CN102718183A - High-hydrogen-storage-capacity lithium borohydride/graphene (LiBH4/RGO) composite hydrogen storage material and preparation method thereof - Google Patents

High-hydrogen-storage-capacity lithium borohydride/graphene (LiBH4/RGO) composite hydrogen storage material and preparation method thereof Download PDF

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CN102718183A
CN102718183A CN2012102451711A CN201210245171A CN102718183A CN 102718183 A CN102718183 A CN 102718183A CN 2012102451711 A CN2012102451711 A CN 2012102451711A CN 201210245171 A CN201210245171 A CN 201210245171A CN 102718183 A CN102718183 A CN 102718183A
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rgo
libh
hydrogen storage
hydrogen
storage material
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CN102718183B (en
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陈智栋
齐中清
许娟
曹剑瑜
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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Abstract

The invention relates to the field of the modification of hydrogen storage materials and provides a high-hydrogen-storage-capacity lithium borohydride/graphene (LiBH4/RGO) composite hydrogen storage material and a preparation method thereof. According to the preparation method, the LiBH4 is uniformly dispersed into pore channels of the RGO which is prepared through a chemical redox method by adopting a melt infiltration method or a high-speed ball milling method under the protective atmosphere of inert gas. In the composite material, the RGO which is prepared through the chemical redox method has the pore diameter of 2-10 nm, the pore volume of 0.08-1.9 cm<3>/g and the specific surface area of 800-2540 m<2>/g, and the mass percent of the LiBH4 is 10-80 wt%. According to the LiBH4/RGO composite hydrogen storage material provided by the invention, the initial hydrogen generation temperature is lower than 100 DEG C, the hydrogen generation volume at the temperature below 500 DEG C is 5-18 wt%, and the LiBH4/RGO composite hydrogen storage material can be applied to the fields of hydrogen supply sources of fuel cells, hydrogen energy source vehicles and the like.

Description

LiBH 4/ RGO high 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 the LiBH of hydrogen 4/ RGO high hydrogen storage composite hydrogen storage material and preparation method.
Background technology
Rapid development of economy impels the world that demands for energy is increased just day by day; But as the fossil energy exhaustion day by day of main energy sources at present; And a large amount of uses of fossil energy cause serious environmental to pollute and climatic anomaly, so the development of new clean energy is the significant problem that countries in the world are paid close attention to.Advantages such as Hydrogen Energy is high owing to thermo-efficiency in the combustion processes, non-exhaust emission and product are water become a kind of novel clean energy that 21 century has development potentiality, a large amount of example use occurred at the numerous areas electromobile of power (especially with the hydrogen-oxygen fuel cell be aspect).
The storaging and transport technology of fuel hydrogen has become the technical bottleneck of restriction Hydrogen Energy development.Storage hydrogen mode mainly contains high-pressure gaseous storage hydrogen, low-temperature liquefaction storage hydrogen and three kinds of modes of solid-state material storage hydrogen.High-pressure gaseous storage hydrogen and low-temperature liquefaction storage hydrogen exist poor safety performance, energy consumption height, the storage tank heat-insulating property are required problems such as high and with high costs, and solid-state material storage hydrogen need not high pressure and heat-insulated container because of having, security is good, low cost and other advantages becomes the hydrogen of research prospect accumulating mode are arranged most.
Solid-state hydrogen storage material can be divided into two big types according to the mechanism of inhaling/putting hydrogen: with the nano-sized carbon of physisorption storage hydrogen, zeolite, metallic organic framework compound with metal hydride, hydrogen storage alloy, the light metal complex hydrides of chemical action storage hydrogen.Wherein with AlH 4-and BH 4-wait that light metal (like Li, Na, K, Be, Mg, Ca etc.) complex hydrides for group is big because of storage hydrogen specific storage, advantages such as degree of safety is high, convenient transport become the important hydrogen supply material of hydrogen fuel cell.In these light metal complex hydrides, LiBH 4Have very high theoretical hydrogen storage capability (up to 18.5wt.%), can satisfy the requirement (USDOE's requirement reached 9.0wt.% in 2015) of vehicle-mounted power hydrogen source in theory fully.But pure LiBH 4Initial hydrogen discharging temperature up to 400 ℃, even temperature is elevated to the 600 ℃ of capacity that also only can emit 8wt.%, and the condition of reversible suction hydrogen is extremely harsh, need 600 ℃ with 350atm hydrogen pressure condition under inhale hydrogen.This has just greatly limited LiBH 4Practical application as hydrogen storage material.
As everyone knows, nanostructure adjustment, anion/cation substitute and catalyzer mixes is to reduce LiBH 4Hydrogen discharging temperature and the good method that relaxes its hydrogen uptake condition, and the method for nanostructure adjustment is simple, effect is the most remarkable.With LiBH 4Be dispersed in the nano material with size adjustable aperture and high-specific surface area is to improve this material to put hydrogen capacity and reduce its reversible prerequisite that charges and discharge hydrogen condition.
Graphene (RGO) 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 blacking (like zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).Graphene has advantages such as light weight, high chemical stability and high-specific surface area.Therefore, Graphene (RGO) can be used as and disperses LiBH 4Nano material.
Summary of the invention
The technical problem that the present invention will solve is to overcome existing LiBH 4Hydrogen discharging temperature is crossed high shortcoming, provides a kind of with LiBH 4Be dispersed in and have aperture size and can be in harmonious proportion the method among the RGO of high-specific surface area, preparation LiBH 4/ RGO high hydrogen storage composite hydrogen storage material.Prepared hydrogen storage material 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 LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises LiBH 4Material and RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.
As preferably, the general formula of described hydrogen storage material is x LiBH 4+ (100-x) RGO, the mass percent of x is 10 ~ 80wt%.
As preferably, described RGO prepares through the chemistry redox method.
As preferably, described RGO has aperture, the 800 ~ 2540m of 2 ~ 10nm 2The specific surface area of/g and 0.08 ~ 1.9cm 3The pore volume of/g.
Aforesaid LiBH 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is with LiBH 4Behind the RGO uniform mixing, 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 RGO of chemistry redox method preparation.
Further: described melt infiltration method concrete steps are earlier with RGO and LiBH 4Mix and be placed in the stainless steel cauldron, charge into the H that initial pressure is 20 ~ 200atm then 2, again biased sample is heated to 270 ~ 350 ℃ with the speed of 1 ~ 5 ℃/min, keep 5 ~ 60min, cool to room temperature discharges H then 2, take out sample.
Aforesaid LiBH 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is with LiBH 4Behind the RGO uniform mixing, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt the high speed ball milled with LiBH 4Be dispersed in the duct of RGO.
Further, described high speed ball milled is specially under argon atmospher protection and anhydrous and oxygen-free condition according to the different mass ratio RGO and LiBH 4Mix in the sealing ball grinder that is placed on a ball mill, mechanical ball milling 1 ~ 8h under the room temperature, wherein, rotating speed is 580 ~ 1000rpm, and ball-to-powder weight ratio is 20:1 ~ 60:1, and the diameter of used agate ball is 5 ~ 20mm.
Further: described ball mill adopts planetary ball mill.
The invention has the beneficial effects as follows: LiBH of the present invention 4The initial hydrogen discharging temperature of/RGO composite hydrogen storage material is lower than 100 ℃, is 5 ~ 18wt.% at the hydrogen desorption capacity below 500 ℃, has remedied LiBH 4The shortcoming that hydrogen discharging temperature is too high can be more widely used this material in a plurality of fields.
Description of drawings
The N of the RGO of Fig. 1 oxidation reduction process preparation 2(77K) adsorption desorption curve;
The graph of pore diameter distribution of the RGO of Fig. 2 oxidation reduction process preparation;
Fig. 3 LiBH 4Mass percent is (a) 100wt%, (b) 80wt%, (c) 60wt%, (d) 30wt% and (e) LiBH of 10wt% 4The TG figure of/RGO composite hydrogen storage material;
The pure LiBH of Fig. 4 4At 400 ℃ (a) and LiBH 4Mass percent is the LiBH of 30wt% 4/ RGO composite hydrogen storage material is at the PCT curve of 300 ℃ (b), 350 ℃ (c) and 400 ℃.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1
A kind of LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises the LiBH of 30wt% 4The RGO material of material and 70wt%, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO prepares through the chemistry redox method.RGO has aperture and the 2540m of 2 ~ 10nm 2The specific surface area of/g.
Above-mentioned LiBH 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material:
1) the chemistry redox method has been synthesized the Graphene (RGO) of aperture and controllable specific surface area
Adopt improved Hummers legal system to be equipped with graphite oxide (GO).At first take by weighing 0.5g graphite, 0.25gKNO 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.Slowly add 1.5g KMnO then 4, 35 ℃ are stirred 24h down, slowly splash into 150mLH again 2O stirs 12h.There-necked flask is moved in the oil bath pan, 98 ℃ are reacted 24h down again.To be cooled to the room temperature filtering and washing, with the HCl washing, use H more earlier 2O is washed till neutrality, is dispersed in the water GO 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, magnetic agitation 24h then.Move into there-necked flask 95 ℃ oil bath pan then, slowly splash into 12mL1% Hydrazine Hydrate 80 (0.12mL Hydrazine Hydrate 80+11.8mL H simultaneously 2O) and 1mL ammoniacal liquor, make the pH ﹥ 10 of reaction system, reaction 8h.To be cooled to room temperature, the suction filtration washing is to neutral, and the RGO ultra-sonic dispersion 8h that makes is stored in the absolute ethyl alcohol.
The RGO that takes a morsel is N 2(77K) adsorption desorption curve, as shown in Figure 1:
In low pressure end (P/Po=0.0 ~ 0.1), curve deflection Y axle, 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, obtains Fig. 2 according to the BJH method, and the curve among Fig. 2 has reacted the mesoporous distribution situation of material.
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 obtains is usually normally got relative pressure (P/Po) and is 0.99 left and right sides.
2) the melt infiltration legal system is equipped with the adulterated LiBH of RGO 4
Under argon atmospher protection and anhydrous and oxygen-free condition with RGO and LiBH 4Mix according to mass ratio 70:30 and to be placed in the stainless steel cauldron, charge into the H that initial pressure is 100atm then 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, cool to room temperature discharges H then 2, take out sample.
Embodiment 2
A kind of LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises 30wt%LiBH 4Material and 70wt%RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO prepares through the chemistry redox method.RGO has aperture and the 2540m of 2 ~ 10nm 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) the adulterated LiBH of high speed Prepared by Ball Milling RGO 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 70:30 with RGO and LiBH 4Mix back (amount of about 0.1g) and place the ball grinder of a sealing, mechanical ball milling 4.5h under the room temperature (planetary ball mill QM-1SP2).Wherein, rotating speed is 580rpm, and ball-to-powder weight ratio is 30:1, and the diameter of used agate ball is 10mm.
Embodiment 3:
A kind of LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises 60wt%LiBH 4Material and 40wt%RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO prepares through the chemistry redox method.RGO has aperture and the 2540m of 2 ~ 10nm 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) the melt infiltration legal system is equipped with the adulterated LiBH of RGO 4
Under argon atmospher protection and anhydrous and oxygen-free condition with RGO and LiBH 4Mix according to mass ratio 40:60 and to be placed in the stainless steel cauldron, charge into the H that initial pressure is 100atm then 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, cool to room temperature discharges H then 2, take out sample.
Embodiment 4:
A kind of LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises 80wt%LiBH 4Material and 20wt%RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO prepares through the chemistry redox method.RGO has aperture and the 2540m of 2 ~ 10nm 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) the adulterated LiBH of high speed Prepared by Ball Milling RGO 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 20:80 with RGO and LiBH 4Mix back (amount of about 0.1g) and place the ball grinder of a sealing, mechanical ball milling 4.5h under the room temperature (planetary ball mill QM-1SP2).Wherein, rotating speed is 580rpm, and ball-to-powder weight ratio is 30:1, and the diameter of used agate ball is 10mm.
Embodiment 5:
A kind of LiBH 4/ RGO high hydrogen storage composite hydrogen storage material comprises 10wt%LiBH 4Material and 90wt%RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.RGO prepares through the chemistry redox method.RGO has aperture and the 2540m of 2 ~ 10nm 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) the adulterated LiBH of high speed Prepared by Ball Milling RGO 4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 90:10 with RGO and LiBH 4Mix back (amount of about 0.1g) and place the ball grinder of a sealing, mechanical ball milling 4.5h under the room temperature (planetary ball mill QM-1SP2).Wherein, rotating speed is 580rpm, and ball-to-powder weight ratio is 30:1, and the diameter of used agate ball is 10mm.
Fig. 3 has reacted as RGO and LiBH 4When mixing in varing proportions, the quality of mixture as can be seen from Figure 3, along with the increase of RGO add-on, is emitted H with the situation that temperature raises and changes 2Amount also increase to some extent, explain LiBH 4Being dispersed among the RGO is a kind of good hydrogen storage material method of modifying.
Comparative example 1: LiBH behind the high speed ball milling 4The hydrogen discharging performance of/RGO hydrogen storage material
Under argon atmospher protection and anhydrous and oxygen-free condition with LiBH 4/ RGO hydrogen storage material (amount of about 0.1g) places the ball grinder of a sealing, mechanical ball milling 4.5h under the room temperature (planetary ball mill QM-1SP2).Wherein, rotating speed is 580rpm, and ball-to-powder weight ratio is 30:1, and the diameter of used agate ball is 10mm.Utilization thermogravimetric analyzer and mass spectrum are tested LiBH behind the high speed ball milling 4The hydrogen discharging temperature and the hydrogen desorption capacity of/RGO hydrogen storage material sample.Vacuumize logical high-purity N before the thermogravimetric analysis test earlier 2The 30min post-heating.Again with the LiBH behind the high speed ball milling 4/ RGO hydrogen storage material sample is loaded in the stainless steel reactor of pressure-composition-temperature (PCT) storage hydrogen testing apparatus, is evacuated to 0.5Pa at 450 ℃, keeps 3h, charges into high-purity H of 90atm then 2, keep 10h.Again pressure is dropped to 1atm, transfer hydrogen 5h at 450 ℃, through cmf record LiBH 4The hydrogen desorption capacity of hydrogen storage material with put the hydrogen platform.
Comparative example 2: the thermogravimetric of RGO (TG) curve behind the high speed ball milling
Under argon atmospher protection and anhydrous and oxygen-free condition, RGO (amount of about 0.1g) is placed the ball grinder of a sealing, mechanical ball milling 4.5h under the room temperature (planetary ball mill QM-1SP2).Wherein, rotating speed is 580rpm, and ball-to-powder weight ratio is 30:1, and the diameter of used agate ball is 10mm.The utilization thermogravimetric analyzer is tested the TG curve of RGO behind the high speed ball milling.Vacuumize logical high-purity N before the test earlier 2The 30min post-heating.Experimental result finds not have weightlessness to take place.
LiBH 4The measuring method of/RGO high hydrogen storage composite hydrogen storage material hydrogen discharging performance:
Utilization thermogravimetric analyzer and mass spectrum are studied the adulterated LiBH of RGO 4The hydrogen desorption capacity of hydrogen storage material.With RGO and hydrogen storage material LiBH 4Behind the thorough 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.
Adopt pressure-composition-temperature (PCT) storage hydrogen testing apparatus test LiBH 4The hydrogen desorption kinetics performance of/RGO composite hydrogen storage material.Under argon atmospher protection and anhydrous and oxygen-free condition, with the adulterated LiBH of RGO 4Be loaded in the stainless steel reactor, under 450 ℃, be evacuated to 0.5Pa, keep 3h, charge into high-purity H of 90atm then 2, keep 10h.Again pressure is dropped to 1atm, transfer hydrogen 5h at 450 ℃, through cmf record LiBH 4The hydrogen desorption capacity of/RGO composite hydrogen storage material with put the hydrogen platform.
Fig. 4 has explained LiBH 4Be scattered in before and after the duct of RGO material hydrogen desorption capacity with put the hydrogen platform.As can be seen from Figure 4, pure LiBH 4Do not have must put the hydrogen platform gently, and 400 ℃ hydrogen desorption capacity is much smaller than LiBH 4/ RGO matrix material.According to LiBH 4The hydrogen desorption capacity of/RGO matrix material under differing temps with put the hydrogen platform and can Theoretical Calculation put reaction enthalpy change and Entropy Changes in the hydrogen process.

Claims (9)

1. LiBH 4/ RGO high hydrogen storage composite hydrogen storage material is characterized in that: comprise LiBH 4Material and RGO material, the RGO material surface has intensive duct, LiBH 4Material is dispersed in the duct of RGO material.
2. LiBH as claimed in claim 1 4/ RGO high hydrogen storage composite hydrogen storage material is characterized in that: the general formula of described hydrogen storage material is x LiBH 4+ (100-x) RGO, the mass percent of x is 10 ~ 80wt%.
3. LiBH as claimed in claim 1 4/ RGO high hydrogen storage composite hydrogen storage material is characterized in that: described RGO prepares through the chemistry redox method.
4. LiBH as claimed in claim 1 4/ RGO high hydrogen storage composite hydrogen storage material is characterized in that: described RGO has aperture, the 800 ~ 2540sm of 2 ~ 10nm 2The specific surface area of/g and 0.08 ~ 1.9cm 3The pore volume of/g.
5. like each described LiBH of claim 1 to 4 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is characterized in that: with LiBH 4Behind the RGO uniform mixing, 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 RGO of chemistry redox method preparation.
6. LiBH as claimed in claim 5 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is characterized in that: described melt infiltration method concrete steps are earlier with RGO and LiBH 4Mix and be placed in the stainless steel cauldron, charge into the H that initial pressure is 20 ~ 200atm then 2, again biased sample is heated to 270 ~ 350 ℃ with the speed of 1 ~ 5 ℃/min, keep 5 ~ 60min, cool to room temperature discharges H then 2, take out sample.
7. like each described LiBH of claim 1 to 4 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is characterized in that: with LiBH 4Behind the RGO uniform mixing, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt the high speed ball milled with LiBH 4Be dispersed in the duct of RGO.
8. LiBH as claimed in claim 7 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is characterized in that: described high speed ball milled is specially under argon atmospher protection and anhydrous and oxygen-free condition according to the different mass ratio RGO and LiBH 4Mix in the sealing ball grinder that is placed on a ball mill, mechanical ball milling 1 ~ 8h under the room temperature, wherein, rotating speed is 580 ~ 1000rpm, and ball-to-powder weight ratio is 20:1 ~ 60:1, and the diameter of used agate ball is 5 ~ 20mm.
9. LiBH as claimed in claim 8 4The preparation method of/RGO high hydrogen storage composite hydrogen storage material is characterized in that: described ball mill adopts planetary ball mill.
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