CN103420336A - Al-NaBiO3 composite materials used for hydrogen generation by hydrolysis and preparation thereof - Google Patents

Al-NaBiO3 composite materials used for hydrogen generation by hydrolysis and preparation thereof Download PDF

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Publication number
CN103420336A
CN103420336A CN2012101602292A CN201210160229A CN103420336A CN 103420336 A CN103420336 A CN 103420336A CN 2012101602292 A CN2012101602292 A CN 2012101602292A CN 201210160229 A CN201210160229 A CN 201210160229A CN 103420336 A CN103420336 A CN 103420336A
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hydrogen
nabio
matrix material
preparation
composite materials
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CN103420336B (en
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孙立贤
王爽
徐芬
张箭
李芬
刘加成
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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 discloses preparation of a series of efficient composite materials used for hydrogen generation by hydrolysis. According to the composite materials, a material which is used for hydrogen generation by hydrolysis and has excellent performances is obtained by adding a small amount of sodium bismuthate into an aluminum substrate. Based on the Al-NaBiO3 composite material, a small amount of NaCl or KCl is added to improve oxidation resistance of the composite materials in air at room temperature. A preparation method comprises steps of weighing various raw material powder needed according to a ratio and adding into a steel ball milling jar, performing high-speed ball-milling in a QM-3SP2 planetary ball mill, and feeding argon into the ball milling jar for protection to obtain the hydrogen generating materials with uniform components and high activity. According to the composite materials and the preparation, the preparation technology is simple; the cost for the raw materials is low; and the composite materials have high energy density, high hydrogen releasing rate and good oxidation resistance in air, and are suitable for applications in real-time vehicle-loading hydrogen supplying, and the like.

Description

A kind of Al-NaBiO 3Matrix material and preparation thereof for hydrolytic hydrogen production
Technical field
The present invention relates to onboard hydrogen source high reactivity aluminum matrix composite, be specially by adding specific additive, the hydrolysis property of metallic aluminium is improved greatly, meet the needs of practical application under normal condition.
Background technology
Hydrogen Energy, as a kind of very promising energy carrier, is studied widely and is applied in recent years.The fast development of hydrogen economy, stimulated the research of hydrogen producing technology, but the hydrogen storage cost is very high, and the unit mass hydrogen content is low, and exist various safety problems, thereby develop small inexpensive, pollution-free, safe and reliable, can become urgent demand (1.T.Ma with the hydrogen producing technology be connected with hydrogen storage equipment, J.Ji, M.Q.Chen, Int.J.Hydrogen Energy 35 (2010) 3114-3119.2.M.Hori, R.S.Hayano, M.Fukuta, T.Koyama, H.Nobusue, J.Tanaka, Rev.Sci.Instrum.80 (2009) 3.J.Graetz, Chem.Soc.Rev.38 (2009) 73-82.).Vehicle-mounted hydrogen production is a kind of hydrogen source material to be stored onboard, realizes that the Hydrogen Energy of instant hydrogen making and hydrogen supply is utilized method.Because do not need the auxiliary facilities such as hydrogen feeding pipe road, at current various hydrogen storage materials, apart from commercial applications, also have under the background of larger distance, be hopeful to meet in a short time the real-time hydrogen supply problem of hydrogen energy source power truck, thereby at the focus (4.Z.Y.Deng that becomes in recent years various countries' research and development, J.M.F.Ferreira, Y.Sakka, J.Am.Ceram.Soc.91 (2008) 3825-3834.5.R.von Helmolt, U.Eberle, J.Power Sources 165 (2007) 833-843.).
The metallic aluminium quality is light, and energy density is high, and aboundresources is cheap, and the hydrolysate safety non-pollution is desirable hydrolytic hydrogen production raw material.Generally, the metallic aluminium surface is covered with the oxide film of one deck densification, and the hydrolysis temperature in neutral water is very high, needs the above high temperature of 1,000 degree to react with water.If use basic solution, alkali can serve as the catalyzer of aluminium hydrolysis reaction, thereby effectively improve the dynamic performance of aluminium hydrolysis still in actual applications, basic solution is had relatively high expectations to the anticorrosive of equipment, and can be to the user being caused to potential harm (6.J.Bernard, M.Boinet, M.Chatenet, F.Dalard, Electrochemical and Solid State Letters 8 (2005) E53-E55.7.K.Eom, M.Kim, S.Oh, E.Cho, H.Kwon, Int.J.Hydrogen Energy 36 (2011) 11825-11831.8.H.-B.Dai, G.-L.Ma, H.-J.Xia, P.Wang, Energ Environ.Sci (2011)).
Soler etc. attempt using NaBH 4, NaAlO 2, Na 2SnO 3Solution replaces a part of basic solution, and hydrolysis reaction releasing hydrogen gas fast just can occur metallic aluminium at normal temperatures, at 0.075M Na 2SnO 3In solution, the initial hydrogen discharging rate of aluminium water reaction can reach 213mL/min*g(9.L.Soler, A.M.Candela, J.Macanas, M.Munoz, J.Casado, J.Power Sources 192 (2009) 21-26.10.L.Soler, A.M.Candela, J.Macanas, M.Munoz, J.Casado, Int.J.Hydrogen Energy 34 (2009) 8511-8518.11.L.Soler, J.Macanas, M.Munoz, J.Casado, J.Power Sources 169 (2007) 144-149.).Model is U.S. strong wait use ball milling and/or melting method to prepare contain Zn, Ca, Ga, Bi, Mg, the Al base of In additive meets material, studies discovery, Al-10%Sn-5%Zn-5%MgH 2Mixture has the hydrogen output of 785ml/g and the hydrogen-producing speed of 78.5ml/ (min.g) after ball milling 10h.And introducing SnCl 2, MgCl 2, after the muriate such as NaCl, the hydrolysis hydrogen discharging performance of material has obtained further raising, Al-10wt%Sn-5wt%Zn-5wt%MgCl 2The hydrogen desorption capacity of material can reach 866mL/g(12.M.Q.Fan, F.Xu, L.X.Sun, International Journal of Hydrogen Energy 32 (2007) 2809-2815.13.M.Q.Fan, L.X.Sun, F.Xu, Renewable Energy 36 (2011) 519-524.14.M.Q.Fan, L.X.Sun, F.Xu, Energy convers.Manage.51 (2010) 594-599.).
The main performance index of hydrolytic hydrogen production material is initial hydrogen discharging rate and hydrogen desorption capacity.Under same temperature condition, the material property that has the highest hydrogen discharging rate and hydrogen desorption capacity is best.
Summary of the invention
The object of the present invention is to provide under a kind of high reactivity high-energy-density, normal temperature with regard to bootable onboard hydrogen source matrix material, solve the problem that the too high and reaction of aluminium water reaction start-up temperature can not be lasting.At first the present invention by add a small amount of sodium bismuthate in base aluminum, has effectively improved the activity of matrix material.Preparation technology is simple, and raw materials cost is cheap, meets the needs of large-scale commercial production practical application.In addition, due to hydrolysis reaction mild condition of the present invention, put hydrogen rapidly fast and energy density is high, so also can be used as a kind of high performance hydrogen source material, be applied to the occasion of the aspects such as fuel cell.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of Al-NaBiO 3The hydrolytic hydrogen production matrix material adds the compound sodium bismuthate and is composited on the basis of metallic aluminium.Al-NaBiO 3The quality proportioning of matrix material is m (Al): m (NaBiO 3)=x:1-x, (x=0.1-0.99).
Taking respectively in proportion required aluminium powder and sodium bismuthate powder adds in the steel ball grinder; high speed ball milling on the QM-3SP2 planetary ball mill, ball material mass ratio is 20-40:1, rotating speed is turn/min of 300-500; Ball-milling Time 0.5-24 hour, be filled with argon shield in tank.
A kind of Al-NaBiO 3-NaCl/KCl hydrolytic hydrogen production matrix material, at the Al-NaBiO of above-mentioned gained 3On the basis of matrix material, a small amount of NaCl of interpolation or KCl are composited as additive;
Al-NaBiO 3-NaCl/KCl hydrolytic hydrogen production is m (Al): m (Bi): m (NaCl/KCl)=x:y:z by the quality proportioning of matrix material, x=0.5-0.98, y=0.001-0.5, z=0.001-0.2, and x+y+z=1.
Take respectively in proportion required aluminium powder, sodium bismuthate powder, sodium-chlor powder or Repone K powder and add in the steel ball grinder, high speed ball milling on the QM-3SP2 planetary ball mill, ball milling parameter and Al-NaBiO 3Matrix material is identical.
Resulting matrix material is for carrying out the hydrolysis hydrogen discharging performance test under normal temperature.
Means of testing to matrix material hydrolysis hydrogen discharging performance is draining water gathering of gas law, experimental temperature 25-90 ℃, hydrolysising experiment adopts deionized water, with the experiment ratio of sample be 100:1, test duration 20min.The start-up temperature that described aluminum matrix composite general script metallic aluminium and water are 1400 ℃ is reduced to room temperature and just can reacts, and initial hydrogen discharging rate has reached 452ml/ (min.g), just can emit the hydrogen (being about 1360mL/gAl) of whole theoretical capacities in 5 minutes.And aerial antioxidant property is good, opens wide in air at normal temperatures and place also still not obviously decline of hydrogen discharging performance after ten days.After adding the 3rd component sodium-chlor or Repone K, matrix material hydrolysis rate at normal temperatures is lower, illustrates that its aerial antioxidant property is more good.
The present invention has following advantage:
1. energy density is high.With other raw materials, compare, the metallic aluminium quality is light, and energy density is high, is desirable real-time hydrogen manufacturing material.
2. put the hydrogen condition gentleness.The present invention effectively raises the reactive behavior of metallic aluminium in water.The needs of applying have been met under normal condition.
3. cost of material is cheap.The aboundresources of metallic aluminium in the earth's crust, cheap, meet the requirement of suitability for industrialized production.
4. technological process is simple.The present invention utilizes planetary ball mill, and feed metal aluminium powder and additive is evenly compound, simple.
5. safety non-pollution.The products of combustion of hydrogen is water, is a kind of very clean alternative new forms of energy.And the product of aluminium water hydrogen production reaction safety and stability too meets eco-friendly requirement.
6. use and put in real time the hydrogen mode, solved the storage problem of hydrogen, the hydrogen storage cost of reduction.
7. aerial resistance of oxidation is good, reduces the storage request of matrix material, improves security.
The contriver adds sodium bismuthate in having attempted first in metallic aluminium and improves the reactive behavior of metallic aluminium in water.The matrix material energy density obtained is high, and the reaction conditions gentleness, put hydrogen rapid, the hydrolysate safety non-pollution.The needs of suitability for industrialized production and practical application have well been met.
The accompanying drawing explanation
Fig. 1 is Al-10wt%NaBiO in embodiment 1 3The hydrolysis Hydrogen desorption isotherms at normal temperatures at the deionized water that adds different ratios;
Fig. 2 is Al-10wt%NaBiO in embodiment 1 3The hydrolysis Hydrogen desorption isotherms of different probe temperatures;
Fig. 3 is Al-10wt%NaBiO in embodiment 2 3The hydrolysis Hydrogen desorption isotherms under 90 ℃ of probe temperatures after the exposure different time in air;
The Al-NaBiO that Fig. 4 is different ratios in embodiment 3 3Matrix material hydrolysis Hydrogen desorption isotherms at normal temperatures;
The Al-NaBiO that Fig. 5 is different ratios in embodiment 4 3-NaCl trielement composite material hydrolysis Hydrogen desorption isotherms at normal temperatures.
Embodiment
Embodiment 1
Under argon shield, by quality, join for m (Al): m (NaBiO 3The aluminium of)=0.9:0.1 and sodium bismuthate component join in the steel ball grinder, select turn/min of rotating speed 500, the ball milling parameter of ratio of grinding media to material 60:1, be placed in high speed ball milling on the QM-3SP2 planetary ball mill by ball grinder, and ball milling obtains the uniform high reactivity hydrolysis of composition composite material for manufacturing hydrogen in 10 hours.
Take the 0.05g sample in reaction flask, add the deionized water of different ratios after good seal.The hydrogen that experiment produces is imported in water-filled inversion graduated cylinder by a conduit, adopts manual time-keeping, manually record data.Change experimental temperature, obtain the hydrolysis hydrogen discharging performance of sample under normal temperature and differing temps.
By Fig. 1 and 2, can be found out, described aluminum matrix composite has very good hydrolysis hydrogen discharging performance, and add-on or raising temperature of reaction by reducing water, can make the hydrogen discharging rate of matrix material significantly rise.
Embodiment 2
Under argon shield, by quality, join for m (Al): m (NaBiO 3The aluminium of)=0.9:0.1 and sodium bismuthate component join in the steel ball grinder, and the ball milling parameter is consistent with embodiment 1.
After obtaining composite sample, in air, open wide and place, after making it and airborne water, oxygen fully contacting different time, take the 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, the sample test method is consistent with embodiment 1.
As seen from Figure 3, Al-NaBiO 3The aerial antioxidant property of matrix material is good, opens wide in air at normal temperatures and places also still not obviously decline of hydrogen discharging performance after ten days.
Embodiment 3
Aluminium and sodium bismuthate component by the different mass proportioning under argon shield join in the steel ball grinder, and the ball milling parameter is consistent with embodiment 1.Take the 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, the sample test method is consistent with embodiment 1.
As seen from Figure 4, Al-NaBiO 3The hydrolysis hydrogen discharging performance of matrix material is along with NaBiO 3The increase of doping and rising rapidly, illustrate NaBiO 3Be one to activation aluminium very effective dopant.
Embodiment 4
Aluminium, sodium bismuthate and sodium-chlor component by the different mass proportioning under argon shield join in the steel ball grinder, and the ball milling parameter is consistent with embodiment 1.Take the 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, the sample test method is consistent with embodiment 1.
As seen from Figure 5, after adding the 3rd component sodium-chlor or Repone K, matrix material hydrolysis rate at normal temperatures is lower, illustrates that its aerial antioxidant property is more good.

Claims (4)

1. an Al-NaBiO 3The hydrolytic hydrogen production matrix material is characterized in that:
Adding sodium bismuthate in base aluminum is composited as additive;
Al-NaBiO 3The quality proportioning of matrix material is m (Al): m (NaBiO 3)=x:1-x, x=0.1-0.99..
2. the preparation method of the described matrix material of claim 1; it is characterized in that: take respectively in proportion required aluminium powder and sodium bismuthate powder and add in the steel ball grinder; high speed ball milling on the QM-3SP2 planetary ball mill; ball material mass ratio is 20-40:1; rotating speed is turn/min of 300-500; Ball-milling Time 0.5-24 hour, be filled with argon shield in tank.
3. an Al-NaBiO 3-NaCl/KCl hydrolytic hydrogen production matrix material is characterized in that:
At Al-NaBiO 3On the basis of matrix material, a small amount of NaCl of interpolation or KCl are composited as additive;
Al-NaBiO 3-NaCl/KCl hydrolytic hydrogen production is m (Al): m (Bi): m (NaCl or KCl)=x:y:z by the quality proportioning of matrix material, x=0.5-0.98, y=0.001-0.5, z=0.001-0.2, and x+y+z=1.
4. the preparation method of the described matrix material of claim 3; it is characterized in that: take respectively in proportion required aluminium powder, sodium bismuthate powder, sodium-chlor powder or Repone K powder and add in the steel ball grinder; high speed ball milling on the QM-3SP2 planetary ball mill; ball material mass ratio is 20-40:1; rotating speed is turn/min of 300-500; Ball-milling Time 0.5-24 hour, be filled with argon shield in tank.
CN201210160229.2A 2012-05-22 2012-05-22 A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof Expired - Fee Related CN103420336B (en)

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CN108176391A (en) * 2017-12-19 2018-06-19 浙江大学城市学院 NaBiO is enhanced based on metal nanoparticle3The method of visible light catalytic effect

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108176391A (en) * 2017-12-19 2018-06-19 浙江大学城市学院 NaBiO is enhanced based on metal nanoparticle3The method of visible light catalytic effect
CN108176391B (en) * 2017-12-19 2020-10-02 浙江大学城市学院 Enhancement of NaBiO based on metal nanoparticles3Visible light catalytic method

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