CN105584989A - Amorphous magnesium-aluminum-base composite hydrogen storage material and preparation method thereof - Google Patents
Amorphous magnesium-aluminum-base composite hydrogen storage material and preparation method thereof Download PDFInfo
- Publication number
- CN105584989A CN105584989A CN201610118105.6A CN201610118105A CN105584989A CN 105584989 A CN105584989 A CN 105584989A CN 201610118105 A CN201610118105 A CN 201610118105A CN 105584989 A CN105584989 A CN 105584989A
- Authority
- CN
- China
- Prior art keywords
- hydrogen storage
- storage material
- amorphous
- base composite
- composite hydrogen
- 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.)
- Granted
Links
Classifications
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses an amorphous magnesium-aluminum-base composite hydrogen storage material and a preparation method thereof. The amorphous magnesium-aluminum-base composite hydrogen storage material is prepared from an amorphous Mg17Al12 matrix and a transition metal hydride in a mass ratio of 100:(0.5-10), wherein the transition metal hydride is one or more of TiH2, ZrH2 and ScH2. The preparation method comprises the following steps: a) in an inert atmosphere, uniformly mixing raw materials Mg powder and Al powder according to the proportioning of the Mg17Al12, and preparing amorphous Mg17Al12 matrix powder by low-temperature ball milling; and b) carrying out mechanical ball milling on the prepared amorphous Mg17Al12 matrix powder and transition metal hydride powder under the protection of the inert gas to obtain the amorphous magnesium-aluminum-base composite hydrogen storage material. The composite hydrogen storage material has excellent medium/low-temperature hydrogen absorption/desorption properties.
Description
Technical field
The present invention relates to light hydrogen occluding Material Field, be specifically related to a kind of amorphous magnesium aluminum-base composite hydrogen storage materialAnd preparation method thereof.
Background technology
Hydrogen is a kind of energy carrier of clean and effective, and its combustion product is pollution-free, have combustibility good,Light fast, also advantages of higher of calorific value, it develops both can solve the fossil energy energy danger of shortage increasinglyMachine, can eliminate again a series of problem of environmental pollutions such as greenhouse effects, haze that combustion of fossil fuel causes.Utilizing hydride hydrogen-storing is a kind of safety and the approach that has unusual Fabrication of High Specific Capacitance and store up hydrogen density, twoInferior energy field has irreplaceable effect, particularly in fuel cell, Ni-MH battery material, and toolThere is very important status. Metal M g is owing to having relatively high quality hydrogen-storage density (7.6wt.%)Be considered to have the metal hydrogen storage material of good development prospect with cheap price. But its actual suction is put400 DEG C of hydrogen operating temperatures too high (>), kinetics poor-performing, has seriously restricted practical application.At present adopt compound effect can effectively improve its hydrogen storage property to magnesium-base hydrogen storage material, mainly comprise:Mg+Mg2Ni，Mg+LaNi5, Mg+FeTi etc., but the hydrogen discharging temperature of above-mentioned compound system is still too high.In addition Mg,17Al12The theoretical hydrogen storage content of-H is 4.4wt.%, compares Mg2NiH4Hydrogen storage content high (3.6wt.%),And Mg17Al12The hydrogen decomposition temperature of putting of-H system compares MgH2And Mg2NiH4Low " HydridingbehaviorofMg–AlandleachedMg–Alcompoundspreparedbyhigh-energyBall-milling, J.AlloysComp., 2000,297:282-293 ". Further research is found, amorphous stateMg17Al12The hydrogen storage property of alloy is obviously better than nanocrystalline and Mg as cast condition17Al12Alloy " ball millingMg17Al12The micro-structural of nanocrystalline/non-crystaline amorphous metal and hydrogen storage property, XI AN JIAOTONG UNIVERSITY Subject Index, 2007;41 (11): 1368-1352. ", but amorphous state Mg17Al12Alloy is under middle low temperature (≤200 DEG C) conditionHydrogen desorption kinetics performance still can not meet the demand of practical application.
Application publication number is China's invention of CN104709873A (application number is 201510109564.3)Patent Application Publication a kind of preparation method of novel Mg-Li-Al-Ti hydrogen storage material, comprise the steps:(1) by LiH and LiAlH4Put into ball grinder by the mol ratio of 1～3:1, under the protection of inert gasCarry out mechanical mixture, Ball-milling Time is 5～10 hours, and rotating speed is 150～300rpm, and ratio of grinding media to material is 200:1, make Li3AlH6; (2) by MgH2With Li3AlH6Taking mol ratio as (2～5): 1 ratio is putEnter ball grinder, then by x%Al/AlCl3+y％Ti/TiF3The mixture of (5 < x < 20,5 < y < 15) is put intoIn ball grinder, ratio of grinding media to material is 100～300:1, ball milling 1～6h under the protection of inert gas, and rotating speed is50～300rpm, makes Mg-Li-Al-Ti hydrogen storage material. The method generates catalyst A l by original position3Ti，Efficient catalytic MgH2Hydrogen storage material carries out can inverse put hydrogen. This technical scheme has not only kept MgH2Gao RongAmount hydrogen storage property, and generated in-situ catalyst can obviously improve MgH2The dynamics of hydrogen storage materialCan, obviously reduce its reversible hydrogen uptake condition simultaneously. Consisting of of this Mg-Li-Al-Ti hydrogen storage material:MgH2、Li3AlH6、Al/AlCl3And Ti/TiF3. But this Mg-Li-Al-Ti hydrogen storage material is inhaled and is put hydrogen temperatureSpend still higherly, and its quality hydrogen-storage density also needs further raising.
Summary of the invention
The object of the present invention is to provide a kind of amorphous magnesium aluminum-base composite hydrogen storage material, it has solved the storage of magnesium baseThe problem that hydrogen material hydrogen discharging temperature is too high, it is compared with keeping the good dynamics of system under low operating temperaturePerformance.
A kind of amorphous magnesium aluminum-base composite hydrogen storage material, by the amorphous state Mg of mass ratio 100:0.5～1017Al12Matrix and transition metal hydride are made, and described transition metal hydride is TiH2、ZrH2、ScH2In one or more (comprising two kinds).
Further preferably, described amorphous magnesium aluminum-base composite hydrogen storage material, by mass ratio 100:5～10Amorphous state Mg17Al12Matrix and transition metal hydride are made, and have excellent middle low temperature hydrogen storage property.
Further preferred, described amorphous magnesium aluminum-base composite hydrogen storage material, non-by mass ratio 100:5Crystalline state Mg17Al12Matrix and transition metal hydride are made, and have more excellent middle low temperature suction and put hydrogenEnergy.
Most preferred, described amorphous magnesium aluminum-base composite hydrogen storage material, by the amorphous state of mass ratio 100:5Mg17Al12Matrix and transition metal hydride are made, and described transition metal hydride is ScH2。
This composite hydrogen storage material has excellent middle low temperature hydrogen storage property. Can in 30min at 200 DEG CInhale fast the capacity of putting hydrogen and reach 4.0wt.%.
Another object of the present invention is to provide a kind of preparation method of amorphous magnesium aluminum-base composite hydrogen storage material,Prepare easyly, be easy to obtain.
A preparation method for amorphous magnesium aluminum-base composite hydrogen storage material, comprises the following steps:
A), under inert atmosphere conditions, Mg powder and Al powder raw material are pressed to Mg17Al12Proportioning evenly mixedClose, prepare amorphous state Mg through ball milling17Al12Matrix powder;
B) by prepared amorphous state Mg17Al12Matrix powder and transition metal hydride powder are in inertiaUnder the protection of gas, carry out mechanical ball milling, after ball milling, obtain amorphous magnesium aluminum-base composite hydrogen storage material.
Step a) in, the condition of described ball milling is: ball milling temperature is lower than 1 DEG C, and Ball-milling Time is littleIn 50h. Further preferably, the condition of described ball milling is: ball milling temperature-10 DEG C～1 DEG C, Ball-milling Time10～50h. Described inert atmosphere is argon gas. Further preferred, the condition of described ball milling is: ballMill temperature-5 DEG C～1 DEG C, Ball-milling Time 30～50h.
Described Mg powder and the particle diameter of Al powder are 50～200 μ m, further preferred, described MgThe particle diameter of powder and Al powder is 74～154 μ m.
Step b) in, the condition of mechanical ball milling is: Ball-milling Time 2～30h, ratio of grinding media to material is 20～40:1,Rotational speed of ball-mill is 200～450rpm. Machinery ball milling carries out at ambient temperature, at 10～35 DEG C, describedInert gas is argon gas. The pressure of the inert gas of milling protection is 0.2～2.5MPa.
Above-mentioned prepared amorphous magnesium aluminum-base composite hydrogen storage material powder takes out and carries out under anaerobic anhydrous conditionDependency structure and performance test.
This composite hydrogen storage material has excellent middle low temperature hydrogen storage property. Can in 30min at 200 DEG CInhale fast the capacity of putting hydrogen and reach 4.0wt.%.
Compared with prior art, beneficial effect of the present invention is:
(1) the prepared amorphous magnesium aluminum-base composite storage hydrogen material of the present invention's (lower than 1 DEG C) under cryogenic conditionsMaterial powder craft is relatively easy. Than the mechanical milling process in other cryogenic media (as liquid nitrogen, liquid argon),Medium (brine ice) that the present invention utilizes is cheap and be easy to obtain, and can effectively save this type of amorphousThe preparation cost of magnesium-aluminum-based composite hydrogen storage material.
(2) in the present invention, utilize the prepared brilliant magnesium-aluminum-based composite hydrogen storage material of low temperature ball grinding method to compareThere is significant advantage in traditional room-temperature ball-milling method: this method can be at the particle of very big refinement hydrogen storage materialWhen/crystallite dimension, effectively avoid because extreme low temperature condition causes lacking that the diffusivity of material dies downPoint, thus this amorphous magnesium aluminum-base composite hydrogen storage material preparation efficiency greatly improved. And prepared materialHave good activity function, circulation first can reach excellent suction and put hydrogen characteristic, and particularly this is compoundHydrogen discharging performance under the middle low temperature (≤200 DEG C) of material is obviously better than traditional magnesium-base hydrogen storage material MgH2。
(3) TiH that the present invention adds2、ZrH2With ScH2Transition metal hydride fine catalyst withThe form disperse of nanocrystalline structure is distributed in a-Mg17Al12Around non-crystaline amorphous metal, these catalyst not only canBecome the activated centre that hydrogen decomposes, can be used as " hydrogen pump " simultaneously and allow the base of H atom at Mg-Al alloyBody surface is bright carries out rapid diffusion, thereby has effectively accelerated the storage hydrogen process of Mg. In addition the transition of interpolation,Metal hydride powder is carried out ball milling while preparing, and the crystallite dimension of composite hydrogen storage material can further attenuate,Increase the degree of disorder, also produced more interface and defect, be more conducive to reduce H atom diffusion institute simultaneouslyThe activation energy needing, and further improve the hydrogen storage property of composite.
(4) because raw material Al is than more aboundresources and cheap of Ni, exploitation Mg-Al alloyLarger competitive advantage and application prospect will be there is as hydrogen storage material than Mg-Ni alloy.
Brief description of the drawings
Fig. 1 is the a-Mg of preparation17Al12Amorphous alloy and a-Mg17Al12+10wt.％TiH2AmorphousThe XRD collection of illustrative plates of magnesium-aluminum-based composite hydrogen storage material, in Fig. 1, (a) is prepared a-Mg17Al12Amorphous stateThe XRD curve of alloy, in Fig. 1, (b) is prepared a-Mg17Al12+10wt.％TiH2Amorphous magnesiumThe XRD curve of aluminum-base composite hydrogen storage material, in Fig. 1, (c) is prepared a-Mg17Al12Amorphous state is closedThe TEM picture of gold;
Fig. 2 is the a-Mg of preparation17Al12+8wt.％TiH2The SEM of amorphous magnesium aluminum-base composite hydrogen storage materialThe EDS face scanning spectral distribution figure of pattern and each element, wherein, in Fig. 2, (d) is a-Mg17Al12+8wt.％TiH2The SEM pattern of amorphous magnesium aluminum-base composite hydrogen storage material, in Fig. 2, (e) is Mg elementEDS face scanning spectral distribution figure, in Fig. 2, (f) be that the EDS face of Al element scans spectral distributionFigure, in Fig. 2, (g) is the EDS face scanning spectral distribution figure of Ti element;
Fig. 3 is amorphous a-Mg17Al12Alloy and prepared a-Mg17Al12+xwt.％TiH2(x＝5,10)The suction hydrogen curve of composite hydrogen storage material under 200 DEG C, 6.0MPa hydrogen pressure;
Fig. 4 is the a-Mg of preparation17Al12+5wt.％MH2(M=Ti, Zr, Sc) Mg-based composite hydrogen storage materialHydrogen desorption isotherms under 200 DEG C, 0.1MPa hydrogen pressure.
Detailed description of the invention
The percentage that following examples relate to, in case of no particular description, is mass percent.
Embodiment 1
According to Mg17Al12The composition proportion of alloy, raw material choose Mg and Al powder diameter are 74～154μ m, purity is 99%, under inert atmosphere (argon gas) condition, first Mg powder and Al powder is pressedMg17Al12Proportioning evenly mix and be placed in and utilize brine ice to carry out the double-deck ball milling of the ball mill of temperature controlTank, at 0 DEG C, ball milling 50h is to prepare amorphous state Mg17Al12Matrix powder material. Subsequently, selectTransition metal hydride is TiH2Powder, purity is 99%, by prepared amorphous state Mg17Al12BaseBody powder with account for described Mg17Al12The TiH of matrix total amount 10wt.%2Powder is mechanical ball at 25 DEG C of room temperaturesMill 20h, milling protection atmosphere is respectively that purity is 99.99% argon gas, protective atmosphere pressure is 0.2MPa,Ratio of grinding media to material in mechanical milling process is 40:1, and drum's speed of rotation is 450rpm, finally prepares amorphous a-Mg17Al12+10wt.％TiH2Mg-based composite hydrogen storage material.
Fig. 1 is the a-Mg of preparation17Al12Amorphous alloy and a-Mg17Al12+10wt.％TiH2AmorphousThe XRD collection of illustrative plates of magnesium-aluminum-based composite hydrogen storage material. Can be found out by (a) in Fig. 1, through ball milling at 0 DEG CAfter 50h, the crystalline state diffraction maximum of the contained raw material Mg of sample and Al all disappears completely, and its XRD collection of illustrative plates onlyRemaining Mg17Al12Amorphous disperse peak, this disordering degree that shows sample significantly improves, alloy is finalChange amorphous structure completely into. Also can be demonstrate,proved by the amorphous diffraction ring in the TEM illustration in (c) in Fig. 1Real prepared Mg17Al12For amorphous alloy. From Fig. 1, the XRD collection of illustrative plates of (b) can further be found,By amorphous state Mg17Al12With TiH2Carry out after 20h ball-milling amorphous state Mg in composite17Al12Still keep its non crystalline structure; And TiH2Show the XRD diffraction maximum of broadening, according to TiH2Main peakHalfwidth can calculate its crystallite dimension and be about 40nm. That is to say prepared a-Mg17Al12+10wt.％TiH2Mg-based composite hydrogen storage material is by a large amount of amorphous state Mg17Al12With a small amount of crystalline state nanometerTiH2Mix composition. Hot analysis result is found, in above-mentioned Mg-based composite hydrogen storage material, due to nanocrystallineTiH2Be evenly distributed in amorphous Mg17Al12Around matrix material, make under cryogenic conditions prepared non-Brilliant magnesium-aluminum-based composite hydrogen storage material has good heat endurance, and it can keep good non-at 320 DEG CBrilliant characteristic.
Embodiment 2
According to Mg17Al12The composition proportion of alloy, raw material choose Mg and Al powder diameter are 74～154μ m, purity is 99%, under inert atmosphere conditions, first Mg powder and Al powder is pressed to Mg17Al12'sProportioning is evenly mixed and is placed in and utilizes brine ice to carry out the double-deck ball grinder of the ball mill of temperature control, at-1 DEG CLower ball milling 50h is to prepare amorphous state Mg17Al12Matrix powder material. Subsequently, select transition metal hydrogenCompound is TiH2Powder, purity is 99%, by prepared amorphous state Mg17Al12Matrix powder with account for instituteState Mg17Al12The TiH of matrix total amount 8wt.%2Powder is mechanical ball milling 30h at 25 DEG C of room temperatures, other systemStandby process, with embodiment 1, is finally prepared amorphous a-Mg17Al12+8wt.％TiH2Magnesium base composite hydrogen storageMaterial.
For analyzing amorphous a-Mg17Al12With TiH2Combining case, utilize ESEM to carry out sampleThe energy spectrum analysis of EDS face scanning. Fig. 2 is the amorphous a-Mg of preparation17Al12+8wt.％TiH2Magnesium base is multipleClose the SEM pattern of hydrogen storage material and the EDS face of each element scanning spectral distribution figure. As seen from the figure, multipleThe element that closes Mg and Al in hydrogen storage material distributes corresponding consistent with particle SEM pattern, shows materialMatrix composition is Mg-Al alloy; The element of Ti distributes basically identical with particle SEM pattern, shows TiUnit's crude granule can comparatively be evenly distributed on Mg-Al matrix.
Embodiment 3
According to Mg17Al12The composition proportion of alloy, raw material choose Mg and Al powder diameter are 74～154μ m, purity is 99%, under inert atmosphere conditions, first Mg powder and Al powder is pressed to Mg17Al12'sProportioning is evenly mixed and is placed in and utilizes brine ice to carry out the double-deck ball grinder of the ball mill of temperature control, at-5 DEG CLower ball milling 35h is to prepare amorphous state Mg17Al12Matrix powder material. Subsequently, select transition metal hydrogenCompound is TiH2Powder, purity is 99%, by prepared amorphous state Mg17Al12Matrix powder with account for instituteState Mg17Al12The TiH of matrix total amount 10wt.%2Powder is mechanical ball milling 2h at 25 DEG C of room temperatures, ball millingProtective atmosphere is respectively that purity is 99.99% hydrogen, and protective atmosphere pressure is 2.5MPa, mechanical milling processIn ratio of grinding media to material be 20:1, drum's speed of rotation is 200rpm, finally prepares amorphous a-Mg17Al12+10wt.％TiH2Mg-based composite hydrogen storage material.
Embodiment 4
Amorphous state Mg17Al12The preparation process of matrix powder material is with embodiment 3. Subsequently, select transitionMetal hydride is TiH2Powder, purity is 99%, by prepared amorphous state Mg17Al12Matrix powderWith account for described Mg17Al12The TiH of matrix total amount 5wt.%2Powder is mechanical ball milling at 25 DEG C of room temperatures, itsPreparation process, with embodiment 3, is finally prepared amorphous a-Mg17Al12+5wt.％TiH2The compound storage of magnesium baseHydrogen material.
According to embodiment 3 and embodiment 4, further under anaerobic anhydrous condition, the amorphous of gained will be preparedMagnesium-aluminum-based composite hydrogen storage material powder takes out its hydrogen sucking function of test. Fig. 3 is amorphous a-Mg17Al12AlloyWith prepared a-Mg17Al12+xwt.％TiH2(x=5,10) composite hydrogen storage material is at 200 DEG C, 6.0Suction hydrogen curve under MPa hydrogen pressure. Can find out amorphous a-Mg17Al12Alloy is at the hydrogen-sucking amount of 200 DEG CBe only 2.84wt.%; And interpolation TiH2After composite modified, amorphous a-Mg17Al12+xwt.％TiH2MagnesiumThe suction hydrogen speed of base composite hydrogen storage material and hydrogen-sucking amount are all than independent a-Mg17Al12Non-crystaline amorphous metal is obviously carriedHigh. At amorphous a-Mg17Al12+xwt.％TiH2In Mg-based composite hydrogen storage material, hydrogen-sucking amount when x=5For 4.22wt.%, and be 4.06wt.% when x=10. Research is also found, adds TiH2Rear composite hydrogen occludingMaterial has good activity function, can reach its maximum hydrogen-sucking amount in the time inhaling hydrogen for the first time.
Embodiment 5
Amorphous state Mg17Al12The preparation process of matrix powder material is with embodiment 3. Subsequently, select respectivelyTransition metal hydride is ZrH2And ScH2Powder, purity is 99%, by prepared amorphous stateMg17Al12Matrix powder with account for described Mg17Al12The MH of matrix total amount 5wt.%2(M=Zr, Sc) powderEnd is lower mechanical ball milling at 25 DEG C of room temperatures, and its preparation process, with embodiment 4, is finally prepared amorphousa-Mg17Al12The MH of+5wt.%2(M=Zr, Sc) Mg-based composite hydrogen storage material.
According to embodiment 4 and embodiment 5, further under anaerobic anhydrous condition, the amorphous of gained will be preparedMagnesium-aluminum-based composite hydrogen storage material powder takes out its hydrogen discharging performance of test. Fig. 4 is amorphous a-Mg17Al12AlloyWith prepared a-Mg17Al12+5wt.％MH2(M=Ti, Zr, Sc) Mg-based composite hydrogen storage material existsHydrogen desorption isotherms under 200 DEG C, 0.1MPa hydrogen pressure. As seen from the figure, add ZrH2And ScH2Ball-millingThe hydrogen discharging performance of rear material and interpolation TiH2The hydrogen discharging performance of ball-milling material is suitable, all can effectively changeThe hydrogen desorption kinetics performance of kind amorphous magnesium aluminum-base composite hydrogen storage material, wherein a-Mg17Al12+5wt.％ScH2Compound hydrogen discharging performance the best, the hydrogen desorption capacity in the time of 200 DEG C in 30min can reach 4.00wt.%.Research also finds, prepared Mg-based composite hydrogen storage material can reach its maximum and puts hydrogen putting for the first time hydrogenAmount, has good activity function.
Claims (10)
1. an amorphous magnesium aluminum-base composite hydrogen storage material, is characterized in that, by mass ratio 100:0.5～10Amorphous state Mg17Al12Matrix and transition metal hydride are made, and described transition metal hydride isTiH2、ZrH2、ScH2In one or more.
2. amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 1, is characterized in that, by matterAmount is than the amorphous state Mg of 100:5～1017Al12Matrix and transition metal hydride are made.
3. a preparation method for amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 1 or 2,It is characterized in that, comprise the following steps:
A), under inert atmosphere conditions, Mg powder and Al powder raw material are pressed to Mg17Al12Proportioning evenly mixedClose, prepare amorphous state Mg through ball milling17Al12Matrix powder;
B) by prepared amorphous state Mg17Al12Matrix powder and transition metal hydride powder are in inertiaUnder the protection of gas, carry out mechanical ball milling, after ball milling, obtain amorphous magnesium aluminum-base composite hydrogen storage material.
4. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step a) in, described Mg powder and the particle diameter of Al powder are 50～200 μ m.
5. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step a) in, the condition of described ball milling is: ball milling temperature is lower than 1 DEG C, and Ball-milling Time is notBe greater than 50h.
6. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 5, its featureBe, step a) in, the condition of described ball milling is: ball milling temperature-10 DEG C～1 DEG C, Ball-milling Time10～50h。
7. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step a) in, described inert atmosphere is argon gas.
8. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step b) in, the condition of mechanical ball milling is: Ball-milling Time 2～30h, ratio of grinding media to material is 20～40:1, rotational speed of ball-mill is 200～450rpm.
9. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step b) in, described inert gas is argon gas.
10. the preparation method of amorphous magnesium aluminum-base composite hydrogen storage material as claimed in claim 3, its featureBe, step b) in, the pressure of inert gas is 0.2～2.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118105.6A CN105584989B (en) | 2016-03-02 | 2016-03-02 | A kind of amorphous magnesium aluminum-base composite hydrogen storage material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118105.6A CN105584989B (en) | 2016-03-02 | 2016-03-02 | A kind of amorphous magnesium aluminum-base composite hydrogen storage material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105584989A true CN105584989A (en) | 2016-05-18 |
| CN105584989B CN105584989B (en) | 2018-01-02 |
Family
ID=55924940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610118105.6A Expired - Fee Related CN105584989B (en) | 2016-03-02 | 2016-03-02 | A kind of amorphous magnesium aluminum-base composite hydrogen storage material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105584989B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782968A (en) * | 2017-01-13 | 2017-05-31 | 西安理工大学 | A kind of La (Fe, Si)13HxThe preparation method of hydride magnetic refrigerating material |
| CN108439330A (en) * | 2018-04-20 | 2018-08-24 | 常州达奥新材料科技有限公司 | A kind of preparation method of compound magnalium based hydrogen storage material |
| CN108796326A (en) * | 2018-06-29 | 2018-11-13 | 南通志乐新材料有限公司 | A kind of MgAl based hydrogen storage materials of catalyst enhancing |
| CN109550963A (en) * | 2018-12-13 | 2019-04-02 | 华南理工大学 | A kind of sub-micron hydride particle enhancing aluminium base raw powder's production technology for 3D printing |
| CN110270683A (en) * | 2018-03-16 | 2019-09-24 | 武汉理工大学 | A kind of Fe/ZrH2Nanocomposite particle and its preparation method and application |
| CN110405219A (en) * | 2019-07-29 | 2019-11-05 | 四川大学 | The preparation method and high power hydrogen-bearing alloy powder of high power hydrogen-bearing alloy powder |
| CN111533086A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院长春应用化学研究所 | Short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound |
| CN114348958A (en) * | 2022-01-27 | 2022-04-15 | 徐州工程学院 | Amorphous trace lanthanum composite layered magnesium composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
-
2016
- 2016-03-02 CN CN201610118105.6A patent/CN105584989B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XUEZHANG XIAO等: "Microstructures and electrochemical hydrogen storage properties of novel Mg-Al-Ni amorphous composites", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782968A (en) * | 2017-01-13 | 2017-05-31 | 西安理工大学 | A kind of La (Fe, Si)13HxThe preparation method of hydride magnetic refrigerating material |
| CN110270683A (en) * | 2018-03-16 | 2019-09-24 | 武汉理工大学 | A kind of Fe/ZrH2Nanocomposite particle and its preparation method and application |
| CN108439330A (en) * | 2018-04-20 | 2018-08-24 | 常州达奥新材料科技有限公司 | A kind of preparation method of compound magnalium based hydrogen storage material |
| CN108796326A (en) * | 2018-06-29 | 2018-11-13 | 南通志乐新材料有限公司 | A kind of MgAl based hydrogen storage materials of catalyst enhancing |
| CN108796326B (en) * | 2018-06-29 | 2019-11-15 | 江西增孚新材料科技有限公司 | A kind of MgAl based hydrogen storage material of catalyst enhancing |
| CN109550963A (en) * | 2018-12-13 | 2019-04-02 | 华南理工大学 | A kind of sub-micron hydride particle enhancing aluminium base raw powder's production technology for 3D printing |
| CN110405219A (en) * | 2019-07-29 | 2019-11-05 | 四川大学 | The preparation method and high power hydrogen-bearing alloy powder of high power hydrogen-bearing alloy powder |
| CN111533086A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院长春应用化学研究所 | Short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound |
| CN111533086B (en) * | 2020-05-11 | 2023-12-01 | 中国科学院长春应用化学研究所 | Short-flow preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compound |
| CN114348958A (en) * | 2022-01-27 | 2022-04-15 | 徐州工程学院 | Amorphous trace lanthanum composite layered magnesium composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105584989B (en) | 2018-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105584989A (en) | Amorphous magnesium-aluminum-base composite hydrogen storage material and preparation method thereof | |
| Ouyang et al. | Hydrogen storage in light-metal based systems: a review | |
| CN101837953A (en) | Novel ammonia borane composite material for hydrolysis hydrogen production | |
| Ma et al. | Effects of trimesic acid-Ni based metal organic framework on the hydrogen sorption performances of MgH2 | |
| Song et al. | Recent advances of magnesium hydride as an energy storage material | |
| CN110963461A (en) | Metal oxide and porous material composite hydrogen storage material and preparation method thereof | |
| CN113896167B (en) | Composite hydrogen storage material, preparation method and application thereof | |
| CN105132770A (en) | Mg2Ni-based ternary Mg-Ni-Cu reversible hydrogen storage material and preparation method thereof | |
| Guo et al. | Precipitation of nanocrystalline LaH3 and Mg2Ni and its effect on de-/hydrogenation thermodynamics of Mg-rich alloys | |
| Zhang et al. | Catalytic effect comparison of TiO2 and La2O3 on hydrogen storage thermodynamics and kinetics of the as-milled La-Sm-Mg-Ni-based alloy | |
| Chen et al. | A comparative study on hydrogen storage properties of as-cast and extruded Mg-4.7 Y-4.1 Nd-0.5 Zr alloys | |
| Yin et al. | Enhanced hydrogen storage performance of Mg-Cu-Ni system catalyzed by CeO2 additive | |
| CN106756361B (en) | A kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation method | |
| Wei et al. | Improved hydrogen storage performances of the as-milled Mg-Al-Y alloy by co-doping of Tm@ C (Tm= Fe, Co, Cu) | |
| CN110656272A (en) | Magnesium-based hydrogen storage material based on high entropy effect and preparation method thereof | |
| CN109012664A (en) | A kind of amorphous carbon supported nano-gold metal particles catalyst and its preparation method and application | |
| CN111515380B (en) | High-capacity magnesium-based composite hydrogen storage material and preparation method thereof | |
| CN102502488B (en) | Method for improving hydrogen storage property of lithium borohydride | |
| Xie et al. | High-performance La–Mg–Ni-based alloys prepared with low cost raw materials | |
| CN111515405A (en) | Preparation method of magnesium-based nano composite hydrogen storage material | |
| CN103183314A (en) | Composite hydrogen storage material with foamed structure and preparation method thereof | |
| WO2006005892A1 (en) | Hydrogen storage materials | |
| CN104030246B (en) | A kind of aluminium lithium hydrogen storage material and preparation method thereof | |
| CN108193113B (en) | Preparation method of nano-confinement magnesium-rich alloy | |
| Shao et al. | Nanostructured Mg‐Based Hydrogen Storage Materials: Synthesis and Properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180102 Termination date: 20190302 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |