CN107777661A - A kind of Al LiCl Bi2O3The preparation method and applications of aluminum-based composite hydrogen manufacturing material - Google Patents

A kind of Al LiCl Bi2O3The preparation method and applications of aluminum-based composite hydrogen manufacturing material Download PDF

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CN107777661A
CN107777661A CN201711161209.6A CN201711161209A CN107777661A CN 107777661 A CN107777661 A CN 107777661A CN 201711161209 A CN201711161209 A CN 201711161209A CN 107777661 A CN107777661 A CN 107777661A
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licl
aluminum
based composite
ball
manufacturing material
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CN107777661B (en
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徐芬
陈俊
孙立贤
李鹏
吴燚鹏
杨侠
彭洪亮
闫二虎
张焕芝
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Guilin University of Electronic Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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 discloses a kind of Al LiCl Bi2O3The preparation method of aluminum-based composite hydrogen manufacturing material, the material are mixed by aluminium powder and additive through mechanical ball mill.Additive is by LiCl and Bi2O3Mix；The mass percent of aluminium powder is 50 95%, and additive mass percent is 5 50%.The aluminum-based composite hydrogen manufacturing material preparation method includes：1）Weigh aluminium powder, LiCl and Bi respectively in proportion2O3Add in ball grinder, then by ratio of grinding media to material, add abrading-ball, seal, argon gas protection is filled with tank；2）Ball grinder is put into ball mill ball milling, sets rotational speed of ball-mill, Ball-milling Time；3）Finally take out obtained aluminum matrix composite.The present invention have H2-producing capacity it is good, cost is cheap, and technique is simple, and Portable movable hydrogen source, fuel cell hydrogen-feeding etc. field have broad application prospects.

Description

A kind of Al-LiCl-Bi2O3The preparation method and applications of aluminum-based composite hydrogen manufacturing material
Technical field
The invention belongs to technical field of hydrogen preparation, specifically a kind of Al-LiCl-Bi2O3The system of aluminum-based composite hydrogen manufacturing material Preparation Method and its application.
Background technology
Hydrogen Energy is the secondary energy sources most with prospects that the 21 century mankind generally acknowledge, has the combustion heat compared with other energy Value is high, and abundance is pollution-free, it is efficiently controllable a little.
Aluminium base hydrogen manufacturing material has that energy density is big, is easy to storage, low raw-material cost, raw material easily to obtain, aluminum-water reaction Product is environment-friendly, the advantages that can be recycled.Widely should have in fields such as Portable movable hydrogen source, fuel cell hydrogen-feedings Use prospect.But aluminium surface easily forms one layer of dense oxidation film, suppress the reaction that aluminium most starts with water, and hydrolysis reaction In can also generate Al (OH)3Depositing thin films, hinder the progress of aluminum-water reaction, therefore the oxide-film for how abolishing aluminium surface turns into aluminium The key of water hydrogen producing technology.
At present, in the preparation field of alumina-base material, most methods or mechanical ball that domestic and international researcher uses Mill method, wherein the bowl mill-type being applied primarily to is high-energy planetary ball mill mechanical attrition method.Xu in 2007 et al.（Fan M Q, Xu F, Sun L X, et al. Hydrolysis of ball milling Al–Bi–hydride and Al–Bi–salt mixture for hydrogen generation[J]. Journal of Alloys & Compounds, 2008, 460 (1–2):125-129.）Al-Bi- inorganic salts hydrogen manufacturing materials, wherein Al-10%Bi-10%MgCl are prepared for using mechanical attrition method2 Hydrogen output is 1050ml.g-1, production hydrogen conversion ratio is 93.4%.But there is problems with the material：1st, metal simple-substance ball milling is added, Specimen material is easily reunited；The hydrogen-producing speed of 2 hydrogen manufacturing materials is low；3 materials A l content is less than 80%, and the amount of additive is big, Unit mass hydrogen output is low.
Dupiano in 2011 et al.（Dupiano P, Stamatis D, Dreizin E L. Hydrogen production by reacting water with mechanically milled composite aluminum- metal oxide powders. Fuel & Energy Abstracts, 2011, 36(8): 4781-4791）By aluminium powder with MgO、CuO、Al2O3、MoO3And Bi2O3Mechanical ball mill is carried out respectively, and discovery can effectively facilitate aluminum-water reaction.Wherein Al-Bi2O3Effect Fruit is best, and hydrogen output is 1150 ml.g-1, hydrogen rate is produced up to 100%.But there is problems with the material：The H2-producing capacity of material needs To realize at 80 degrees celsius, its H2-producing capacity significantly reduces under normal temperature condition.
Oxide CaO and inorganic salts NaCl are carried out ball milling with mechanical attrition method and prepared for Al- by Chen in 2013 et al. CaO-NaCl hydrogen manufacturing materials（Chen X, Zhao Z, Hao M, et al. Research of hydrogen generation by the reaction of Al-based materials with water[J]. Journal of Power Sources, 2013, 222(2):188-195.）, the production hydrogen rate of Al-35%CaO-7%NaCl hydrogen manufacturing materials can reach 100%, but problems be present in the material：Materials A l content is less than 70%, and the amount of additive is big, and unit mass hydrogen output is low.
The content of the invention
It is an object of the invention to provide a kind of Al-LiCl-Bi2O3The preparation method and applications of aluminum-based composite hydrogen manufacturing material. By adding LiCl and Bi simultaneously2O3Synergy is played to aluminum-water reaction, relatively individually addition greatly improves to H2-producing capacity, On the one hand hydrogen-producing speed is substantially improved, on the other hand reduces hydrolysis start-up temperature.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of Al-LiCl-Bi2O3Aluminum-based composite hydrogen manufacturing material, by aluminium powder, LiCl and Bi2O3Mixing and ball milling is made；The aluminium powder, LiCl and Bi2O3Mass ratio be（15~18）:（1~3）:（1~3）；Described aluminium powder is metallic aluminium elemental powders, preferably micron The aluminium powder of level, when react at room temperature with water for 25 DEG C, its production hydrogen rate up to 90 ~ 100%, unit mass hydrogen output can reach 1000 ~ 1200ml/g。
A kind of Al-LiCl-Bi2O3The preparation method of aluminum-based composite hydrogen manufacturing material, comprises the following steps：
Step 1）Al-LiCl-Bi2O3The preparation of aluminum-based composite hydrogen manufacturing material, under the protection of argon gas, by certain mass ratio（15~ 18）:（1~3）:（1~3）, weigh required aluminium powder, LiCl and Bi2O3Add in ball grinder and press certain ratio of grinding media to material 30-120 again:1 Sealed after being put into abrading-ball；
Step 2）Ball grinder is put into ball mill, it is 1-7 h to set ball milling condition as Ball-milling Time, and the rotating speed of ball milling is 200- 250r/min carries out ball milling, and prepared Al-LiCl-Bi is then taken out under the conditions of argon gas2O3Aluminum-based composite hydrogen manufacturing material.
Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material, by aluminium powder, LiCl and Bi2O3Mixing, passes through mechanical ball Mill method, makes Bi2O3Ball milling generates Bi simple substance, and it is dispersed in aluminium base, is effectively catalyzed the progress of aluminum-water reaction, gram The problems such as having taken cold welding, the reunion that direct ball milling Al-metal simple-substance is brought, while in mechanical milling process, by adding inorganic salts LiCl, it is utilized the fragility of itself, can be crushed in mechanical milling process, produce sharp edge, bulk alumina particles can be cut Into tiny particulate, the hydrogen-producing speed of aluminum matrix composite is improved, so as to improve the chemism of aluminium, while adds LiCl And Bi2O3Synergy is played to aluminum-water reaction, relatively individually addition greatly improves to H2-producing capacity, makes Al-LiCl-Bi2O3Aluminium Base composite hydrogen manufacturing material has very high H2-producing capacity.
In order to verify Al-LiCl-Bi2O3In aluminum-based composite hydrogen manufacturing material, the Bi of different content2O3To the shadow of H2-producing capacity Ring, the method for being prepared as described above prepares different Bi2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material, and system is hydrolyzed Hydrogen performance test.As a result show, as increase Bi2O3Content prepare Al-LiCl-Bi2O3Aluminum matrix composite, its hydrogen output The phenomenon declined afterwards in first rising, works as Bi2O3Addition mass percent be 5%, production hydrogen rate be only 37.87%, work as Bi2O3 When content increases to 10%, substantially significantly lifting reaches highest to aluminum-based composite hydrogen manufacturing material production hydrogen rate, and production hydrogen rate is 95.5%, production Hydrogen amount is 1104.4 mL/g.
In order to verify Al-LiCl-Bi2O3In aluminum-based composite hydrogen manufacturing material, the shadow of the LiCl of different content to H2-producing capacity Ring, the method for being prepared as described above prepares the Al-LiCl-Bi of different LiCl contents2O3Aluminum-based composite hydrogen manufacturing material, and system is hydrolyzed Hydrogen performance test.As a result show, Al-LiCl-Bi is prepared when increase LiCl content2O3Aluminum matrix composite hydrogen output is in first The phenomenon declined after rising, when the mass percent of LiCl addition is 5%, Al-LiCl-Bi2O3Aluminum-based composite hydrogen manufacturing material Hydrogen rate is produced up to 95.5%, unit mass hydrogen output can reach 1104.4 mL/g, and when LiCl contents increase to 15%, aluminium base is multiple Close hydrogen manufacturing material production hydrogen rate to have declined, production hydrogen rate is 91.9%, but hydrogen-producing speed is up to 6570 mL g-1 min-1.It can be seen that Al-LiCl-Bi2O3Aluminum-based composite hydrogen manufacturing material has very high H2-producing capacity, and independent ball milling Al- is avoided by adding LiCl Bi2O3Alumina-base material needs the hydrolysis start-up temperature of 80 degree of high temperature, Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material exists It can be achieved with producing hydrogen at room temperature, reduce the cost used, and hydrogen-producing speed increases substantially.
The present invention has advantages below relative to prior art：
1st, Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material has very high chemism, in neutral solution and room temperature Under conditions of, production hydrogen rate reaches 90 ~ 100%, and hydrogen output reaches 1000 ~ 1200mL/g；
2nd, Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material, when LiCl contents increase to 15%, aluminum-base composite hydrogen manufacturing Material hydrogen-producing speed is up to 6570 mL g-1 min-1, with regard to current document report, at room temperature, the maximum production hydrogen speed of aluminium water hydrogen manufacturing Rate is also not reaching to 5000mL g-1 min-1More than；
3rd, Al-LiCl-Bi of the present invention2O3Immediate response after aluminum-based composite hydrogen manufacturing material contacts with water, start the time less than 5 seconds, It can be reacted completely in 300 seconds, reaction rate is fast, and without the sign of burning；
4th, Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material can be realized relative to Al- oxide aluminum matrix composites It can just be reacted under normal temperature with water and release substantial amounts of hydrogen, and hydrogen-producing speed increases substantially, and avoids aluminum matrix composite and exists 80 degree of high temperature just have good performance, and so as to reduce use cost, and effect is more preferable.
5th, Al-LiCl-Bi of the present invention2O3It is uniform in Al to realize Li and Bi by ball milling for aluminum-based composite hydrogen manufacturing material Distribution, using the synergy between them, aluminium/water reaction is effectively facilitated, compared to other kinds of aluminum matrix composite With higher synthesis H2-producing capacity, unit mass hydrogen output, production hydrogen rate and the production of aluminum-based composite hydrogen manufacturing material are not only increased Hydrogen speed, the addition of bismuth oxide is also greatly decreased, effectively reduces the cost of composite.
6th, Al-LiCl-Bi of the present invention2O3Aluminum-based composite hydrogen manufacturing material preparation method technique is simple, environment-friendly, Ke Yishi Now hydrogen making and hydrogen supply at any time, is easy to carry, therefore, in hydrogen preparation field, particularly extensive energy storage, Portable movable hydrogen Source, fuel cell hydrogen-feeding etc. field have broad application prospects.
Brief description of the drawings：
Fig. 1 is Al-LiCl-Bi2O3Before aluminum-based composite hydrogen manufacturing material reaction（a）After reaction（b）XRD curves；
Fig. 2 is different Bi2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material normal temperature and the unit mass of water reaction are produced Hydrogen amount curve；
Fig. 3 is 5%, 7%Bi2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material normal temperature and the unit mass of water reaction are produced Hydrogen amount curve；
Fig. 4 is the Al-LiCl-Bi of different LiCl contents2O3Aluminum-based composite hydrogen manufacturing material normal temperature and the unit mass of water reaction are produced Hydrogen amount curve；
Fig. 5 is the Al-LiCl-Bi of 3%LiCl contents2O3Aluminum-based composite hydrogen manufacturing material normal temperature and the unit mass production hydrogen of water reaction Measure curve；
Fig. 6 is the Al-LiCl-Bi of different LiCl contents2O3Aluminum-based composite hydrogen manufacturing material normal temperature and the unit mass of water reaction are produced Hydrogen rate curve.
Embodiment
The present invention is described in further detail, but be not pair by embodiment with reference to Figure of description to present invention The restriction of the present invention.
Embodiment
Al-LiCl-Bi2O3The preparation method of aluminum-based composite hydrogen manufacturing material, comprises the following steps：
Step 1）Al-LiCl-Bi2O3The preparation of aluminum-based composite hydrogen manufacturing material, under the protection of argon gas, the g of precise 0.85 Al, 0.05 g LiCl and 0.1 g Bi2O3It is put into ball grinder, then by 60:1 ratio of grinding media to material seals after loading 60 g abrading-balls；
Step 2）Ball grinder is put into ball mill, setting rotational speed of ball-mill is set to 250 r/min, and Ball-milling Time is 5 h, ball milling, i.e., Obtain Al-LiCl-Bi2O3Aluminum-based composite hydrogen manufacturing material.
The present embodiment whole aluminum-based composite hydrogen manufacturing material hydrolytic hydrogen production performance test methods are as follows：Weigh 0.1g aluminum-base composites Hydrogen manufacturing material, at 25 DEG C, add 10ml water to react, determine its H2-producing capacity.
The Al-LiCl-Bi that ball milling is obtained2O3Aluminum-based composite hydrogen manufacturing material and the complete aluminum-base composite hydrogen manufacturing material of hydrolysis Product carries out XRD tests after the reaction of material, as a result as shown in figure 1, Al-LiCl-Bi after ball milling2O3Aluminum-based composite hydrogen manufacturing material shows Show main or Al characteristic peak, have also appeared Bi2Al4O9、Li5AlO4And Al2O3Peak, the effect for illustrating ball milling is not Simple to produce physical action, also novel substance produces, and is advantageous to the hydrolysis of alumina-base material, after hydrolysis Product be more Al (OH)2, it can be seen that Al has obtained sufficient reaction, in addition with AlH3The generation of material, says AlH caused by bright course of reaction3Reaction with water makes the H2-producing capacity of alumina-base material be further enhanced.
In order to verify influences of the LiCl to Al activation effects, the Al-LiCl of different LiCl contents is prepared for as stated above Aluminum-based composite hydrogen manufacturing material, in specific steps, not specified step is identical with the above-mentioned preparation method of the present embodiment, difference Be in：The step 1）The quality for weighing LiCl respectively is 0.1g, 0.2g.
Different Bi manufactured in the present embodiment2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material hydrolytic hydrogen production performance Test result such as table 1, as a result show, when increase LiCl content prepares Al-LiCl aluminum matrix composites, its hydrogen output be by Gradually elevated, when the mass percent of LiCl addition is 20%, production hydrogen rate is 30.33%.
Table 1 is at 25 DEG C, the Al-LiCl aluminum-based composite hydrogen manufacturing material H2-producing capacities of different LiCl contents
In order to verify Al-LiCl-Bi2O3In aluminum-based composite hydrogen manufacturing material, different Bi2O3Influence of the content to H2-producing capacity, by upper State preparation method and prepare different Bi2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material, in specific steps, do not say especially Bright step is identical with the above-mentioned preparation method of the present embodiment, and difference is：The step 1）Bi is weighed respectively2O3Quality For 0.05g, 0.07g, 0.1g, 0.13g and 0.15g.
Different Bi manufactured in the present embodiment2O3The Al-LiCl-Bi of content2O3Aluminum-based composite hydrogen manufacturing material hydrolytic hydrogen production performance As a result test result is shown as shown in table 2, Fig. 2 and Fig. 3, as increase Bi2O3Content prepare Al-LiCl-Bi2O3Aluminium base is answered Condensation material, its hydrogen output are in the phenomenon for first rising and declining afterwards, work as Bi2O3Addition mass percent be 5%, production hydrogen rate be only 37.87%, work as Bi2O3When content increases to 10%, substantially significantly lifting reaches highest, production to aluminum-based composite hydrogen manufacturing material production hydrogen rate Hydrogen rate is 95.5%, and hydrogen output is 1104.4 mL/g.
Table 2. is at 25 DEG C, different Bi2O3Content aluminum-based composite hydrogen manufacturing material H2-producing capacity
In order to verify Al-LiCl-Bi2O3In aluminum-based composite hydrogen manufacturing material, influence of the different LiCl contents to H2-producing capacity, by upper State the Al-LiCl-Bi that preparation method prepares different LiCl contents2O3Aluminum-based composite hydrogen manufacturing material, in specific steps, do not say especially Bright step is identical with the above-mentioned preparation method of the present embodiment, and difference is：The step 1）LiCl quality is weighed respectively For 0.03g, 0.05g, 0.07g, 0.1g and 0.15g.
The Al-LiCl-Bi of different LiCl contents manufactured in the present embodiment2O3Aluminum-based composite hydrogen manufacturing material hydrolytic hydrogen production performance Test result is as shown in Figure 4, Figure 5 and Figure 6, the results showed that, prepare Al-LiCl-Bi when increase LiCl content2O3Aluminium base is answered Condensation material hydrogen output is in the phenomenon for first rising and declining afterwards, when the mass percent of LiCl addition is 5%, Al-LiCl-Bi2O3 Aluminum-based composite hydrogen manufacturing material produces hydrogen rate up to 95.5%, and unit mass hydrogen output can reach 1104.4 mL/g, and hydrogen-producing speed is 1527 mL g-1 min-1, when LiCl contents increase to 15%, aluminum-based composite hydrogen manufacturing material production hydrogen rate has declined, and produces hydrogen rate For 91.9%, but hydrogen-producing speed is up to 6570 mL g-1 min-1.Independent ball milling Al-Bi is avoided by adding LiCl2O3Aluminium Sill needs the hydrolysis start-up temperature of 80 degree of high temperature, can be achieved with producing hydrogen at room temperature, reduces the cost used, and produce Hydrogen speed increases substantially.

Claims (8)

  1. A kind of 1. Al-LiCl-Bi2O3Aluminum-based composite hydrogen manufacturing material, it is characterised in that：The aluminum-based composite hydrogen manufacturing material by aluminium powder, LiCl and Bi2O3Mixing and ball milling is compared with certain mass.
  2. 2. Al-LiCl-Bi according to claim 12O3Aluminum-based composite hydrogen manufacturing material, it is characterised in that：The aluminium powder, LiCl and Bi2O3Mass ratio be（15~18）:（1~3）:（1~3）.
  3. 3. Al-LiCl-Bi according to claim 12O3Aluminum-based composite hydrogen manufacturing material, it is characterised in that：The aluminium powder is micro- Meter level aluminium powder.
  4. 4. Al-LiCl-Bi according to claim 12O3Aluminum-based composite hydrogen manufacturing material, it is characterised in that：25 DEG C at room temperature with When water reacts, it produces hydrogen rate up to 90 ~ 100%, and unit mass hydrogen output can reach 1000 ~ 1200ml/g.
  5. 5. Al-LiCl-Bi according to claim 12O3The preparation method of aluminum-based composite hydrogen manufacturing material, comprises the following steps：
    Step 1）By certain mass ratio, required aluminium powder, LiCl and Bi are weighed2O3Add in ball grinder and press certain ratio of grinding media to material again Sealed after being put into abrading-ball；
    Step 2）Ball grinder is put into ball mill, sets certain ball milling condition ball milling, then takes out prepared Al-LiCl- Bi2O3Aluminum-based composite hydrogen manufacturing material.
  6. 6. preparation method according to claim 5, it is characterised in that：The step 1）Aluminium powder, LiCl and Bi2O3Quality Than for（15~18）:（1~3）:（1~3）, the step 1）Ratio of grinding media to material be 30-120：1.
  7. 7. preparation method according to claim 4, it is characterised in that：The step 2）Ball milling condition be Ball-milling Time It is 1-7 h, the rotating speed of ball milling is 200-300 r/min.
  8. 8. preparation method according to claim 4, it is characterised in that：The Overall Steps are carried out under the conditions of argon gas.
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CN117583594A (en) * 2023-11-20 2024-02-23 南京工程学院 Waste aluminum alloy modified hydrolysis hydrogen production composite material and preparation method thereof
CN117583594B (en) * 2023-11-20 2024-04-26 南京工程学院 Waste aluminum alloy modified hydrolysis hydrogen production composite material and preparation method thereof

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