CN108793069A - A kind of zinc borohydride system hydrogen storage material - Google Patents
A kind of zinc borohydride system hydrogen storage material Download PDFInfo
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- CN108793069A CN108793069A CN201810716909.5A CN201810716909A CN108793069A CN 108793069 A CN108793069 A CN 108793069A CN 201810716909 A CN201810716909 A CN 201810716909A CN 108793069 A CN108793069 A CN 108793069A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—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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- 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
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- 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
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Abstract
The present invention provides a kind of zinc borohydride system hydrogen storage material, zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat treatment is carried out to primary zinc borohydride powder；Ti, Al, Ni and Cu metal powder are provided；Primary zinc borohydride powder after Ti, Al, Ni and Cu metal powder and heat treatment is mixed, the first mixed-powder is obtained；Second ball milling is carried out to the first mixed-powder, obtains the second mixed-powder；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder, obtains the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.The zinc borohydride material hydrogen storage ability prepared using the method for the present invention is strong, and cycle hydrogen storage stability is good, and basic performance can maintain an equal level or due to the prior art with the laboratory level zinc borohydride of the prior art.
Description
Technical field
The present invention relates to novel energy resource material technology field, more particularly to a kind of zinc borohydride system hydrogen storage material.
Background technology
Solid-state material hydrogen storage is that a kind of reacted using hydrogen-absorbing material and hydrogen generates the hydrogen storage of solid solution and hydride
Technology.This method hydrogen is generally stored in the form of atom or ion in material, and taking off again for hydrogen releases needs by diffusion, phase
It in the stages such as change and chemical combination, is during which mainly influenced by fuel factor and speed.It is stored up with traditional high-pressure cylinder hydrogen storage and low-temperature liquefaction
Hydrogen is compared, and the distinguishing feature that solid-state material hydrogen storage has safety good, of low cost and high hydrogen-storage density is especially suitable for space
The stringenter occasion of volume requirement, such as the application on on-vehicle fuel.Therefore solid-state material hydrogen storage is carried out in countries in the world
A large amount of research, has obtained rapid development in recent years.Currently, solid-state hydrogen storage technology mainly include hydride hydrogen-storing,
Novel carbon-based material hydrogen storage, metal organic framework object hydrogen storage, metal nitrogen hydrogen-based material hydrogen storage and complex metal hydride hydrogen storage etc..Metal
The mechanism of hydride hydrogen storage is that hydrogen atom enters in the tetrahedron or octahedral interstice of metal lattice and forms metal hydride.The storage
Hydrogen material can release hydrogen when being heated to certain temperature again, using this characteristic to realize the storage of hydrogen.Tradition
Hydride hydrogen-storing material can be divided into lanthanon hydrogen storage alloy, titanium base hydrogen storage alloy, magnesium microalloying, zirconium system hydrogen storage
Alloy and vanadium base solid solution type hydrogen storage alloy.Representational metal hydride has LaNi5, TiFe hydrogen bearing alloy.Although metal
Hydride has many advantages, such as higher volume hydrogen-storage density and safety, but its effective mass hydrogen-storage density is less than 3wt% mostly,
It cannot be satisfied requirement of the on-vehicle fuel to its hydrogen-feeding system quality hydrogen-storage density.In addition, metal hydride is in hydrogen release
Heat is absorbed from the external world, lead to hydrogen storage high expensive.
Being disclosed in the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without answering
It has been the prior art well known to persons skilled in the art when being considered as recognizing or imply that the information is constituted in any form.
Invention content
The purpose of the present invention is to provide a kind of zinc borohydride system hydrogen storage material, the shortcomings that overcome the prior art.
To achieve the above object, the present invention provides a kind of zinc borohydride system hydrogen storage materials, it is characterised in that：Zinc borohydride
It is that hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4And ZnCl2Raw material powder into
The first ball milling of row obtains primary zinc borohydride powder；First heat treatment is carried out to primary zinc borohydride powder；Ti, Al, Ni are provided
And Cu metal powders；Primary zinc borohydride powder after Ti, Al, Ni and Cu metal powder and heat treatment is mixed,
Obtain the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed-powder；To the second mixed-powder into
Row second is heat-treated, and obtains third mixed-powder；Third ball milling is carried out to third mixed-powder, obtains the 4th mixed-powder；It is right
4th mixed-powder carries out third heat treatment.
Preferably, in above-mentioned technical proposal, to NaBH4And ZnCl2Raw material powder carries out the first ball milling：Ratio of grinding media to material
It is 5:1-7:1, milling atmosphere is argon gas atmosphere, ball milling speed 500-600r/min, Ball-milling Time 150-180min, in ball
Per ball milling 10-15min during mill, suspend ball milling 2-4min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Preferably, in above-mentioned technical proposal, carrying out the first heat treatment to primary zinc borohydride powder is specially：It is heat-treated gas
Atmosphere is hydrogen atmosphere, and heat treatment temperature is 200-250 DEG C, heat treatment time 5-10min, and heating rate is 30-40 DEG C/min.
Preferably, in above-mentioned technical proposal, in the first mixed-powder, in parts by weight, the primary boron after being heat-treated
Hydrogenation zinc powder accounts for 100-120 parts, Ti metal powders account for 3-5 parts, Al metal powders account for 2-4 parts, Ni metal powders account for 1-3 parts
And Cu metal powders account for 8-10 parts.
Preferably, in above-mentioned technical proposal, carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 8:1-
10:1, milling atmosphere is argon gas atmosphere, ball milling speed 700-800r/min, Ball-milling Time 80-100min, in ball milling mistake
Per ball milling 10-15min in journey, suspend ball milling 2-4min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Preferably, in above-mentioned technical proposal, carrying out the second heat treatment to the second mixed-powder is specially：Heat-treating atmosphere is
Hydrogen atmosphere, heat treatment temperature are 180-220 DEG C, heat treatment time 4-8min, and heating rate is 30-40 DEG C/min.
Preferably, in above-mentioned technical proposal, carrying out third ball milling to third mixed-powder is specially：Ratio of grinding media to material is 10:1-
12:1, milling atmosphere is argon gas atmosphere, ball milling speed 850-1000r/min, Ball-milling Time 100-150min, in ball milling mistake
Per ball milling 5-10min in journey, suspend ball milling 2-4min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Preferably, in above-mentioned technical proposal, carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is
Hydrogen atmosphere, heat treatment temperature are 160-200 DEG C, heat treatment time 4-8min, and heating rate is 30-40 DEG C/min.
Compared with prior art, the present invention has the advantages that：Zinc borohydride belongs to a kind of complex hydrides hydrogen storage
Material.Coordinate hydride hydrogen-storing material has been carried out more research in the prior art, also discloses that a variety of coordination hydrogenations
The ingredient and preparation method thereof of object hydrogen storage material.But these prior arts generally existing person some defects：First, existing at present
The method for preparing coordinate hydride hydrogen-storing material of Technology design belongs to preparation method and technique in laboratory, this kind of preparation
Method and technique are generally needed strictly to control technological reaction condition, reaction speed while also be proposed to operating personnel very high
It is required that and this kind of laboratory process be not required for yield rate.This preparation method is in practice for industrial production and does not have
Actual directive significance.How to realize that industrialized coordinate hydride hydrogen-storing material production has become the difficulty of the prior art
Topic.The present invention is directed to problem of the prior art, it is proposed that a kind of complex hydrides hydrogen storage material that can be suitable for industrialized production
Preparation method for material, although the present processes processing step is more, operation requirement of the present invention for these processing steps
It is not high with numerical value deviation requirement, such as during heating, temperature overshoot is inevitable problem, the application is super for temperature
The degrees of tolerance of tune can reach 50-80 DEG C.This greatly reduces temperature control difficulty, and realizes and can be rapidly heated, instead
And the production time is saved.Meanwhile it is strong using zinc borohydride material hydrogen storage ability prepared by the method for the present invention, cycle hydrogen storage is steady
Qualitative good, basic performance can maintain an equal level or due to the prior art with the laboratory level zinc borohydride of the prior art.
Specific implementation mode
The illustrative embodiments of the disclosure are described in more detail below.Specific implementation mode only discloses exemplary reality
Apply mode, it should be understood that may be realized in various forms the disclosure without should be limited by embodiments set forth herein.Phase
Instead, it provides these embodiments to be to be able to be best understood from the disclosure, and can be complete by the scope of the present disclosure
It is communicated to those skilled in the art.
Embodiment 1
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 5:1, milling atmosphere is argon gas atmosphere, ball milling speed 500r/min, Ball-milling Time 150min,
Per ball milling 10min in mechanical milling process, suspend ball milling 2min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 200
DEG C, heat treatment time 5min, heating rate is 30 DEG C/min.In the first mixed-powder, in parts by weight, after heat treatment
Primary zinc borohydride powder account for 100 parts, Ti metal powders account for 3 parts, Al metal powders account for 2 parts, Ni metal powders account for 1 part with
And Cu metal powders account for 8 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 8:1, milling atmosphere is argon gas
Atmosphere, ball milling speed 700r/min, Ball-milling Time 80min suspend ball milling 2min per ball milling 10min in mechanical milling process,
The temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.Carrying out the second heat treatment to the second mixed-powder is specially：At heat
Qi-regulating atmosphere is hydrogen atmosphere, and heat treatment temperature is 180 DEG C, heat treatment time 4min, and heating rate is 30 DEG C/min.To
Three mixed-powders carry out third ball milling：Ratio of grinding media to material is 10:1, milling atmosphere is argon gas atmosphere, ball milling speed 850r/
Min, Ball-milling Time 100min suspend ball milling 2min, ball grinder are controlled in mechanical milling process per ball milling 5min in mechanical milling process
In temperature be less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat
Treatment temperature is 160 DEG C, heat treatment time 4min, and heating rate is 30 DEG C/min.
Embodiment 2
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 7:1, milling atmosphere is argon gas atmosphere, ball milling speed 600r/min, Ball-milling Time 180min,
Per ball milling 15min in mechanical milling process, suspend ball milling 4min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 250
DEG C, heat treatment time 10min, heating rate is 40 DEG C/min.In the first mixed-powder, in parts by weight, it is heat-treated it
Primary zinc borohydride powder afterwards accounts for 120 parts, Ti metal powders account for 5 parts, Al metal powders account for 4 parts, Ni metal powders account for 3 parts
And Cu metal powders account for 10 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 10:1, milling atmosphere is
Argon gas atmosphere, ball milling speed 800r/min, Ball-milling Time 100min suspend ball milling per ball milling 15min in mechanical milling process
4min, the temperature in mechanical milling process in control ball grinder are less than 200 DEG C.It is specific that second heat treatment is carried out to the second mixed-powder
For：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 220 DEG C, heat treatment time 8min, heating rate is 40 DEG C/
min.Carrying out third ball milling to third mixed-powder is specially：Ratio of grinding media to material is 12:1, milling atmosphere is argon gas atmosphere, ball milling speed
For 1000r/min, Ball-milling Time 150min, per ball milling 10min in mechanical milling process, suspend ball milling 4min, in mechanical milling process
The temperature controlled in ball grinder is less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen
Gas atmosphere, heat treatment temperature are 200 DEG C, heat treatment time 8min, and heating rate is 40 DEG C/min.
Embodiment 3
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 6:1, milling atmosphere is argon gas atmosphere, ball milling speed 550r/min, Ball-milling Time 160min,
Per ball milling 12min in mechanical milling process, suspend ball milling 3min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 220
DEG C, heat treatment time 8min, heating rate is 35 DEG C/min.In the first mixed-powder, in parts by weight, after heat treatment
Primary zinc borohydride powder account for 110 parts, Ti metal powders account for 4 parts, Al metal powders account for 3 parts, Ni metal powders account for 2 parts with
And Cu metal powders account for 9 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 9:1, milling atmosphere is argon gas
Atmosphere, ball milling speed 750r/min, Ball-milling Time 90min suspend ball milling 3min per ball milling 12min in mechanical milling process,
The temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.Carrying out the second heat treatment to the second mixed-powder is specially：At heat
Qi-regulating atmosphere is hydrogen atmosphere, and heat treatment temperature is 200 DEG C, heat treatment time 6min, and heating rate is 35 DEG C/min.To
Three mixed-powders carry out third ball milling：Ratio of grinding media to material is 11:1, milling atmosphere is argon gas atmosphere, ball milling speed 900r/
Min, Ball-milling Time 120min suspend ball milling 3min, ball grinder are controlled in mechanical milling process per ball milling 8min in mechanical milling process
In temperature be less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat
Treatment temperature is 180 DEG C, heat treatment time 6min, and heating rate is 3 DEG C/min.
Embodiment 4
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 8:1, milling atmosphere is argon gas atmosphere, ball milling speed 800r/min, Ball-milling Time 210min,
Per ball milling 20min in mechanical milling process, suspends ball milling 5min, do not control the temperature in ball grinder.To primary zinc borohydride powder
Carrying out the first heat treatment is specially：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 220 DEG C, heat treatment time 8min,
Heating rate is 35 DEG C/min.In the first mixed-powder, in parts by weight, the primary zinc borohydride powder after being heat-treated accounts for
110 parts, Ti metal powders account for 4 parts, Al metal powders account for 3 parts, Ni metal powders account for 2 parts and Cu metal powders account for 9 parts.It is right
First mixed-powder carries out the second ball milling：Ratio of grinding media to material is 9:1, milling atmosphere is argon gas atmosphere, and ball milling speed is
750r/min, Ball-milling Time 90min suspend ball milling 3min, are controlled in mechanical milling process per ball milling 12min in mechanical milling process
Temperature in ball grinder is less than 200 DEG C.Carrying out the second heat treatment to the second mixed-powder is specially：Heat-treating atmosphere is hydrogen gas
Atmosphere, heat treatment temperature are 200 DEG C, heat treatment time 6min, and heating rate is 35 DEG C/min.The is carried out to third mixed-powder
Three ball millings are specially：Ratio of grinding media to material is 11:1, milling atmosphere is argon gas atmosphere, ball milling speed 900r/min, and Ball-milling Time is
120min suspends ball milling 3min per ball milling 8min in mechanical milling process, and the temperature controlled in ball grinder in mechanical milling process is less than
200℃.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 180
DEG C, heat treatment time 6min, heating rate is 3 DEG C/min.
Embodiment 5
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 6:1, milling atmosphere is argon gas atmosphere, ball milling speed 550r/min, Ball-milling Time 160min,
Per ball milling 12min in mechanical milling process, suspend ball milling 3min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 300
DEG C, heat treatment time 20min, heating rate is 50 DEG C/min.In the first mixed-powder, in parts by weight, it is heat-treated it
Primary zinc borohydride powder afterwards accounts for 150 parts, Ti metal powders account for 2 parts, Al metal powders account for 1 part, Ni metal powders account for 0 part
And Cu metal powders account for 5 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 9:1, milling atmosphere is argon
Gas atmosphere, ball milling speed 750r/min, Ball-milling Time 90min suspend ball milling per ball milling 12min in mechanical milling process
3min, the temperature in mechanical milling process in control ball grinder are less than 200 DEG C.It is specific that second heat treatment is carried out to the second mixed-powder
For：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 200 DEG C, heat treatment time 6min, heating rate is 35 DEG C/
min.Carrying out third ball milling to third mixed-powder is specially：Ratio of grinding media to material is 11:1, milling atmosphere is argon gas atmosphere, ball milling speed
Suspend ball milling 3min per ball milling 8min in mechanical milling process for 900r/min, Ball-milling Time 120min, controlled in mechanical milling process
Temperature in ball grinder processed is less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen
Atmosphere, heat treatment temperature are 180 DEG C, heat treatment time 6min, and heating rate is 3 DEG C/min.
Embodiment 6
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 6:1, milling atmosphere is argon gas atmosphere, ball milling speed 550r/min, Ball-milling Time 160min,
Per ball milling 12min in mechanical milling process, suspend ball milling 3min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 220
DEG C, heat treatment time 8min, heating rate is 35 DEG C/min.In the first mixed-powder, in parts by weight, after heat treatment
Primary zinc borohydride powder account for 110 parts, Ti metal powders account for 4 parts, Al metal powders account for 3 parts, Ni metal powders account for 2 parts with
And Cu metal powders account for 9 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 15:1, milling atmosphere is argon
Gas atmosphere, ball milling speed 1000r/min, Ball-milling Time 120min suspend ball milling per ball milling 20min in mechanical milling process
8min, the temperature in mechanical milling process in control ball grinder are less than 200 DEG C.It is specific that second heat treatment is carried out to the second mixed-powder
For：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 250 DEG C, heat treatment time 10min, heating rate is 50 DEG C/
min.Carrying out third ball milling to third mixed-powder is specially：Ratio of grinding media to material is 11:1, milling atmosphere is argon gas atmosphere, ball milling speed
Suspend ball milling 3min per ball milling 8min in mechanical milling process for 900r/min, Ball-milling Time 120min, controlled in mechanical milling process
Temperature in ball grinder processed is less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen
Atmosphere, heat treatment temperature are 180 DEG C, heat treatment time 6min, and heating rate is 3 DEG C/min.
Embodiment 7
Zinc borohydride system hydrogen storage material is prepared by the following method：NaBH is provided4And ZnCl2Raw material powder；To NaBH4
And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；First heat is carried out to primary zinc borohydride powder
Processing；Ti, Al, Ni and Cu metal powder are provided；By the primary after Ti, Al, Ni and Cu metal powder and heat treatment
Zinc borohydride powder mixes, and obtains the first mixed-powder；Second ball milling is carried out to the first mixed-powder, obtains the second mixed powder
End；Second heat treatment is carried out to the second mixed-powder, obtains third mixed-powder；Third ball milling is carried out to third mixed-powder,
Obtain the 4th mixed-powder；Third heat treatment is carried out to the 4th mixed-powder.To NaBH4And ZnCl2Raw material powder carries out the first ball
Mill is specially：Ratio of grinding media to material is 6:1, milling atmosphere is argon gas atmosphere, ball milling speed 550r/min, Ball-milling Time 160min,
Per ball milling 12min in mechanical milling process, suspend ball milling 3min, the temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.
Carrying out the first heat treatment to primary zinc borohydride powder is specially：Heat-treating atmosphere is hydrogen atmosphere, heat treatment temperature 220
DEG C, heat treatment time 8min, heating rate is 35 DEG C/min.In the first mixed-powder, in parts by weight, after heat treatment
Primary zinc borohydride powder account for 110 parts, Ti metal powders account for 4 parts, Al metal powders account for 3 parts, Ni metal powders account for 2 parts with
And Cu metal powders account for 9 parts.Carrying out the second ball milling to the first mixed-powder is specially：Ratio of grinding media to material is 9:1, milling atmosphere is argon gas
Atmosphere, ball milling speed 750r/min, Ball-milling Time 90min suspend ball milling 3min per ball milling 12min in mechanical milling process,
The temperature controlled in mechanical milling process in ball grinder is less than 200 DEG C.Carrying out the second heat treatment to the second mixed-powder is specially：At heat
Qi-regulating atmosphere is hydrogen atmosphere, and heat treatment temperature is 200 DEG C, heat treatment time 6min, and heating rate is 35 DEG C/min.To
Three mixed-powders carry out third ball milling：Ratio of grinding media to material is 15:1, milling atmosphere is argon gas atmosphere, ball milling speed 1500r/
Min, Ball-milling Time 200min suspend ball milling 8min, ball milling are controlled in mechanical milling process per ball milling 20min in mechanical milling process
Temperature in tank is less than 200 DEG C.Carrying out third heat treatment to the 4th mixed-powder is specially：Heat-treating atmosphere is hydrogen atmosphere,
Heat treatment temperature is 150 DEG C, heat treatment time 10min, and heating rate is 20 DEG C/min.
After inhale the test of hydrogen mass percent and at room temperature 100 cycles (100 times suction hydrogen release) to embodiment 1-7
The test of hydrogen mass percent is inhaled, test mode is mode well known in the art, and test result is normalized based on embodiment 1,
Test result is listed in table 1.
Table 1
The description of the aforementioned specific exemplary embodiment to the present invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining the specific principle of the present invention and its actually answering
With so that those skilled in the art can realize and utilize the present invention a variety of different exemplary implementation schemes and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (8)
1. a kind of zinc borohydride system hydrogen storage material, it is characterised in that：Zinc borohydride system hydrogen storage material is to make by the following method
Standby：
NaBH is provided4And ZnCl2Raw material powder；
To the NaBH4And ZnCl2Raw material powder carries out the first ball milling, obtains primary zinc borohydride powder；
First heat treatment is carried out to the primary zinc borohydride powder；
Ti, Al, Ni and Cu metal powder are provided；
Primary zinc borohydride powder after Ti, Al, Ni and Cu metal powder and heat treatment is mixed, obtains first
Mixed-powder；
Second ball milling is carried out to first mixed-powder, obtains the second mixed-powder；
Second heat treatment is carried out to second mixed-powder, obtains third mixed-powder；
Third ball milling is carried out to the third mixed-powder, obtains the 4th mixed-powder；
Third heat treatment is carried out to the 4th mixed-powder.
2. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：To the NaBH4And ZnCl2Raw material powder
End carries out the first ball milling：Ratio of grinding media to material is 5:1-7:1, milling atmosphere is argon gas atmosphere, ball milling speed 500-600r/
Min, Ball-milling Time 150-180min suspend ball milling 2-4min per ball milling 10-15min in mechanical milling process, in mechanical milling process
The temperature controlled in ball grinder is less than 200 DEG C.
3. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：To the primary zinc borohydride powder into
Row first is heat-treated：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 200-250 DEG C, heat treatment time 5-
10min, heating rate are 30-40 DEG C/min.
4. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：In first mixed-powder, with
Parts by weight meter, the primary zinc borohydride powder after the heat treatment account for 100-120 parts, and Ti metal powders account for 3-5 parts, Al metals
Powder accounts for 2-4 parts, Ni metal powders account for 1-3 parts and Cu metal powders account for 8-10 parts.
5. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：The is carried out to first mixed-powder
Two ball millings are specially：Ratio of grinding media to material is 8:1-10:1, milling atmosphere is argon gas atmosphere, ball milling speed 700-800r/min, ball milling
Time is 80-100min, per ball milling 10-15min in mechanical milling process, suspends ball milling 2-4min, ball milling is controlled in mechanical milling process
Temperature in tank is less than 200 DEG C.
6. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：The is carried out to second mixed-powder
Two heat treatment be specially：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 180-220 DEG C, heat treatment time 4-8min,
Heating rate is 30-40 DEG C/min.
7. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：The is carried out to the third mixed-powder
Three ball millings are specially：Ratio of grinding media to material is 10:1-12:1, milling atmosphere is argon gas atmosphere, ball milling speed 850-1000r/min, ball
Time consuming is 100-150min, every ball milling 5-10min in mechanical milling process, pause ball milling 2-4min, control ball in mechanical milling process
Temperature in grinding jar is less than 200 DEG C.
8. zinc borohydride system as described in claim 1 hydrogen storage material, it is characterised in that：The is carried out to the 4th mixed-powder
Three heat treatment be specially：Heat-treating atmosphere is hydrogen atmosphere, and heat treatment temperature is 160-200 DEG C, heat treatment time 4-8min,
Heating rate is 30-40 DEG C/min.
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| PCT/CN2018/102075 WO2020006839A1 (en) | 2018-07-03 | 2018-08-24 | Zinc borohydride hydrogen storage material |
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|---|---|---|---|---|
| US20070140944A1 (en) * | 2005-12-19 | 2007-06-21 | Soloveichik Grigorii L | Method for manufacturing magnesium borohydride |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
| CN101811669A (en) * | 2010-04-22 | 2010-08-25 | 复旦大学 | High-capacity hydrogen storage material Zn(BH4)2.2NH3 and preparation method thereof |
| CN102205946A (en) * | 2011-05-03 | 2011-10-05 | 浙江大学 | Liquid phase synthesis method of non-alkali-metal type metal hydroboron |
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| CN1958823A (en) * | 2006-11-17 | 2007-05-09 | 中国科学院上海微系统与信息技术研究所 | Magnesium based alloy of storing up hydrogen with Li based hydride being added |
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|---|---|---|---|---|
| US20070140944A1 (en) * | 2005-12-19 | 2007-06-21 | Soloveichik Grigorii L | Method for manufacturing magnesium borohydride |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
| CN101811669A (en) * | 2010-04-22 | 2010-08-25 | 复旦大学 | High-capacity hydrogen storage material Zn(BH4)2.2NH3 and preparation method thereof |
| CN102205946A (en) * | 2011-05-03 | 2011-10-05 | 浙江大学 | Liquid phase synthesis method of non-alkali-metal type metal hydroboron |
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