CN107758611A - A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof - Google Patents
A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof Download PDFInfo
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
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- 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
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Abstract
The present invention relates to a kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof, belong to technical field of function materials.The present invention by magnesium borohydride and ammonia by forming ammino boron hydride, so as to meet the temperature requirement of application, and NH3The positive Hydrogen Energy and BH introduced in group4 ﹣Negative hydrogen in group, which combines, puts hydrogen, so as to change the release put hydrogen path and effectively reduce the foreign gases such as diborane of boron hydride, and change ammonia complexing numeral system into an ammino magnesium borohydride with ammonia redistribution procedure, adjust the number of ortho-hydrogen and the number of negative hydrogen in magnesium borohydride ammonate, the efficiency highest for being allowed to combine from charge balance, the release of ammonia in magnesium borohydride ammonate decomposable process can effectively be suppressed, improve the purity of discharged hydrogen, combined simultaneously with magnesium base alloy, change the crystal structure of alloy hydride and play catalytic action, so as to be advantageous to the diffusion of hydrogen atom, improve alloy hydride and inhale hydrogen desorption kineticses performance.
Description
Technical field
The present invention relates to a kind of magnesium-base nanometer composite hydrogen-storing material and preparation method thereof, belong to technical field of function materials.
Background technology
In numerous new energy, Hydrogen Energy due to aboundresources, high energy density and mass values, it is environment-friendly,
Have good burning performance, the features such as storage form is various, potential high financial profit, be referred to as the ultimate clean energy resource of the mankind, be expected into
For one of new energy mostly important in future world energy stage.The circulation of preferable hydrogen is related to producing, store, transporting for hydrogen
The four processes such as defeated and application.Following critical problem in the exploitation of Hydrogen Energy and application process be present:Hydrogen preparation technique,
The application of hydrogen storaging and transport technology and hydrogen.
Excellent hydrogen bearing alloy should possess following characteristics:(1)There must be good thermodynamic property.Except higher storage
Outside hydrogen capacity and reversible hydrogen-sucking amount, hydrogen bearing alloy should have relatively low dissociation temperature under 1 atmospheric pressure, and inhale hydrogen discharge reaction enthalpy change
Absolute value it is small.(2)Excellent dynamic performance.This is to put hydrogen machine by material self character and the suction under specified temp pressure
What reason determined.(3)Stable recycling.Hydrogen bearing alloy will resist poisoning performance good in hydrogen cyclic process is put in suction, anti-powdering
Performance is good.(4)It is easily-activated.Easily-activated hydrogen storage material can relatively easily destroy the oxide layer on surface.(5)Practicality
It is good.The hydrogen bearing alloy system of research comparative maturity mainly has at present:Rare Earth Lanthanum nickel system, ferrotianium system, titanium zirconium system, vanadium base solid solution,
Mg base hydrogen bearing alloy etc..
Mg base hydrogen bearing alloy is acknowledged as most one of hydrogen storage material of application prospect, but its suction put hydrogen thermodynamics and
Dynamic performance is poor, seriously hinders its application in practice.Most researchers research thinks, the suction of pure magnesium is put hydrogen and moved
The main reason for mechanical property is poor be:(1)H2It is slower in absorption dissociation/molecular recombination desorption rate of magnesium surface;(2)Due to
Magnesium is very active, it is easy to aoxidizes the MgO or Mg (OH) that densification is formed in alloy surface2, hydrogen molecule is hindered in alloy surface
Activation dissociation(Alloy surface can dissociate for hydrogen molecule and provide avtive spot);(3)Hydrogen is in MgH2With the diffusion velocity in Mg
It is slow, especially in MgH2In diffusion be even more difficulty.At a temperature of higher 300 DEG C, H-In MgH2In diffusivity be only
10-18m2/s.If Mg particle sizes are larger, MgH2The surface of Mg particles is completely covered on, hydrogenation rate is slow, and Mg will be hydrogenated not
Completely.Substantial amounts of research work is all to put hydrogen thermodynamic property and dynamics around the suction for how improving Mg base hydrogen bearing alloy at present
Performance and deploy.
The content of the invention
The technical problems to be solved by the invention:For magnesium-base hydrogen storage material hydrogen storage thermodynamics and kinetics poor-performing,
Serious the problem of limiting magnesium-base hydrogen storage material large-scale application, there is provided a kind of magnesium-base nanometer composite hydrogen-storing material and its preparation
Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of magnesium-base nanometer composite hydrogen-storing material, it is characterised in that the hydrogen storage material is by magnesium base alloy and magnesium borohydride ammonia
Compound forms.
The magnesium base alloy is by magnesium, aluminium, lithium, titanium in molar ratio 10:5:1:Ball milling is made after 1 mixing.
The magnesium borohydride ammonate is an ammino magnesium borohydride, be by magnesium borohydride and six ammino magnesium borohydrides by mole
Than 5:1 is made under argon atmosphere with 10 ~ 12h of positive and negative alternate ball-milling method ball milling.
The six amminos magnesium borohydride be by magnesium borohydride under ammonia atmosphere with 10 ~ 12h of positive and negative alternate ball-milling method ball milling
It is made.
The magnesium borohydride is by sodium borohydride and magnesium chloride in molar ratio 2:1 under argon atmosphere 20 ~ 24h of ball milling, then
Filtered to get filtrate after adding 20 ~ 24h of absolute ether wet-milling, go solvent to be made after filtrate is evaporated.
The positive and negative alternate ball-milling method is to suspend 15 ~ 30s reverse direction operations again after often running 60 ~ 120s.
The preparation method of described a kind of magnesium-base nanometer composite hydrogen-storing material, it is characterised in that concretely comprise the following steps:
(1)By sodium borohydride and magnesium chloride in molar ratio 2:1 under argon atmosphere 20 ~ 24h of ball milling, add absolute ether wet-milling
Filtered to get filtrate after 20 ~ 24h, remove solvent after filtrate is evaporated, obtain magnesium borohydride;
(2)By magnesium borohydride under ammonia atmosphere with positive and negative alternate ball-milling method 10 ~ 12h of ball milling, obtain six ammino magnesium borohydrides;
(3)By six ammino magnesium borohydrides and magnesium borohydride in molar ratio 5:1 under argon atmosphere with positive and negative alternate ball-milling method ball milling
10 ~ 12h, obtain an ammino magnesium borohydride;
(4)Magnesium powder, aluminium powder, lithium powder, titanium valve are taken, is fitted into ball mill with 300 ~ 400r/min, 60 ~ 80h of ball milling, adds an ammonia
Magnesium borohydride is closed, with 200 ~ 300r/min positive and negative alternate 20 ~ 30h of ball milling, obtains magnesium-base nanometer composite hydrogen-storing material.
Compared with other method, advantageous effects are the present invention:
The present invention by the way that magnesium borohydride and ammonia are formed into ammino boron hydride, can on the premise of the high hydrogen capacity of system is kept,
The boron hydride of activation stable reduces hydrogen discharging temperature or surely changes active boron hydride to improve hydrogen discharging temperature, so as to meet
The temperature requirement of application, and NH3The positive Hydrogen Energy and BH introduced in group4 ﹣Negative hydrogen in group, which combines, puts hydrogen, so as to change boron
The release put hydrogen path and effectively reduce the foreign gases such as diborane of hydride, and with ammonia redistribution procedure change ammonia complexing numeral system into
One ammino magnesium borohydride, that is, the number of ortho-hydrogen and the number of negative hydrogen in magnesium borohydride ammonate are adjusted, is made from charge balance
Combination efficiency highest, can effectively suppress the release of ammonia in magnesium borohydride ammonate decomposable process, improve discharged hydrogen
The purity of gas, while combined with magnesium base alloy, change the crystal structure of alloy hydride and play catalytic action, so as to be advantageous to
The diffusion of hydrogen atom, improve alloy hydride and inhale hydrogen desorption kineticses performance.
Embodiment
0.2 ~ 0.4mol sodium borohydrides and 0.1 ~ 0.2mol magnesium chlorides is taken to be fitted into ball grinder, under argon atmosphere, with 300
~ 500r/min 20 ~ 24h of ball milling, 300 ~ 500mL absolute ethers are added, continue 20 ~ 24h of ball milling, filter and must filter after ball milling
Liquid, filtrate is placed on Rotary Evaporators, be evaporated to dryness under reduced pressure, then product is placed in vacuum drying chamber, at 150 ~ 250 DEG C
10 ~ 20h is dried, magnesium borohydride is obtained, takes 0.01 ~ 0.02mol magnesium borohydrides to be fitted into ball grinder, with reciprocal cross under ammonia atmosphere
For ball-milling method 10 ~ 12h of ball milling, i.e., suspend 15 ~ 30s reverse direction operations again after often running 60 ~ 120s, six amminos are obtained after ball milling
Magnesium borohydride, the ammino magnesium borohydrides of 0.01 ~ 0.02mol six and 0.05 ~ 0.10mol magnesium borohydrides are taken, is fitted into ball grinder, in argon
Atmosphere enclose under with positive and negative alternate ball-milling method 10 ~ 12h of ball milling, i.e., suspend 15 ~ 30s reverse direction operations again, ball after often running 60 ~ 120s
After mill an ammino magnesium borohydride, take 0.1 ~ 0.2mol magnesium powders, 0.05 ~ 0.10mol aluminium powders, 0.02 ~ 0.04mol lithium powder,
0.02 ~ 0.04mol titanium valves, are fitted into ball mill, with 300 ~ 400r/min, 60 ~ 80h of ball milling, obtain magnesium base alloy, add
The ammino magnesium borohydrides of 0.05mol ~ 0.10mol mono-, with 200 ~ 300r/min positive and negative alternate 20 ~ 30h of ball milling, i.e., often operation 60 ~
Suspend 15 ~ 30s reverse direction operations again after 120s, magnesium-base nanometer composite hydrogen-storing material is obtained after ball milling.
Example 1
0.2mol sodium borohydrides and 0.1mol magnesium chlorides is taken to be fitted into ball grinder, under argon atmosphere, with 300r/min ball millings
20h, 300mL absolute ethers are added, continue ball milling 20h, filtered to get filtrate after ball milling, filtrate is placed in Rotary Evaporators
On, it is evaporated to dryness under reduced pressure, then product is placed in vacuum drying chamber, 10h is dried at 150 DEG C, magnesium borohydride is obtained, takes
0.01mol magnesium borohydrides are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 10h under ammonia atmosphere, i.e., after often running 60s
Suspend 15s reverse direction operations again, after ball milling six ammino magnesium borohydrides, take the ammino magnesium borohydrides of 0.01mol six with
0.05mol magnesium borohydrides, are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 10h under argon atmosphere, i.e., often run 60s
Suspend 15s reverse direction operations again afterwards, after ball milling an ammino magnesium borohydride, take 0.1mol magnesium powders, 0.05mol aluminium powders,
0.02mol lithium powder, 0.02mol titanium valves, is fitted into ball mill, with 300r/min ball milling 60h, obtains magnesium base alloy, adds
The ammino magnesium borohydrides of 0.05moll mono-, with 200r/min positive and negative alternate ball milling 20h, i.e., suspend 15s opposite directions again after often running 60s
Run, magnesium-base nanometer composite hydrogen-storing material is obtained after ball milling.
Example 2
0.3mol sodium borohydrides and 0.1mol magnesium chlorides is taken to be fitted into ball grinder, under argon atmosphere, with 400r/min ball millings
22h, 400mL absolute ethers are added, continue ball milling 22h, filtered to get filtrate after ball milling, filtrate is placed in Rotary Evaporators
On, it is evaporated to dryness under reduced pressure, then product is placed in vacuum drying chamber, 15h is dried at 200 DEG C, magnesium borohydride is obtained, takes
0.01mol magnesium borohydrides are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 11h under ammonia atmosphere, i.e., after often running 90s
Suspend 20s reverse direction operations again, after ball milling six ammino magnesium borohydrides, take the ammino magnesium borohydrides of 0.01mol six with
0.08mol magnesium borohydrides, are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 11h under argon atmosphere, i.e., often run 90s
Suspend 20s reverse direction operations again afterwards, after ball milling an ammino magnesium borohydride, take 0.1mol magnesium powders, 0.08mol aluminium powders,
0.03mol lithium powder, 0.03mol titanium valves, is fitted into ball mill, with 350r/min ball milling 70h, obtains magnesium base alloy, adds
The ammino magnesium borohydrides of 0.08mol mono-, with 250r/min positive and negative alternate ball milling 25h, i.e., suspend 20s opposite directions again after often running 90s
Run, magnesium-base nanometer composite hydrogen-storing material is obtained after ball milling.
Example 3
0.4mol sodium borohydrides and 0.2mol magnesium chlorides is taken to be fitted into ball grinder, under argon atmosphere, with 500r/min ball millings
24h, 500mL absolute ethers are added, continue ball milling 24h, filtered to get filtrate after ball milling, filtrate is placed in Rotary Evaporators
On, it is evaporated to dryness under reduced pressure, then product is placed in vacuum drying chamber, 20h is dried at 250 DEG C, magnesium borohydride is obtained, takes
0.02mol magnesium borohydrides are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 12h under ammonia atmosphere, i.e., often run 120s
Suspend 30s reverse direction operations again afterwards, after ball milling six ammino magnesium borohydrides, take the ammino magnesium borohydrides of 0.02mol six with
0.10mol magnesium borohydrides, are fitted into ball grinder, with positive and negative alternate ball-milling method ball milling 12h under argon atmosphere, i.e., often run 120s
Suspend 30s reverse direction operations again afterwards, after ball milling an ammino magnesium borohydride, take 0.2mol magnesium powders, 0.10mol aluminium powders,
0.04mol lithium powder, 0.04mol titanium valves, is fitted into ball mill, with 400r/min ball milling 80h, obtains magnesium base alloy, adds
The ammino magnesium borohydrides of 0.10mol mono-, with 300r/min positive and negative alternate ball milling 30h, i.e., suspend 30s opposite directions again after often running 120s
Run, magnesium-base nanometer composite hydrogen-storing material is obtained after ball milling.
Reference examples:The hydrogen storage material of Shanghai company production.
The hydrogen storage material of example and reference examples is detected, specific detection is as follows:
It is to weigh the another important indicator of hydrogen bearing alloy to put hydrogen activation energy.Under the conditions of different programming rates, nanometer Mg's after hydrogenation
DSC curve only has one narrower symmetrical endothermic peak, shows that it puts the completion of the step of hydrogen process one, by MgH2→Mg.Programming rate 3
DEG C/min, 5 DEG C/min, 10 DEG C/min DSC curve peak temperature is respectively 332.7 DEG C, 340.8 DEG C, 352.9 DEG C.By heating up
Speed is 3 DEG C/min DSC curve, it is known that nanometer Mg initial hydrogen discharging temperature is 311.1 DEG C after hydrogenation.Study MgH2Particle
Influence of the size to its hydrogen discharging performance, business MgH2Initial hydrogen discharging temperature be higher than 400 DEG C, after ball milling 100h, it is initially put
Hydrogen temperature is reduced to 340 DEG C.The nanometer MgH that the carbon gel prepared by nanometer confinement method loads2Under the same conditions initial is put
358.7 DEG C of hydrogen temperature.The MgH prepared with ball-milling method2And the nanometer MgH of the carbon gel load of nanometer confinement method2Compare, after hydrogenation
Nanometer Mg there is preferable hydrogen discharging performance.
Claims (7)
1. a kind of magnesium-base nanometer composite hydrogen-storing material, it is characterised in that the hydrogen storage material is by magnesium base alloy and magnesium borohydride
Ammonate forms.
A kind of 2. magnesium-base nanometer composite hydrogen-storing material as claimed in claim 1, it is characterised in that the magnesium base alloy be by
Magnesium, aluminium, lithium, titanium in molar ratio 10:5:1:Ball milling is made after 1 mixing.
A kind of 3. magnesium-base nanometer composite hydrogen-storing material as claimed in claim 1, it is characterised in that the magnesium borohydride ammonate
It is by magnesium borohydride and six ammino magnesium borohydrides in molar ratio 5 for an ammino magnesium borohydride:1 under argon atmosphere with reciprocal cross
It is made for 10 ~ 12h of ball-milling method ball milling.
A kind of 4. magnesium-base nanometer composite hydrogen-storing material as claimed in claim 3, it is characterised in that the six amminos magnesium borohydride
It is to be made by magnesium borohydride under ammonia atmosphere with 10 ~ 12h of positive and negative alternate ball-milling method ball milling.
5. a kind of magnesium-base nanometer composite hydrogen-storing material as described in claim 3 or 4, it is characterised in that the magnesium borohydride is
By sodium borohydride and magnesium chloride in molar ratio 2:1 under argon atmosphere 20 ~ 24h of ball milling, add 20 ~ 24h of absolute ether wet-milling
After filter to get filtrate, go solvent to be made after filtrate is evaporated.
A kind of 6. magnesium-base nanometer composite hydrogen-storing material as described in claim 3 or 4, it is characterised in that the positive and negative alternate ball
Mill method is to suspend 15 ~ 30s reverse direction operations again after often running 60 ~ 120s.
7. a kind of preparation method of magnesium-base nanometer composite hydrogen-storing material as described in claim 1 ~ 6 any one, its feature exist
In concretely comprising the following steps:
(1)By sodium borohydride and magnesium chloride in molar ratio 2:1 under argon atmosphere 20 ~ 24h of ball milling, add absolute ether wet-milling
Filtered to get filtrate after 20 ~ 24h, remove solvent after filtrate is evaporated, obtain magnesium borohydride;
(2)By magnesium borohydride under ammonia atmosphere with positive and negative alternate ball-milling method 10 ~ 12h of ball milling, obtain six ammino magnesium borohydrides;
(3)By six ammino magnesium borohydrides and magnesium borohydride in molar ratio 5:1 under argon atmosphere with positive and negative alternate ball-milling method ball milling
10 ~ 12h, obtain an ammino magnesium borohydride;
(4)Magnesium powder, aluminium powder, lithium powder, titanium valve are taken, is fitted into ball mill with 300 ~ 400r/min, 60 ~ 80h of ball milling, adds an ammonia
Magnesium borohydride is closed, with 200 ~ 300r/min positive and negative alternate 20 ~ 30h of ball milling, obtains magnesium-base nanometer composite hydrogen-storing material.
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CN114538379A (en) * | 2022-02-28 | 2022-05-27 | 四川大学 | Metal oxide/magnesium borohydride amide high-conductivity solid electrolyte composite material containing interface defects and preparation method thereof |
CN114538379B (en) * | 2022-02-28 | 2024-01-30 | 四川大学 | High-conductivity solid electrolyte composite material containing interface defect metal oxide/magnesium borohydride amide and preparation method thereof |
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