CN102718183B - 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 PDFInfo
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- CN102718183B CN102718183B CN201210245171.1A CN201210245171A CN102718183B CN 102718183 B CN102718183 B CN 102718183B CN 201210245171 A CN201210245171 A CN 201210245171A CN 102718183 B CN102718183 B CN 102718183B
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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
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
Economic develop rapidly impels the world just day by day to increase the demand of the energy, but as the fossil energy exhaustion increasingly of main energy sources at present, and a large amount of uses of fossil energy cause serious environmental pollution and climatic anomaly, so development of new clean energy is the significant problem that countries in the world are paid close attention to.Hydrogen Energy because thermo-efficiency in combustion processes is high, non-exhaust emission and product be that the advantages such as water become extremely potential a kind of new cleaning fuel of 21 century, occurred a large amount of example use at numerous areas (especially aspect the electromobile take hydrogen-oxygen fuel cell as power).
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 high, storage tank heat-insulating property is required to the problems such as high and with high costs, and solid-state material storage hydrogen because having without high pressure and heat-insulated container, security is good, low cost and other advantages becomes the hydrogen of Research Prospects accumulating mode most.
Solid-state hydrogen storage material can be divided into two large classes according to the mechanism of inhaling/putting hydrogen: with nano-sized carbon, zeolite, metallic organic framework compound and metal hydride, hydrogen storage alloy, the light metal complex hydrides with chemical action storage hydrogen of physisorption storage hydrogen.Wherein with AlH
4-and BH
4-wait light metal (as Li, Na, K, Be, Mg, Ca etc.) complex hydrides for group to become the important hydrogen supply material of hydrogen fuel cell because of advantages such as storage hydrogen specific storage is large, degree of safety is high, convenient transport.In these light metal complex hydrides, LiBH
4have very high theoretical hydrogen storage capability (up to 18.5wt.%), can meet in theory the requirement (USDOE requires to reach for 2015 9.0wt.%) of vehicle-mounted power hydrogen source completely.But pure LiBH
4initial hydrogen discharging temperature up to 400 ℃, raise the temperature to the 600 ℃ of capacity that also only can emit 8wt.%, and the condition of reversible suction hydrogen is extremely harsh, need under 600 ℃ and 350atm hydrogen pressure condition, inhale hydrogen.This has just greatly limited LiBH
4as the practical application of hydrogen storage material.
As everyone knows, nanostructure adjustment, anion/cation substitute and catalyzer doping is to reduce LiBH
4the good method of hydrogen discharging temperature and its hydrogen uptake condition of mitigation, and the method that nanostructure is adjusted is simple, effect is the most remarkable.By 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 builds other dimension carbonaceous material (as zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).The advantages such as Graphene has that quality is light, 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 to be solved in the present invention is to overcome existing LiBH
4hydrogen discharging temperature is crossed the shortcomings such as high, provides a kind of by LiBH
4be dispersed in and there is the method that aperture size can be in harmonious proportion in 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 fields such as the mass-producing transportations 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, 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 is standby by chemistry redox legal system.
As preferably, described RGO has the aperture of 2 ~ 10nm, 800 ~ 2540m
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 by LiBH
4after evenly mixing with RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt melt infiltration method by 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 by RGO and LiBH
4mix and be placed in a stainless steel cauldron, be then filled with the H that initial pressure is 20 ~ 200atm
2, then biased sample is heated to 270 ~ 350 ℃ with the speed of 1 ~ 5 ℃/min, and keeping 5 ~ 60min, then cool to room temperature, discharges H
2, take out sample.
Aforesaid LiBH
4the preparation method of/RGO high hydrogen storage composite hydrogen storage material is by LiBH
4after evenly mixing with RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt high speed ball milled by 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 different mass ratio RGO and LiBH
4mix in the ball sealer grinding jar that is placed on a ball mill, mechanical ball milling 1 ~ 8h under room temperature, wherein, rotating speed is 580 ~ 1000rpm, and ratio of grinding media to material is 20:1 ~ 60:1, and the diameter of agate ball used 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 ℃, and the hydrogen desorption capacity below 500 ℃ is 5 ~ 18wt.%, has made up LiBH
4the shortcoming that hydrogen discharging temperature is too high can be more widely used this material in multiple fields.
Accompanying drawing explanation
The N of RGO prepared by Fig. 1 oxidation reduction process
2(77K) adsorption desorption curve;
The graph of pore diameter distribution of RGO prepared by Fig. 2 oxidation reduction process;
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:
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%, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material.RGO is standby by chemistry redox legal system.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) chemistry redox method has been synthesized aperture and the controlled Graphene (RGO) of specific surface area
Adopt improved Hummers legal system for graphite oxide (GO).First take 0.5g graphite, 0.25gKNO
3, be placed in 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, stir 24h at 35 ℃, more slowly splash into 150mLH
2o, stirs 12h.Again there-necked flask is moved in oil bath pan, react 24h at 98 ℃.To be cooled to filtering and washing after room temperature, first with HCl washing, then use H
2o is washed till neutrality, and GO is dispersed in water for subsequent use.
Adopt chemical reduction method reduction GO to make RGO.Get 50mg GO, be made into the dispersion liquid of 1mg/mL.Separately take 0.3g PVP, be made into 5% solution after adding 60mL water.Two kinds of solution are mixed in the there-necked flask of 250mL, first ultrasonic three hours, then magnetic agitation 24h.Then there-necked flask is moved into the oil bath pan of 95 ℃, slowly splash into 12mL1% hydrazine hydrate (0.12mL hydrazine hydrate+11.8mL H simultaneously
2and 1mL ammoniacal liquor O), make the pH ﹥ 10 of reaction system, reaction 8h.To be cooled to room temperature, suction filtration is washed to neutrality, and the ultrasonic dispersion of the RGO 8h making, is stored in dehydrated alcohol.
The RGO taking 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-axis, illustrative material and N
2have stronger reactive force, this is while existing due to more micropore, and in micropore, strong adsorption potential causes.
Intermediate voltage terminal (P/Po=0.3 ~ 0.8) is N
2in material duct, condensation is gathered, and mesoporous analysis derives from this segment data, obtains Fig. 2 according to BJH method, and the curve in Fig. 2 has reacted the mesoporous distribution situation of material.
High-pressure side (P/Po=0.9～1.0) can be found out build-up of particles degree roughly, the cryolac number of nitrogen adsorption amount when the total pore volume usually obtaining is normally got relative pressure (P/Po) and is 0.99 left and right.
2) melt infiltration legal system is for the LiBH of RGO doping
4
Under argon atmospher protection and anhydrous and oxygen-free condition by RGO and LiBH
4mix and be placed in a stainless steel cauldron according to mass ratio 70:30, be then filled with the H that initial pressure is 100atm
2, then according to LiBH
4268 ℃ of theoretical fusing points and biased sample is heated to 300 ℃ with the speed of 3 ℃/min, record now H
2pressure be 180atm, and keep 30min, then cool to room temperature, discharges H
2, take out sample.
A kind of LiBH
4/ RGO high hydrogen storage composite hydrogen storage material, comprises 30wt%LiBH
4material and 70wt%RGO material, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material.RGO is standby by chemistry redox legal system.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) high speed ball milling legal system is for the LiBH of RGO doping
4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 70:30 by RGO and LiBH
4after mixing, (amount of about 0.1g) is placed in the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of agate ball used 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, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material.RGO is standby by chemistry redox legal system.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) melt infiltration legal system is for the LiBH of RGO doping
4
Under argon atmospher protection and anhydrous and oxygen-free condition by RGO and LiBH
4mix and be placed in a stainless steel cauldron according to mass ratio 40:60, be then filled with the H that initial pressure is 100atm
2, then according to LiBH
4268 ℃ of theoretical fusing points and biased sample is heated to 300 ℃ with the speed of 3 ℃/min, record now H
2pressure be 180atm, and keep 30min, then cool to room temperature, discharges H
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, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material.RGO is standby by chemistry redox legal system.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) high speed ball milling legal system is for the LiBH of RGO doping
4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 20:80 by RGO and LiBH
4after mixing, (amount of about 0.1g) is placed in the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of agate ball used 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, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material.RGO is standby by chemistry redox legal system.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) high speed ball milling legal system is for the LiBH of RGO doping
4
Under argon atmospher protection and anhydrous and oxygen-free condition according to mass ratio 90:10 by RGO and LiBH
4after mixing, (amount of about 0.1g) is placed in the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of agate ball used is 10mm.
Fig. 3 has reacted as RGO and LiBH
4while mixing in varing proportions, the quality of mixture, with the temperature situation about changing that raises, as can be seen from Figure 3, along with the increase of RGO add-on, is emitted H
2amount also to some extent increase, illustrate LiBH
4being dispersed in RGO is a kind of well hydrogen storage material method of modifying.
Comparative example 1: LiBH after high speed ball milling
4the hydrogen discharging performance of/RGO hydrogen storage material
Under argon atmospher protection and anhydrous and oxygen-free condition by LiBH
4/ RGO hydrogen storage material (amount of about 0.1g) is placed in the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of agate ball used is 10mm.Use thermogravimetric analyzer and mass spectrum to test LiBH after high speed ball milling
4hydrogen discharging temperature and the hydrogen desorption capacity of/RGO hydrogen storage material sample.Before thermogravimetric analysis test, first vacuumize logical high-purity N
230min post-heating.Again by the LiBH after 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 ℃, maintains 3h, is then filled with high-purity H of 90atm
2, keep 10h.Again pressure is dropped to 1atm, transfer hydrogen 5h at 450 ℃, by cmf record LiBH
4the hydrogen desorption capacity of hydrogen storage material and put hydrogen platform.
Comparative example 2: the thermogravimetric of RGO (TG) curve after high speed ball milling
Under argon atmospher protection and anhydrous and oxygen-free condition, RGO (amount of about 0.1g) is placed in to the ball grinder of a sealing, mechanical ball milling 4.5h(planetary ball mill QM-1SP2 under room temperature).Wherein, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, and the diameter of agate ball used is 10mm.Use thermogravimetric analyzer to test the TG curve of RGO after high speed ball milling.Before test, first vacuumize logical high-purity N
230min post-heating.Experimental result finds not have weightlessness to occur.
LiBH
4the measuring method of/RGO high hydrogen storage composite hydrogen storage material hydrogen discharging performance:
Use thermogravimetric analyzer and mass spectrum to study the LiBH of RGO doping
4the hydrogen desorption capacity of hydrogen storage material.By RGO and hydrogen storage material LiBH
4after fully mixing, pack in sample pool, 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, by the LiBH of RGO doping
4be loaded in stainless steel reactor, at 450 ℃, be evacuated to 0.5Pa, maintain 3h, be then filled with high-purity H of 90atm
2, keep 10h.Again pressure is dropped to 1atm, transfer hydrogen 5h at 450 ℃, by cmf record LiBH
4the hydrogen desorption capacity of/RGO composite hydrogen storage material and put hydrogen platform.
Fig. 4 has illustrated LiBH
4be scattered in the hydrogen desorption capacity before and after the duct of RGO material and put hydrogen platform.As can be seen from Figure 4, pure LiBH
4do not have must put hydrogen platform gently, and the hydrogen desorption capacity of 400 ℃ is much smaller than LiBH
4/ RGO matrix material.According to LiBH
4the hydrogen desorption capacity of/RGO matrix material under differing temps and put hydrogen platform and can Theoretical Calculation put reaction enthalpy change and the Entropy Changes in hydrogen process.
Claims (8)
1. a LiBH
4/ RGO high hydrogen storage composite hydrogen storage material, is characterized in that: comprise LiBH
4material and RGO material, RGO material surface has intensive duct, LiBH
4material is dispersed in the duct of RGO material,
Wherein, 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.
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 is standby by chemistry redox legal system.
4. the LiBH as described in claims 1 to 3 any one
4the preparation method of/RGO high hydrogen storage composite hydrogen storage material, is characterized in that: by LiBH
4after evenly mixing with RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt melt infiltration method by LiBH
4be dispersed in the duct of the standby RGO of chemistry redox legal system.
5. LiBH as claimed in claim 4
4the preparation method of/RGO high hydrogen storage composite hydrogen storage material, is characterized in that: described melt infiltration method concrete steps are for first by RGO and LiBH
4mix and be placed in a stainless steel cauldron, be then filled with the H that initial pressure is 20～200atm
2, then biased sample is heated to 270～350 ℃ with the speed of 1～5 ℃/min, and keeping 5～60min, then cool to room temperature, discharges H
2, take out sample.
6. the LiBH as described in claims 1 to 3 any one
4the preparation method of/RGO high hydrogen storage composite hydrogen storage material, is characterized in that: by LiBH
4after evenly mixing with RGO, under protection of inert gas atmosphere and anhydrous and oxygen-free condition, adopt high speed ball milled by LiBH
4be dispersed in the duct of RGO.
7. LiBH as claimed in claim 6
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 different mass ratio RGO and LiBH
4mix in the ball sealer grinding jar that is placed on a ball mill, mechanical ball milling 1～8h under room temperature, wherein, rotating speed is 580～1000rpm, and ratio of grinding media to material is 20:1～60:1, and the diameter of agate ball used is 5～20mm.
8. LiBH as claimed in claim 7
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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| CN102910581A (en) * | 2012-10-22 | 2013-02-06 | 常州大学 | Me-RGO (Reduced Graphene Oxide)/LiBH4 hydrogen storage material with high hydrogen storage capacity and preparation methods of Me-RGO/LiBH4 hydrogen storage material |
| CN104891434B (en) * | 2013-06-04 | 2017-09-29 | 浙江大学 | A kind of Hydroboron/graphite fluoride nano-composite hydrogen storage material and preparation method thereof |
| CN103395779B (en) * | 2013-08-15 | 2015-08-19 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene and preparation method thereof |
| CN104229731B (en) * | 2014-09-16 | 2017-01-18 | 哈尔滨工业大学 | Co9S8/graphene composite hydrogen storage material and preparation method thereof |
| CN104649224B (en) * | 2015-02-06 | 2017-09-26 | 桂林电子科技大学 | A kind of expanded graphite/LiBH4Composite hydrogen storage material and preparation method thereof |
| CN105060246B (en) * | 2015-09-01 | 2017-03-29 | 中国船舶重工集团公司第七一二研究所 | It is a kind of to improve the method that lithium borohydride puts hydrogen |
| CN106744872A (en) * | 2016-12-01 | 2017-05-31 | 安徽工业大学 | A kind of preparation method of the multi-layer graphene nanometer sheet of the boron hydride that adulterates |
| CN106910891A (en) * | 2017-03-06 | 2017-06-30 | 复旦大学 | A kind of transition metal fluorides load the preparation method of boron dopen Nano carbon composite |
| CN106976840B (en) * | 2017-04-05 | 2019-03-01 | 上海理工大学 | A kind of Carbon foam load magnesium ambrose alloy composite hydrogen storage material and preparation method thereof |
| CN107487762B (en) * | 2017-09-20 | 2019-09-20 | 安徽工业大学 | A method of improving the hydrogen sucking function of lithium borohydride hydrogen release/again |
| CN111268642B (en) * | 2020-01-16 | 2022-12-06 | 长沙理工大学 | Sodium borohydride/nitrogen-doped graphene hydrogen storage composite material and preparation method thereof |
| KR20220020076A (en) * | 2020-08-11 | 2022-02-18 | 현대자동차주식회사 | Hydrogen storage composite material and manufacturing method thereof |
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