CN105947976B - A kind of composite hydrogen storage material and preparation method thereof - Google Patents
A kind of composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN105947976B CN105947976B CN201610265793.9A CN201610265793A CN105947976B CN 105947976 B CN105947976 B CN 105947976B CN 201610265793 A CN201610265793 A CN 201610265793A CN 105947976 B CN105947976 B CN 105947976B
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a kind of composite hydrogen storage materials, are combined with ammonium salt by light metal boron hydride, the light metal boron hydride includes Ca (BH4)2、LiBH4Or Mg (BH4)2, ammonium salt includes NH4F、NH4Cl、NH4Br、NH4NO3、(NH4)2CO3、NH4HCO3、(NH4)2SO4、NH4HSO4At least one of；The molar ratio of light metal boron hydride and ammonium salt is 1:0.375~2.The composite hydrogen storage material has hydrogen discharging temperature low, and the advantage that the hydrogen purity discharged is high.The invention also discloses the preparation processes of the composite hydrogen storage material, and light metal boron hydride is mixed with ammonium salt, carry out mixing and ball milling under an ar atmosphere, and ratio of grinding media to material is 10~120:1, rotational speed of ball-mill is 200~500 revs/min, and Ball-milling Time is 4~12h.The simple process and low cost.
Description
Technical field
The present invention relates to hydrogen storage material technical fields, and in particular to a kind of composite hydrogen storage material and preparation method thereof.
Background technology
The efficient storage of hydrogen is the key that Hydrogen Energy large-scale application.The storage of hydrogen is according to physics and chemical two kinds stored
Principle is stored by that can be divided into gaseous state, liquid and solid-state in a manner of three kinds.
It is low etc. to there is big energy-consuming, safety difference and hydrogen-storage density using the gaseous state hydrogen storage of high pressure and the liquefaction storage of low temperature
Problem cannot be satisfied the demand of scale business hydrogen energy source application, such as the demand of fuel cell hydrogen source.The base of hydrogen solid-state storage
Present principles are that solid material reacts generation solid solution or hydride with hydrogen, and which overcome the gaseous states of hydrogen and liquid to store not
Foot, can realize storage and the transport process of high hydrogen-storage density and safe and convenient, be the hydrogen storage mode of great potential.In crowd
In more solid-state hydrogen storage materials, light metal complex boron hydride, such as Ca (BH4)2、LiBH4With Mg (BH4)2Due to high matter
Hydrogen-storage density and volume hydrogen-storage density, great development and application prospect are measured, but due to stronger B-H covalent bonds and coordination gold
Belong to the ionic bond between cation, light metal boron hydride is caused to have very high thermodynamic stability, hydrogen discharging temperature universal
Higher than 320 DEG C, kinetics and reversible hydrogen storage performance are poor, hinder boron hydride as hydrogen storage material it is practical into
Journey.
Recent study personnel have attempted a large amount of method to improve the suction hydrogen release thermodynamics and power of metallic boron hydrides
Performance is learned, such as adds catalyst, but the more effective Ti bases and Nb bases catalyst reported at present can only also make Ca (BH4)2Put
Hydrogen temperature reduces 10-20 DEG C [Kim etc., J.Power Sources, 2008,181,140-143.].By light metal boron hydride with
Compound other hydride are another methods for improving its hydrogen storage property, such as by LiBH4With MgH2The 2LiBH of compound preparation4-
MgH2The invertibity ratio LiBH of compound system4There is considerable degree of improvement, but the starting hydrogen discharging temperature of compound system is still higher than
350 DEG C [Vajo, etc. J.Phys Chem B, 2005,109,3719-3722.]；By Mg (BH4)2With LiNH2Carry out it is compound after,
The starting hydrogen discharging temperature of compound system can be reduced to 160 DEG C [Yu etc., J.Phys Chem C, 2010,114,4733-4737.]
But currently, light metal boron hydride is either by compound with other hydride, or passes through and add catalyst
Method reduce the hydrogen discharging temperature of system, it is to its performance improvement effect all limited, practical requirement cannot be met.
Ammonia can be also used to and light metal boron hydride ball milling (such as Ca (BH4)2,Mg(BH4)2) compound, but ammonia after ball milling
Gas and the formation of light metal boron hydride are a kind of ammino-complexes, have crystal structure, and in general, with light metal boron hydride network
The NH of conjunction3Ligancy be selective, such as Ca (BH4)2Ammonia complexing Ca (BH4)2·nNH3, n is only 1,2,4,6)
[Chen etc., Chem Mater, 2010,46,2599-2601.].
It is proposed that ball-milling method prepares Ca using Chen Ping etc. [Chen etc., Chem Mater, 2010,46,2599-2601.]
(BH4)2·nNH3.Work as n=6, Ca (BH4)2·6NH3It is a kind of phase that cannot be stabilized at ambient temperature, can quickly divides
Solution releases ammonia, generates Ca (BH4)2·4NH3；Work as n=4, is observed from weight loss (TG) curve, Ca (BH4)2·4NH3
Weight loss before 300 DEG C is 44.9w%, and the weight loss in wherein 25-80 DEG C of temperature range is 20.5w%, 80-
Weight loss in 150 DEG C of temperature ranges is 12.4w%, and the weight loss in 150-300 DEG C of temperature range is 12.0w%.From
See in 25-300 DEG C in gas mass spectrum (MS) curve, Ca (BH4)2·4NH3Only ammonia is released, and is released without hydrogen.From
Ca(BH4)2·4NH3Only it is observed that belonging to Ca (BH in the XRD spectrum of decomposition product when being heated to 80 DEG C4)2·2NH3Diffraction
Peak illustrates Ca (BH4)2·4NH3Ammonia is decomposed to give off in 25-80 DEG C of temperature range generates Ca (BH4)2·2NH3；Work as n=2,
Ca (the BH in 80-150 DEG C of temperature range4)2·2NH3Continue only to release ammonia, from Ca (BH4)2·2NH3When being heated to 150 DEG C
Only it is observed that belonging to Ca (BH in the XRD spectrum of decomposition product4)2·NH3Diffraction maximum, illustrate Ca (BH4)2·2NH3In 80-
Ammonia is decomposed to give off in 150 DEG C of temperature ranges generates Ca (BH4)2·NH3；Work as n=1, the Ca in 150-300 DEG C of temperature range
(BH4)2·NH3Ammonia is still only released, from Ca (BH4)2·NH3It is only capable of observing in the XRD spectrum of decomposition product when being heated to 300 DEG C
To belonging to Ca (BH4)2Diffraction maximum, illustrate Ca (BH4)2·NH3Ammonia is decomposed to give off in 150-300 DEG C of temperature range generates Ca
(BH4)2。
Therefore, Ca (BH4)2·nNH3Heat resolve substantially be exactly by Ca (BH4)2It is taken off step by step with the ammonia of complexing
Fall, from newly-generated Ca (BH4)2Process.By Ca (BH4)2Directly it is complexed to form Ca (BH with ammonia4)2·nNH3(n=1,2,4,
6) to original Ca (BH4)2Hydrogen discharging performance can not play the role of improvement.To LiBH4·nNH3Research in have also discovered
Similar phenomenon.
Compared to Mg (BH4)2, Mg (BH4)2·nNH3Hydrogen discharging performance promoted, hydrogen discharging performance and ammonia complexing number are close
Correlation, but it decomposes hydrogen discharging temperature and is above 100 DEG C, and the hydrogen purity released is not generally high.
Yuan Feng (" synthesis of ammino transition metal boron hydride and its hydrogen storage property research ", Yuan Feng, Fudan University, master
Thesis) be prepared for by the solid phase exchange reaction between ammino transition metal chloride and alkali metal borohydride it is a series of
Ammino transition metal boron hydride, but there are still the halogen of byproduct of reaction alkali metal in obtained ammino transition metal boron hydride
Compound causes the theoretical hydrogen storage content of system relatively low, for example, YCl3·NH3/3LiBH4The theoretical hydrogen storage content of mixture is only
7.7wt%, and original simple LiBH4Theoretical hydrogen content be 18.5wt%, the mixture can be with a large amount of during heating
Ammonia release, therefore the purity for the hydrogen released in practical heating process is only 51.3wt%.And its preparation process is multiple
It is miscellaneous, need the mixture that ammino transition metal boron hydride and alkali halide can just be prepared by multistep reaction.
Therefore, develop other new hydrogen storage material systems with low hydrogen discharging temperature and preparation method thereof with important science
Meaning and practical application meaning.
Invention content
The present invention provides a kind of hydrogen storage materials being combined by light metal boron hydride and ammonium salt, have hydrogen discharging temperature
The high advantage of hydrogen purity that is low, and discharging；The hydrogen storage material is formed by ball-milling, simple process and low cost.
The invention discloses a kind of composite hydrogen storage materials, are combined with ammonium salt by light metal boron hydride, described is light
Metallic boron hydrides includes Ca (BH4)2、LiBH4Or Mg (BH4)2, ammonium salt includes NH4F、NH4Cl、NH4Br、NH4NO3、(NH4)2CO3、NH4HCO3、(NH4)2SO4、NH4HSO4At least one of；
The molar ratio of the light metal boron hydride and ammonium salt is 1:0.375~2.
Preferably, the ammonium salt is selected from NH4Cl、NH4Br、(NH4)2CO3Or (NH4)2SO4。
Further preferably, the composite hydrogen storage material is by Ca (BH4)2With NH4Cl is combined, further preferably, Ca (BH4)2
With NH4The molar ratio of Cl is 1:1.5~2.
Or it is that the composite hydrogen storage material is by Mg (BH4)2With NH4Br is combined, Mg (BH4)2With NH4Br's rubs
You are than being 1:1.5~2.
Or it is that the composite hydrogen storage material is by LiBH4With (NH4)2SO4It is combined, LiBH4With (NH4)2SO4Rub
You are than being 1:0.375.
The invention also discloses the preparation methods of the composite hydrogen storage material：
Light metal boron hydride is mixed with ammonium salt, carries out mixing and ball milling under an ar atmosphere, ratio of grinding media to material is 10~120:1,
Rotational speed of ball-mill is 200~500 revs/min, and Ball-milling Time is 4~12h.
Preferably, ball grinding method includes planetary type ball-milling, horizontal ball milling or oscillatory type ball milling.Abrading-ball may be used stainless
Steel ball, agate ball or ceramic/metal composite materials abrading-ball.
Preferably, ball milling temperature is room temperature.
Preferably, mechanical milling process use both forward and reverse directions alternate run, run 0.2~0.5h, suspend 0.05~0.2h or
Without stop, then rerun in the opposite direction.The method of operation can improve grinding efficiency, and material is made to be uniformly mixed, reaction
Fully.
Compared with prior art, the invention has the advantages that：
1, ball grinding method using the present invention can make Ca (BH4)2、LiBH4With Mg (BH4)2Light metal boron hydride is in room temperature
Under can be chemically reacted with ammonia salt, generate a kind of hydrogen storage material of the key containing B-N-H；Preparation method is simple for process, and effect is good,
It is at low cost and environmentally safe.
2, the ammonium salt used in the hydrogen storage material has many advantages, such as that synthesis technology is simple, cheap, nontoxic and pollution-free, but
Up to the present 95% or more ammonium salt is all used only as agricultural nitrogenous fertilizer, developing its application in terms of hydrogen storage material has weight
Want meaning.
3, using above method preparation by Ca (BH4)2、LiBH4With Mg (BH4)2With answering for the compound key containing B-N-H of ammonia salt
Hydrogen storage material is closed, hydrogen storage capability is high, and hydrogen discharging temperature is low, and hydrogen discharging rate is high, and the hydrogen purity of releasing is high.
4, prepared hydrogen storage material system great prospect of the application in fuel cell hydrogen source；Ammonium salt price used is just
Preferably, environmentally safe.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates (a) and fourier infrared of composite hydrogen storage material prepared by embodiment 1
(FTIR) collection of illustrative plates (b) schemes also to provide the Ca (BH after ball milling respectively in (a)4)2And NH4The XRD spectrum of Cl is as a comparison；
Fig. 2 is the volume Hydrogen desorption isotherms of composite hydrogen storage material prepared by embodiment 1, and provides the ball milling of the preparation of comparative example 1
Product is as a comparison；
Fig. 3 is thermogravimetric (TG)-mass spectrum (MS) curve of composite hydrogen storage material prepared by embodiment 1；
Fig. 4 is isothermal dehydrogenation curve of the composite hydrogen storage material of the preparation of embodiment 1 at 140 DEG C；
Fig. 5 is isothermal dehydrogenation curve of the composite hydrogen storage material of the preparation of embodiment 1 at 190 DEG C；
Fig. 6 is the TG-MS curves of ball milling product prepared by comparative example 2；
Fig. 7 is the XRD spectrum (a) and FTIR collection of illustrative plates (b) of ball milling product prepared by comparative example 2, is also provided respectively in figure (a)
Ca (BH after ball milling4)2And NH4The XRD spectrum of Cl is as a comparison；
Fig. 8 is the XRD spectrum (a) and FTIR collection of illustrative plates (b) of composite hydrogen storage material prepared by embodiment 2, is also distinguished in figure (a)
Provide the Mg (BH after ball milling4)2And NH4The XRD spectrum of Br is as a comparison；
Fig. 9 is the volume Hydrogen desorption isotherms of composite hydrogen storage material prepared by embodiment 2；
Figure 10 is the TG-MS curves of composite hydrogen storage material prepared by embodiment 2；
Figure 11 is the XRD spectrum (a) and FTIR collection of illustrative plates (b) of composite hydrogen storage material prepared by embodiment 3, is also divided in figure (a)
Mg (the BH after ball milling are not provided4)2And NH4The XRD spectrum of Br is as a comparison；
Figure 12 is the volume Hydrogen desorption isotherms of composite hydrogen storage material prepared by embodiment 3；
Figure 13 is the TG-MS curves of composite hydrogen storage material prepared by embodiment 3；
Figure 14 is the XRD spectrum (a) and FTIR collection of illustrative plates (b) of composite hydrogen storage material prepared by embodiment 4, is also divided in figure (a)
The LiBH after ball milling is not provided4With (NH4)2SO4XRD spectrum as a comparison；
Figure 15 is the volume Hydrogen desorption isotherms of composite hydrogen storage material prepared by embodiment 4；
Figure 16 is the TG-MS curves of composite hydrogen storage material prepared by embodiment 4.
Specific implementation mode
Embodiment 1
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2With NH4Cl is with molar ratio for 1:1.5 are mixed
It closes, is fitted into stainless cylinder of steel, it is 100 to be put into ratio of grinding media to material:1 stainless steel abrading-ball seals ball grinder, makes to be Ar gas atmosphere in tank.
Rotational speed of ball-mill is 300 revs/min, and Ball-milling Time is 10 hours.It often runs 0.5 hour, suspends 0.1 hour, then in the opposite direction
It reruns.After mechanical milling process, composite hydrogen storage material is obtained.
(a) gives the composite hydrogen storage material obtained after the present embodiment ball milling and Ca (BH in Fig. 14)2With NH4At the beginning of Cl
Beginning material distinguishes the XRD spectrum after ball milling.From (a) in Fig. 1 it is found that ball milling obtain composite material in Ca (BH4)2With NH4Cl's
Diffraction maximum completely disappears, and a kind of amorphous composite material is generated after illustrating ball milling.(b) is answering for ball milling acquisition in Fig. 1
The FTIR collection of illustrative plates of condensation material is located at 3274 and 3150cm-1Two absorption peaks at place are the stretching vibration of N-H keys；Positioned at 2466,
2290 and 2225cm-1The absorption peak at place is the stretching vibration of B-H keys；In 1404cm-1The absorption peak at place is that the bending of N-H keys is shaken
It is dynamic；And 1185 and 1106cm-1Two peaks at place then derive from the bending vibration of B-H keys；In 1020cm-1There is a B-N in place
The absorption peak of key illustrates the Ca (BH in mechanical milling process4)2With NH4Cl is chemically reacted, and generates a kind of storage of the key containing B-N-H
Hydrogen material.
In conjunction with to Ca (BH4)2And NH4Mass spectrum (MS) analysis and ball milling that gas is released in Cl mixture mechanical milling processes terminate
Afterwards in ball grinder pressure mutation analysis, it is known that a small amount of hydrogen is released in mechanical milling process.According in ball grinder before and after ball milling
The variation of gas pressure calculates in mechanical milling process and releases amounts of hydrogen, derives the compound of the key containing B-N-H prepared by the present embodiment
The name composition of hydrogen storage material should be CaB2N1.5H12Cl1.5。
Fig. 2 is the volume Hydrogen desorption isotherms of B-N-H composite hydrogen storage materials manufactured in the present embodiment.It can be seen from the figure that ball
The starting hydrogen discharging temperature of resulting materials is only 60 DEG C after mill, compared with the pure Ca (BH through corresponding ball milling4)2Reduce about 300 DEG C.It is compound
Material is heated to 150 DEG C, can release the hydrogen of about 4.5wt% (weight percent), and through the Ca (BH of corresponding technique ball milling4)2
Basic no hydrogen is released at such a temperature.
Fig. 3 is that the gentle constitution of thermogravimetric (TG) curve of composite hydrogen storage material hydrogen release process obtained by the present embodiment ball milling composes (MS)
Curve.As it can be seen that being mostly hydrogen in hydrogen release product, the NH of denier is contained only3, it is practically free of BH3And B2H6.In conjunction with Fig. 2 and
Fig. 3 can obtain synthesized composite hydrogen storage material and release the purity of hydrogen in gas during heating more than 99mol%
(molar percentage).
Fig. 4 and Fig. 5 is respectively that composite hydrogen storage material constant temperature at a temperature of 140 DEG C and 190 DEG C obtained by the present embodiment ball milling is released
The volume Hydrogen desorption isotherms of deflation body, it can be seen that B-N-H systems manufactured in the present embodiment are de- in 140 DEG C of constant temperature from Fig. 4 and Fig. 5
Hydrogen, amount of dehydrogenation is 4.4 weight percent or so in 15 minutes, and 190 DEG C of constant temperature dehydrogenations, amount of dehydrogenation is 4.7 weight hundred in 10 minutes
Divide than left and right.Composite hydrogen storage material has high dehydrogenation rate, hydrogen desorption kinetics performance good.
Comparative example 1
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2It is fitted into stainless cylinder of steel, ball-milling technology and implementation
Example 1 is identical.
Comparative example 2
In the glove box of argon gas atmosphere, by Ca (BH4)2With NH4Cl is with molar ratio for 1:1.5 are mixed, and loading is placed with
In the stainless cylinder of steel of abrading-ball, is protected using argon gas and carry out solid-state ball milling.Ratio of grinding media to material is 100:1, rotational speed of ball-mill is 150 revs/min, ball
Time consuming is 3 hours.
Fig. 6 is the TG-MS curves of the hydrogen release process of ball milling product obtained by the comparative example.From figure as it can be seen that ball milling product is adding
Larger amount of ammonia is released in thermal process, the purity for releasing hydrogen in gas is low.It can be seen that in the Ca (BH of same ratio4)2With
NH4Under the conditions of Cl, such as using lower ballmilling energy (low rotational speed of ball-mill and short Ball-milling Time), Ca (BH4)2And NH4Cl bases
This is reactionless, cannot synthesize the high composite hydrogen storage material of hydrogen release purity.
(a) and (b) is respectively XRD the and FTIR collection of illustrative plates of ball milling product prepared by this comparative example in Fig. 7.(a) can from figure
To see, Ca (BH in ball milling product4)2And NH4The diffraction maximum of Cl is apparent.FTIR analyses do not find B-N-H keys.
Embodiment 2
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Mg (BH4)2With NH4Br is with molar ratio for 1:1.5 are mixed
It closes, is fitted into the stainless steel jar mill for being placed with stainless steel abrading-ball, seal ball grinder.Carry out solid-state ball milling.Ratio of grinding media to material is 80:1, ball
It is 400 revs/min to grind rotating speed, and Ball-milling Time is 5 hours.Composite hydrogen storage material is obtained after ball milling.
(a) gives the composite hydrogen storage material of the present embodiment ball milling acquisition and the Mg through corresponding technique ball milling in Fig. 8
(BH4)2With NH4The X-ray collection of illustrative plates of Br.Mg (BH in the composite material that ball milling obtains4)2With NH4The diffraction maximum of Br completely disappears,
A kind of amorphous composite material is generated after illustrating ball milling.(b) is the FTIR collection of illustrative plates of composite material after ball milling in Fig. 8,
3025,3184,3261 and 3333cm-1The infrared absorption peak peak at place is the stretching vibration of N-H keys；Positioned at 2205,2287 and
2343cm-1The peak at place is the stretching vibration absworption peak of B-H keys；Positioned at 1401cm-1The absorption peak at place is the bending vibration of N-H keys；
And it is located at 1162,1558 and 1270cm-1The absorption peak peak at place then derives from the bending vibration of B-H keys；In 1065cm-1Place occurs
The absorption peak of one B-N key, illustrates the Mg (BH in mechanical milling process4)2With NH4Br occurs chemical reaction and generates one kind containing B-N-H
The hydrogen storage material of key.
In conjunction with to Mg (BH4)2And NH4Mass spectrum (MS) analysis and ball milling that gas is released in Br mixture mechanical milling processes terminate
Afterwards in ball grinder pressure mutation analysis, it is known that, a small amount of hydrogen is released in mechanical milling process.According in ball grinder before and after ball milling
The variation of gas pressure calculates the amount for releasing hydrogen in mechanical milling process, derives answering for the key manufactured in the present embodiment containing B-N-H
The name composition for closing hydrogen storage material should be MgB2N1.5H12Br1.5。
Fig. 9 is the volume Hydrogen desorption isotherms of the hydrogen storage material of the key manufactured in the present embodiment containing B-N-H.From volume Hydrogen desorption isotherms figure
In as can be seen that ball milling after gained composite hydrogen storage material starting hydrogen discharging temperature down to 75 DEG C, purer Mg (BH4)2(through corresponding ball
Grinding process) reduce 220 DEG C or so.Composite hydrogen storage material is heated to 250 DEG C of hydrogen that just can release about 5.0wt%, and Mg
(BH4)2(through corresponding ball-milling technology) basic no hydrogen is released at such a temperature.
Figure 10 is the TG-MS curves of the hydrogen release process of composite hydrogen storage material obtained by the present embodiment ball milling.As it can be seen that released
Gas is mainly H2, other containing only micro B2H6.In conjunction with Fig. 9 and Figure 10, synthesized composite hydrogen storage material can be obtained and added
The purity that hydrogen in gas is released in thermal process is more than 92mol%.
Embodiment 3
In the glove box of argon gas atmosphere, by Mg (BH4)2With NH4Br is with molar ratio for 1:2 are mixed, and loading is placed with mill
In the stainless cylinder of steel of ball, ball grinder is sealed.Carry out solid-state ball milling.Ratio of grinding media to material is 100:1, rotational speed of ball-mill is 250 revs/min, ball milling
Time is 10 hours.Obtain composite hydrogen storage material.
(a) gives composite hydrogen storage material and Mg (BH obtained by the present embodiment ball milling in Figure 114)2With NH4Br is through corresponding work
X-ray collection of illustrative plates after skill ball milling.Mg (BH in composite material after ball milling4)2With NH4The diffraction maximum of Br completely disappears, and illustrates ball milling
After generate a kind of amorphous material.(b) is the FTIR collection of illustrative plates of composite material in Figure 11, is located at 3031,3174 and 3261cm-1
The infrared absorption peak peak at place is the stretching vibration of N-H keys；In 2287 and 2343cm-1The peak at place is that the stretching vibration of B-H keys absorbs
Peak；Positioned at 1401cm-1The absorption peak at place is the bending vibration of N-H keys；And 1162 and 1246cm-1The absorption peak peak at place then source
In the bending vibration of B-H keys；In 1065cm-1There is the absorption peak of a B-N key in place, illustrates the Mg (BH in mechanical milling process4)2
With NH4Br occurs chemical reaction and generates a kind of compound of the key containing B-N-H of complexity.
In conjunction with to Mg (BH4)2And NH4Mass spectrum (MS) analysis and ball milling that gas is released in Br mixture mechanical milling processes terminate
Afterwards in ball grinder the mutation analysis of pressure it is found that releasing a small amount of hydrogen in mechanical milling process.According in ball grinder before and after ball milling
The variation of gas pressure calculates the amount that hydrogen is released in mechanical milling process, the composite hydrogen occluding of the key manufactured in the present embodiment containing B-N-H
The name composition of material should be MgB2N2H12Br2。
Figure 12 is the volume Hydrogen desorption isotherms of the composite hydrogen storage material of the system manufactured in the present embodiment containing B-N-H.It is put from volume
As can be seen that the starting hydrogen discharging temperature of gained composite material is down to 75 DEG C after ball milling in hydrogen curve graph, the corresponding technique of purer warp
Mg (the BH of ball milling4)2Reduce 220 DEG C or so.Composite hydrogen storage material is heated to 300 DEG C of hydrogen that just can release about 4.5wt%
Gas, and Mg (BH4)2Basic no hydrogen is released at such a temperature.
Figure 13 is the TG-MS curves of the hydrogen release process of composite material obtained by the present embodiment, it is seen then that the gas released is main
It is H2, other containing only micro B2H6.In conjunction with Figure 12 and Figure 13, synthesized composite hydrogen storage material can be obtained in heating process
The purity of hydrogen is more than 92mol% in middle releasing gas.
Embodiment 4
In the glove box of argon gas atmosphere, by LiBH4With (NH4)2SO4With molar ratio for 1:0.375 is mixed, and is packed into
It is placed in the stainless cylinder of steel of abrading-ball, seals.Carry out solid-state ball milling.Ratio of grinding media to material is 120:1, rotational speed of ball-mill is 350 revs/min, ball milling
Time is 8 hours.Composite hydrogen storage material is obtained after ball milling.
(a) gives the obtained composite hydrogen storage material of the present embodiment ball milling and LiBH in Figure 144With (NH4)2SO4Initially
X-ray figure of the material after corresponding technique ball milling.(b) is infrared (FTIR) figure of Fourier of composite material after ball milling in Figure 14
Spectrum.LiBH in composite material after ball milling4With (NH4)2SO4Diffraction maximum completely disappear, illustrate to generate after ball milling and a kind of containing B-
The amorphous state hydrogen storage material of N-H keys.
Figure 15 is the volume Hydrogen desorption isotherms of the B-N-H system hydrogen storage material prepared by the present embodiment.From volume Hydrogen desorption isotherms
It can be seen from the figure that, the starting hydrogen discharging temperature of gained composite hydrogen storage material is down to 50 DEG C after ball milling, compared with through corresponding technique ball milling
Pure LiBH4Sample reduces 350 DEG C or so.Composite hydrogen storage material is heated to 150 DEG C of hydrogen that can release about 4.5wt%
Gas, and LiBH4Not hydrogen release at such a temperature.
Figure 16 is the TG-MS curves of the hydrogen release process of composite material obtained by the present embodiment.In conjunction with Figure 15 and Figure 16, can obtain
The purity for releasing hydrogen in gas during heating to synthesized composite hydrogen storage material is more than 90mol%.
Embodiment 5
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2With NH4Cl is with molar ratio for 1:1.5 are mixed
It closes, is fitted into stainless cylinder of steel, it is 100 to be put into ratio of grinding media to material:1 stainless steel abrading-ball seals ball grinder, makes to be Ar gas atmosphere in tank.
Solid-phase ball milling is carried out to mixture, rotational speed of ball-mill is 500 revs/min, and Ball-milling Time is 8 hours.It often runs 0.5 hour, pause 0.1
Hour, then rerun in the opposite direction.
Through XRD analysis, Ca (BH in composite material after ball milling4)2With NH4The diffraction maximum of Cl completely disappears, and illustrates life after ball milling
At a kind of amorphous composite material.Ball after being analyzed with ball milling in conjunction with the mass spectrum (MS) to releasing gas in mechanical milling process
The mutation analysis of pressure is it is found that Ca (BH in grinding jar4)2With NH4Cl releases a small amount of hydrogen in mechanical milling process.Before ball milling
The variation of gas pressure calculates the amount that hydrogen is released in mechanical milling process, key containing B-N-H manufactured in the present embodiment in ball grinder afterwards
Composite hydrogen storage material name composition should be CaB2N1.5H12Cl1.5。
B-N-H composite hydrogen storage materials prepared by the present embodiment, the starting hydrogen discharging temperature of gained sample is only 60 after ball milling
DEG C, purer Ca (BH4)2Reduce about 300 DEG C.Composite hydrogen storage material is heated to 150 DEG C of hydrogen for just releasing about 4.5wt%, and
Ca(BH4)2Basic no hydrogen is released at such a temperature.
Embodiment 6
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2With NH4Cl is with molar ratio for 1:2 are mixed,
It is fitted into stainless cylinder of steel, it is 120 to be put into ratio of grinding media to material:1 stainless steel abrading-ball seals ball grinder.Carry out solid-state ball milling, rotational speed of ball-mill
It it is 400 revs/min, Ball-milling Time is 6 hours.It often runs 0.5 hour, suspends 0.1 hour, then rerun in the opposite direction.
Through XRD analysis, the Ca (BH of composite material after ball milling4)2With NH4The diffraction maximum of Cl completely disappears, and illustrates life after ball milling
At a kind of amorphous composite material.In conjunction with to Mg (BH4)2And NH4The mass spectrum of gas is released in Br mixture mechanical milling processes
(MS) after analysis and ball milling in ball grinder the mutation analysis of pressure it is found that releasing a small amount of hydrogen in mechanical milling process.Root
The amount that hydrogen is released in mechanical milling process is calculated according to the variation of gas pressure in ball grinder before and after ball milling, it is manufactured in the present embodiment to contain
The name composition of the composite hydrogen storage material of B-N-H keys should be CaB2N2H12Cl2。
B-N-H composite hydrogen storage materials manufactured in the present embodiment, the starting hydrogen discharging temperature of gained sample is only 50 DEG C after ball milling,
Compared with the pure Ca (BH through corresponding technique ball milling4)2Reduce about 300 DEG C.Composite hydrogen storage material is heated to 200 DEG C and just releases about
The hydrogen of 3.8wt%, and Ca (BH4)2Basic no hydrogen is released at such a temperature.
Claims (4)
1. a kind of composite hydrogen storage material, it is characterised in that：
By Ca (BH4)2With NH4Cl is combined, the Ca (BH4)2With NH4The molar ratio of Cl is 1:1.5~2；
Or for by Mg (BH4)2With NH4Br is combined, the Mg (BH4)2With NH4The molar ratio of Br is 1:1.5~2；
Or for by LiBH4With (NH4)2SO4It is combined, the LiBH4With (NH4)2SO4Molar ratio be 1:0.375；
The composite hydrogen storage material is amorphous composite material of the key containing B-N-H, and preparation method includes：
Light metal boron hydride is mixed with ammonium salt, carries out mixing and ball milling under an ar atmosphere, ratio of grinding media to material is 10~120:1, ball milling
Rotating speed is 200~500 revs/min, and Ball-milling Time is 4~12h.
2. composite hydrogen storage material according to claim 1, it is characterised in that：Ball grinding method includes planetary type ball-milling, horizontal
Ball milling or oscillatory type ball milling.
3. composite hydrogen storage material according to claim 1, it is characterised in that：Ball milling temperature is room temperature.
4. composite hydrogen storage material according to claim 1, it is characterised in that：Mechanical milling process is alternately transported using both forward and reverse directions
Row runs 0.2~0.5h, suspends 0.05~0.2h or without stop, then reruns in the opposite direction.
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| CN102530872A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院金属研究所 | Multi-metal ammonia borane compound hydrogen storage material and preparation and composite hydrogen release method thereof |
| CN102556968A (en) * | 2010-12-31 | 2012-07-11 | 中国科学院金属研究所 | Preparation method of hydrogen storage material of borane ammonia compound |
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| CN102530872A (en) * | 2010-12-08 | 2012-07-04 | 中国科学院金属研究所 | Multi-metal ammonia borane compound hydrogen storage material and preparation and composite hydrogen release method thereof |
| CN102556968A (en) * | 2010-12-31 | 2012-07-11 | 中国科学院金属研究所 | Preparation method of hydrogen storage material of borane ammonia compound |
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