in liquefied ammonia, ether, tetrahydrofuran (THF) or fatty amines organic phase.
10. preparation is such as each described a kind of Me-RGO/LiBH of claim 1 to 5 4The method of high hydrogen storage composite hydrogen storage material is characterized in that: with LiBH 4After the even mixing of Me-RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt the melt infiltration method with LiBH 4Be dispersed in the duct of the standby RGO of chemistry redox legal system; Concrete steps are for first with RGO and LiBH 4Mix and be placed in the stainless steel cauldron, then be filled with the H that initial pressure is 20 ~ 200atm 2, again biased sample is heated to 270 ~ 350 ℃ with the speed of 1 ~ 5 ℃/min, keep 5 ~ 60min, then cool to room temperature discharges H 2, take out sample.
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