CN103420336B - A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof - Google Patents

A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof Download PDF

Info

Publication number
CN103420336B
CN103420336B CN201210160229.2A CN201210160229A CN103420336B CN 103420336 B CN103420336 B CN 103420336B CN 201210160229 A CN201210160229 A CN 201210160229A CN 103420336 B CN103420336 B CN 103420336B
Authority
CN
China
Prior art keywords
hydrogen
nabio
matrix material
ball
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210160229.2A
Other languages
Chinese (zh)
Other versions
CN103420336A (en
Inventor
孙立贤
王爽
徐芬
张箭
李芬
刘加成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201210160229.2A priority Critical patent/CN103420336B/en
Publication of CN103420336A publication Critical patent/CN103420336A/en
Application granted granted Critical
Publication of CN103420336B publication Critical patent/CN103420336B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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 present invention is the preparation of a series of effectively hydrolyzing hydrogen manufacturing aluminum matrix composite.This matrix material is in base aluminum, add the hydrolytic hydrogen production material that minority specioz sodium bismuthate obtains superior performance; At Al-NaBiO 3on the basis of matrix material, add a small amount of NaCl or KCl, improve the antioxidant property of matrix material at normal temperatures in air.Preparation method is as follows: take required various raw material powders in proportion respectively and add in steel ball grinder, on QM-3SP2 planetary ball mill, high speed ball milling, is filled with argon shield in ball grinder, obtains the high reactivity hydrogen manufacturing material of uniform composition.Preparation technology of the present invention is simple, and low raw-material cost, has very high energy density and hydrogen discharging rate, and aerial antioxidant property is good, is applicable to the application of the aspects such as vehicle-mounted real-time hydrogen supply.

Description

A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof
Technical field
The present invention relates to onboard hydrogen source high reactivity aluminum matrix composite, specifically by the specific additive of interpolation, the hydrolysis property of metallic aluminium is improved greatly, meet the needs of practical application under normal conditions.
Background technology
Hydrogen Energy as a kind of very promising energy carrier, in recent years by investigation and application widely.The fast development of hydrogen economy, have stimulated the research of hydrogen producing technology, but hydrogen storage cost is very high, and unit mass hydrogen content is low, and there is various safety problem, thus small inexpensive is developed, pollution-free, safe and reliable, the hydrogen producing technology that can be connected with hydrogen storage equipment has become urgent demand (1.T.Ma, J.Ji, M.Q.Chen, Int.J.HydrogenEnergy35 (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 that hydrogen source material stores onboard by one, realizes the hydrogen utilization method of instant hydrogen making and hydrogen supply.Because do not need the auxiliary facilities such as hydrogen feeding pipe road, under current various hydrogen storage material distance commercial applications also has the background of larger distance, be hopeful the real-time hydrogen supply problem meeting hydrogen energy source power truck in a short time, thus focus (the 4.Z.Y.Deng researched and developed various countries is being become in recent years, J.M.F.Ferreira, Y.Sakka, J.Am.Ceram.Soc.91 (2008) 3825-3834.5.R.vonHelmolt, U.Eberle, J.PowerSources165 (2007) 833-843.).
Metallic aluminium quality is light, and energy density is high, and aboundresources is cheap, hydrolysate safety non-pollution, is desirable hydrolytic hydrogen production raw material.Generally, metallic aluminum surface is covered with the oxide film of one deck densification, and the hydrolysis temperature in neutral water is very high, needs the high temperature of more than 1,000 degree could react with water.If use basic solution, alkali can serve as the catalyzer of aluminium hydrolysis reaction, thus effectively improve aluminium hydrolysis dynamic performance but in actual applications, the anticorrosive requirement of basic solution to equipment is higher, and can to user being caused to potential harm (6.J.Bernard, M.Boinet, M.Chatenet, F.Dalard, ElectrochemicalandSolidStateLetters8 (2005) E53-E55.7.K.Eom, M.Kim, S.Oh, E.Cho, H.Kwon, Int.J.HydrogenEnergy36 (2011) 11825-11831.8.H.-B.Dai, G.-L.Ma, H.-J.Xia, P.Wang, EnergEnviron.Sci (2011)).
Soler etc. attempt using NaBH 4, NaAlO 2, Na 2snO 3solution replaces the basic solution of a part, and metallic aluminium at normal temperatures hydrolysis reaction releasing hydrogen gas fast just can occur, at 0.075MNa 2snO 3in solution, the initial hydrogen discharging rate of aluminum-water reaction can reach 213mL/min*g(9.L.Soler, A.M.Candela, J.Macanas, M.Munoz, J.Casado, J.PowerSources192 (2009) 21-26.10.L.Soler, A.M.Candela, J.Macanas, M.Munoz, J.Casado, Int.J.HydrogenEnergy34 (2009) 8511-8518.11.L.Soler, J.Macanas, M.Munoz, J.Casado, J.PowerSources169 (2007) 144-149.).Model is U.S. strong waits the Al base containing Zn, Ca, Ga, Bi, Mg, In additive with prepared by ball milling and/or melting method to meet 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 at introducing SnCl 2, MgCl 2, after the muriate such as NaCl, the hydrolysis hydrogen discharging performance of material obtains 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, InternationalJournalofHydrogenEnergy32 (2007) 2809-2815.13.M.Q.Fan, L.X.Sun, F.Xu, RenewableEnergy36 (2011) 519-524.14.M.Q.Fan, L.X.Sun, F.Xu, Energyconvers.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 having the highest hydrogen discharging rate and hydrogen desorption capacity is best.
Summary of the invention
To the object of the present invention is to provide under a kind of high reactivity high-energy-density, normal temperature just bootable onboard hydrogen source matrix material, solve aluminum-water reaction start-up temperature too high and react the problem that can not continue.First the present invention by adding a small amount of sodium bismuthate in base aluminum, effectively improves the activity of matrix material.Preparation technology is simple, and low raw-material cost, meets the needs of large-scale commercial production practical application.In addition, due to hydrolysis reaction mild condition of the present invention, put that hydrogen is rapidly fast and energy density is high, so also as the high performance hydrogen source material of one, can 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 3hydrolytic hydrogen production matrix material, the basis of metallic aluminium is added compound sodium bismuthate and is composited.Al-NaBiO 3the quality proportioning of matrix material is m (Al): m (NaBiO 3)=x:1-x, (x=0.1-0.99).
Take required aluminium powder in proportion respectively and sodium bismuthate powder adds in steel ball grinder; high speed ball milling on QM-3SP2 planetary ball mill, ball material mass ratio is 20-40:1, and rotating speed is that 300-500 turns/min; Ball-milling Time 0.5-24 hour, is 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 3the basis of matrix material is added a small amount of NaCl or KCl to be composited as additive;
Al-NaBiO 3the quality proportioning of-NaCl/KCl hydrolytic hydrogen production matrix material is m (Al): m (Bi): m (NaCl/KCl)=x:y:z, x=0.5-0.98, y=0.001-0.5, z=0.001-0.2, and x+y+z=1.
Taking required aluminium powder, sodium bismuthate powder, sodium chloride powder or Repone K powder in proportion respectively adds in steel ball grinder, high speed ball milling on QM-3SP2 planetary ball mill, ball milling parameter and Al-NaBiO 3matrix material is identical.
The matrix material obtained is for carrying out the hydrolysis hydrogen discharging performance test under normal temperature.
Means of testing matrix material being hydrolyzed to hydrogen discharging performance is draining water gathering of gas law, experimental temperature 25-90 DEG C, and hydrolysising experiment adopts deionized water, is 100:1 with the trial scale of sample, test duration 20min.The start-up temperature of script metallic aluminium and 1400 DEG C, water is reduced to room temperature and just can reacts by described aluminum matrix composite, and initial hydrogen discharging rate reaches 452ml/ (min.g), just can release the hydrogen (being about 1360mL/gAl) of whole theoretical capacity in 5 minutes.And aerial antioxidant property is excellent, at normal temperatures in air open wide placement after ten days hydrogen discharging performance also still obviously do not decline.After adding three components sodium-chlor or Repone K, matrix material hydrolysis rate is at normal temperatures lower, illustrates that its aerial antioxidant property is more excellent.
Tool of the present invention has the following advantages:
1. energy density is high.Compared with other raw materials, metallic aluminium quality is light, and energy density is high, is desirable real-time hydrogen manufacturing material.
2. put hydrogen condition gentleness.The present invention effectively raises the reactive behavior of metallic aluminium in water.Meet the needs applied under normal conditions.
3. low in raw material price.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, by feed metal aluminium powder and the even compound of additive, 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 safety and stability too of aluminium water hydrogen production reaction, meet eco-friendly requirement.
6. use and put hydrogen mode in real time, solve 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.
Contriver has attempted adding sodium bismuthate in metallic aluminium to improve the reactive behavior of metallic aluminium in water first.The matrix material energy density obtained is high, and reaction conditions is gentle, puts hydrogen rapid, hydrolysate safety non-pollution.Well meet the needs of suitability for industrialized production and practical application.
Accompanying drawing explanation
Fig. 1 is Al-10wt%NaBiO in embodiment 1 3adding the deionized water hydrolysis Hydrogen desorption isotherms at normal temperatures of different ratios;
Fig. 2 is Al-10wt%NaBiO in embodiment 1 3the hydrolysis Hydrogen desorption isotherms of different probe temperature;
Fig. 3 is Al-10wt%NaBiO in embodiment 2 3hydrolysis Hydrogen desorption isotherms in atmosphere after exposure different time under 90 DEG C of probe temperatures;
Fig. 4 is the Al-NaBiO of different ratios in embodiment 3 3matrix material hydrolysis Hydrogen desorption isotherms at normal temperatures;
Fig. 5 is the Al-NaBiO of different ratios in embodiment 4 3-NaCl trielement composite material hydrolysis Hydrogen desorption isotherms at normal temperatures.
Embodiment
Embodiment 1
Join for m (Al) by quality under argon shield: m (NaBiO 3the aluminium of)=0.9:0.1 and sodium bismuthate component join in steel ball grinder, select rotating speed 500 turns/min, the ball milling parameter of ratio of grinding media to material 60:1, is placed in high speed ball milling on QM-3SP2 planetary ball mill by ball grinder, ball milling obtains the high reactivity composite material for hydrolysis hydrogen production of uniform composition for 10 hours.
Take 0.05g sample in reaction flask, after good seal, add the deionized water of different ratios.The hydrogen that experiment produces imports in water-filled inversion graduated cylinder by a conduit, adopts manual time-keeping, manual record data.Change experimental temperature, obtain the hydrolysis hydrogen discharging performance of sample under normal temperature and differing temps.
As can be seen from Fig. 1 and 2, described aluminum matrix composite has very excellent hydrolysis hydrogen discharging performance, by reducing the add-on of water or improving temperature of reaction, the hydrogen discharging rate of matrix material can be made significantly to increase.
Embodiment 2
Join for m (Al) by quality under argon shield: m (NaBiO 3the aluminium of)=0.9:0.1 and sodium bismuthate component join in steel ball grinder, and ball milling parameter is consistent with embodiment 1.
After obtaining composite sample, open wide in atmosphere and place, after making it fully contact different time with the water in air, oxygen, take 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, sample test method is consistent with embodiment 1.
As seen from Figure 3, Al-NaBiO 3the aerial antioxidant property of matrix material is excellent, at normal temperatures in air open wide placement after ten days hydrogen discharging performance also still obviously do not decline.
Embodiment 3
Join in steel ball grinder by the aluminium of different mass proportioning and sodium bismuthate component under argon shield, ball milling parameter is consistent with embodiment 1.Take 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, 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, illustrates NaBiO 3be one to activation aluminium very effective dopant.
Embodiment 4
Join in steel ball grinder by the aluminium of different mass proportioning, sodium bismuthate and sodium-chlor component under argon shield, ball milling parameter is consistent with embodiment 1.Take 0.05g sample in reaction flask, add the deionized water of 5mL after good seal, sample test method is consistent with embodiment 1.
As seen from Figure 5, after adding three components sodium-chlor or Repone K, matrix material hydrolysis rate is at normal temperatures lower, illustrates that its aerial antioxidant property is more excellent.

Claims (2)

1. an Al-NaBiO 3the preparation method of hydrolytic hydrogen production matrix material, it is characterized in that: take required aluminium powder in proportion respectively and sodium bismuthate powder adds in steel ball grinder, high speed ball milling on QM-3SP2 planetary ball mill, ball material mass ratio is 20-40:1, rotating speed is that 300-500 turns/min, Ball-milling Time 0.5-24 hour, is filled with argon shield in tank; In base aluminum, add sodium bismuthate be 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. an Al-NaBiO 3the preparation method of-NaCl/KCl hydrolytic hydrogen production matrix material, is characterized in that: at Al-NaBiO 3the basis of matrix material is added a small amount of NaCl or KCl to be composited as additive;
Al-NaBiO 3the quality proportioning of-NaCl/KCl hydrolytic hydrogen production matrix material is m (Al): m (Bi): m (NaCl or KCl)=x:y:z, x=0.5-0.98, y=0.001-0.5, z=0.001-0.2, and x+y+z=1;
Taking required aluminium powder, sodium bismuthate powder, sodium chloride powder or Repone K powder in proportion respectively adds in steel ball grinder; high speed ball milling on QM-3SP2 planetary ball mill; ball material mass ratio is 20-40:1; rotating speed is that 300-500 turns/min; Ball-milling Time 0.5-24 hour, is 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210160229.2A CN103420336B (en) 2012-05-22 2012-05-22 A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210160229.2A CN103420336B (en) 2012-05-22 2012-05-22 A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof

Publications (2)

Publication Number Publication Date
CN103420336A CN103420336A (en) 2013-12-04
CN103420336B true CN103420336B (en) 2015-12-16

Family

ID=49645786

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210160229.2A Expired - Fee Related CN103420336B (en) 2012-05-22 2012-05-22 A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof

Country Status (1)

Country Link
CN (1) CN103420336B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289163A (en) * 2007-04-20 2008-10-22 中国科学院大连化学物理研究所 Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof
RU2394753C1 (en) * 2009-04-01 2010-07-20 Учреждение Российской Академии Наук Объединенный Институт Высоких Температур Ран (Оивт Ран) Hydroreactive composition for producing hydrogen and method of preparing said composition
CN102009950A (en) * 2010-09-21 2011-04-13 上海大学 Aluminium-based compound capable of having hydrolysis reaction under neutral and normal temperature conditions to produce hydrogen and preparation method thereof
CN102408096A (en) * 2011-07-26 2012-04-11 辽宁师范大学 Aluminum-based composite hydrogen manufacturing material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110262346A1 (en) * 2010-04-15 2011-10-27 Hadasit Medical Research Services & Development Limited Reactors and methods for producing spin enriched hydrogen gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289163A (en) * 2007-04-20 2008-10-22 中国科学院大连化学物理研究所 Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof
RU2394753C1 (en) * 2009-04-01 2010-07-20 Учреждение Российской Академии Наук Объединенный Институт Высоких Температур Ран (Оивт Ран) Hydroreactive composition for producing hydrogen and method of preparing said composition
CN102009950A (en) * 2010-09-21 2011-04-13 上海大学 Aluminium-based compound capable of having hydrolysis reaction under neutral and normal temperature conditions to produce hydrogen and preparation method thereof
CN102408096A (en) * 2011-07-26 2012-04-11 辽宁师范大学 Aluminum-based composite hydrogen manufacturing material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Controlled hydrogen generation by reaction of aluminum/sodium hydroxide/sodium stannate solid mixture with water;Guang-Lu Ma et al.;《international journal of hydrogen energy》;20120123;第37卷;第5811-5816页 *
Studies on hydrogen generation characteristics of hydrolysis of the ball milling Al-based materials in pure water;MQ Fan et al.;《International Journal of Hydrogen Energy》;20070212;第32卷;第2810页实验部分 *

Also Published As

Publication number Publication date
CN103420336A (en) 2013-12-04

Similar Documents

Publication Publication Date Title
Liu et al. Issues and opportunities facing hydrolytic hydrogen production materials
CN102409202A (en) Al-Ga-In-Sn-Zn alloy as well as preparation method and application thereof
CN102009950B (en) Aluminium-based compound capable of having hydrolysis reaction under neutral and normal temperature conditions to produce hydrogen and preparation method thereof
CN101811667B (en) Magnesium base hydride composite system for hydrolysis hydrogen production and preparation method and application thereof
CN102030313B (en) Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof
CN101948093A (en) Method for preparing hydrogen by cracking water by using aluminum-based material
CN102992263A (en) Al-Bi-NaCl-alkali metal or hydride hydrolysis hydrogen production composite materials and preparation thereof
CN105819399A (en) Hydrogen production reaction with controllable hydrogen production speed
CN110184517B (en) Porous ternary magnesium-rich hydrogen production hydrolysis alloy and preparation method thereof
CN103420336B (en) A kind of Al-NaBiO 3hydrolytic hydrogen production matrix material and preparation thereof
CN102583241A (en) Sodium borohydride matrix composite used for generating hydrogen by hydrolysis
CN102225741A (en) Preparation method of ammonia-containing composite ionic hydrogen storage material
CN101920973B (en) Method for preparing porous aluminum diboride
CN111573621B (en) Method for preparing hydrogen by hydrolysis
CN101811669A (en) High-capacity hydrogen storage material Zn(BH4)2.2NH3 and preparation method thereof
CN103787273A (en) Magnesium-calcium-based hydride powder for wide-temperature zone hydrolysis hydrogen generation and preparation method for magnesium-calcium-based hydride powder
CN106185803A (en) A kind of hydrolytic hydrogen production is with containing aluminum composition and its preparation method and application
CN101299471A (en) Composite electrolytic solution of lithium ion power battery and preparation method thereof
CN105800553A (en) Al-BiOCl aluminum-based composite hydrogen production material and preparation method thereof
CN109852847A (en) Al-Ga-In-Sn-Cu alloy of hydrogen manufacturing and preparation method thereof, application in a fuel cell
CN101456535A (en) Method for preparing hydrogen
CN101602485A (en) The NaAlH of Ce hydride catalytic 4Composite hydrogen storage material and preparation method
CN102530871A (en) Modified borane ammoniate hydrogen storage material and preparation method thereof
CN107585738B (en) Mg-Mg2Si composite hydrolysis hydrogen production material, preparation method thereof and method for hydrolysis hydrogen production
CN104030246B (en) A kind of aluminium lithium hydrogen storage material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151216

Termination date: 20180522

CF01 Termination of patent right due to non-payment of annual fee