CN105947976A - Composite hydrogen storage material and preparation method thereof - Google Patents
Composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN105947976A CN105947976A CN201610265793.9A CN201610265793A CN105947976A CN 105947976 A CN105947976 A CN 105947976A CN 201610265793 A CN201610265793 A CN 201610265793A CN 105947976 A CN105947976 A CN 105947976A
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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 composite hydrogen storage material formed by compounding a light metal borohydride and an ammonium salt, wherein the light metal borohydride comprises Ca(BH4)2, LiBH4 or Mg(BH4)2; the ammonium salt includes at least one of NH4F, NH4Cl, NH4Br, NH4NO3, (NH4)2CO3, NH4HCO3, (NH4)2SO4 and NH4HSO4; the molar ratio of the light metal borohydride to the ammonium salt is 1 to (0.375-2). The composite hydrogen storage material has the advantages of low hydrogen release temperature, and high purity of released hydrogen. The invention also discloses a preparation process of the composite hydrogen storage material; the light metal borohydride and the ammonium salt are mixed and are ball-milled in an Ar atmosphere, the ball-feed ratio is (10-120):1, the ball-milling rotating speed is 200-500 r/min, and the ball-milling time is 4-12 h. The process is simple and the cost is low.
Description
Technical field
The present invention relates to hydrogen storage material technical field, be specifically related to a kind of composite hydrogen storage material and preparation thereof
Method.
Background technology
The efficient storage of hydrogen is the key of Hydrogen Energy large-scale application.The storage of hydrogen is according to physics and chemistry
The two kinds of principles stored, can be divided into gaseous state, liquid and solid-state to store three kinds of modes.
The gaseous state hydrogen storage of high pressure and the liquefaction storage of low temperature is used all to there is big energy-consuming, poor stability and storage
The problems such as hydrogen density is low, it is impossible to meet the demand of scale business hydrogen energy source application, as fuel cell is used
The demand of hydrogen source.The ultimate principle of hydrogen solid-state storage be solid material with hydrogen react generation solid solution or
Person's hydride, which overcomes gaseous state and the deficiency of liquid storage of hydrogen, it is possible to realize high hydrogen-storage density
Storage with safe and convenient and transport process, be the hydrogen storage mode of great potential.In numerous solid-states
In hydrogen storage material, light metal complex boron hydride, such as Ca (BH4)2、LiBH4With Mg (BH4)2Due to
There is high quality hydrogen-storage density and volume hydrogen-storage density, great development and application prospect, but due to
Ionic bond between stronger B-H covalent bond and coordinating metal cation, causes light metal hydroboration
Thing has the highest thermodynamic stability, and its hydrogen discharging temperature is generally higher than 320 DEG C, kinetics and
Reversible hydrogen storage poor-performing, hinders the boron hydride practicalization as hydrogen storage material.
Recent study personnel have attempted substantial amounts of method puts hydrogen heat to the suction improving metallic boron hydrides
Mechanics and dynamic performance, as added catalyst, but the more effective Ti base reported at present and Nb
Base catalyst also can only make Ca (BH4)2Hydrogen discharging temperature reduce 10-20 DEG C of [Kim etc., J.Power
Sources,2008,181,140-143.].Being combined with other hydride by light metal boron hydride is another
Plant the method improving its hydrogen storage property, as by LiBH4With MgH2The 2LiBH of compound preparation4-MgH2Multiple
The reversibility of fit system compares LiBH4There is a considerable degree of improvement, but the initial hydrogen discharging temperature of compound system
Still above 350 DEG C [Vajo, etc., J.Phys Chem B, 2005,109,3719-3722.]；Will
Mg(BH4)2With LiNH2After carrying out being combined, the initial hydrogen discharging temperature of compound system can be reduced to
160 DEG C [Yu etc., J.Phys Chem C, 2010,114,4733-4737.]
But at present, light metal boron hydride either compound by with other hydride, still pass through
The method adding catalyst reduces the hydrogen discharging temperature of system, the most limited, no to its performance improvement effect
Practical requirement can be met.
Ammonia also can be used to light metal boron hydride ball milling (such as Ca (BH4)2,Mg(BH4)2) multiple
Close, but after ball milling ammonia and light metal boron hydride formed is a kind of ammino-complex, has crystal
Structure, and generally, with the NH of light metal boron hydride complexation3Ligancy be selectively,
Such as Ca (BH4)2The complexation Ca (BH of ammonia4)2·nNH3, n is only 1,2,4,6) [Chen etc.,
Chem Mater,2010,46,2599-2601.]。
[Chen etc., Chem Mater, 2010,46,2599-2601.] such as Chen Ping is used to propose ball milling legal system
Standby Ca (BH4)2·nNH3.Work as n=6, Ca (BH4)2·6NH3It is that one can not stably be deposited at ambient temperature
Phase, its can fast decoupled release ammonia, generate Ca (BH4)2·4NH3；Work as n=4, damage from weight
Lose in (TG) curve and observe, Ca (BH4)2·4NH3Weight loss before 300 DEG C is 44.9
W%, wherein the loss of the weight in 25-80 DEG C of temperature range is 20.5w%, 80-150 DEG C of temperature range
Interior weight loss is 12.4w%, and the weight loss in 150-300 DEG C of temperature range is 12.0w%.
See in 25-300 DEG C from gas mass spectrum (MS) curve, Ca (BH4)2·4NH3Only ammonia is put
Go out, do not have hydrogen to release.From Ca (BH4)2·4NH3It is heated to the XRD figure spectrum of catabolite when 80 DEG C
In only it is observed that belong to Ca (BH4)2·2NH3Diffraction maximum, Ca (BH is described4)2·4NH3?
Decompose to give off ammonia in 25-80 DEG C of temperature range and generate Ca (BH4)2·2NH3；Work as n=2,
Ca (BH in 80-150 DEG C of temperature range4)2·2NH3Continue only to release ammonia, from Ca (BH4)2·2NH3
Only it is observed that belong to Ca (BH in the XRD figure spectrum of catabolite when being heated to 150 DEG C4)2·NH3's
Diffraction maximum, illustrates Ca (BH4)2·2NH3In 80-150 DEG C of temperature range, decompose to give off ammonia generate
Ca(BH4)2·NH3；Work as n=1, Ca (BH in 150-300 DEG C of temperature range4)2·NH3The most only release ammonia
Gas, from Ca (BH4)2·NH3Only it is heated in the XRD figure spectrum of catabolite when 300 DEG C it is observed that belong to
In Ca (BH4)2Diffraction maximum, Ca (BH is described4)2·NH3Decompose in 150-300 DEG C of temperature range and put
Go out ammonia and generate Ca (BH4)2。
Therefore, Ca (BH4)2·nNH3Heat resolve be exactly substantially by Ca (BH4)2Ammonia with complexation
Take off step by step, from newly-generated Ca (BH4)2Process.By Ca (BH4)2Directly and ammonia complexation shape
Become Ca (BH4)2·nNH3(n=1,2,4,6) is to original Ca (BH4)2Hydrogen discharging performance can not play
The effect improved.To LiBH4·nNH3Research in have also discovered similar phenomenon.
Compared to Mg (BH4)2, Mg (BH4)2·nNH3Hydrogen discharging performance promoted, hydrogen discharging performance with
Ammonia complexing number is closely related, but it decomposes hydrogen discharging temperature and is above 100 DEG C, and the hydrogen released is pure
Degree is the highest.
Yuan Feng (" synthesis of ammino transition metal boron hydride and hydrogen storage property research thereof ", Yuan Feng is multiple
Denier university, master's thesis) by between ammino transition metal chloride and alkali metal borohydride
Solid phase exchange reaction is prepared for a series of ammino transition metal boron hydride, but the ammino transition obtained
Metallic boron hydrides still suffers from the alkali-metal halogenide of byproduct of reaction, causes the theoretical hydrogen storage of system
Measure relatively low, such as, YCl3·NH3/3LiBH4The theoretical hydrogen storage content of mixture is only 7.7wt%, and former
Begin simple LiBH4Theoretical hydrogen content be 18.5wt%, in heating process, this mixture can be with greatly
The ammonia release of amount, the purity of the hydrogen therefore released in actual heating process is only 51.3wt%.
And its complicated process of preparation, needs just to prepare ammino transition metal boron hydrogen through multistep reaction
Compound and the mixture of alkali halide.
Therefore, develop other new hydrogen storage material system with low hydrogen discharging temperature and preparation method thereof to have
Important academic significance and actual application value.
Summary of the invention
The invention provides a kind of hydrogen storage material being composited by light metal boron hydride and ammonium salt, tool
There is hydrogen discharging temperature low, and the high advantage of hydrogen purity of release；This hydrogen storage material is by ball-milling
Becoming, technique is simple, low cost.
The invention discloses a kind of composite hydrogen storage material, by light metal boron hydride and ammonium salt compound and
Becoming, described light metal boron hydride includes Ca (BH4)2、LiBH4Or Mg (BH4)2, ammonium salt includes
NH4F、NH4Cl、NH4Br、NH4NO3、(NH4)2CO3、NH4HCO3、(NH4)2SO4、
NH4HSO4In at least one；
Described light metal boron hydride and the mol ratio of ammonium salt are 1:0.375～2.
As preferably, described ammonium salt is selected from NH4Cl、NH4Br、(NH4)2CO3Or (NH4)2SO4。
Further preferably, described composite hydrogen storage material is by Ca (BH4)2With NH4Cl is composited,
Further preferably, Ca (BH4)2With NH4The mol ratio of Cl is 1:1.5～2.
Or it is that described composite hydrogen storage material is by Mg (BH4)2With NH4Br is composited,
Mg(BH4)2With NH4The mol ratio of Br is 1:1.5～2.
Or it is that described composite hydrogen storage material is by LiBH4With (NH4)2SO4It is composited, LiBH4
With (NH4)2SO4Mol ratio be 1:0.375.
The invention also discloses the preparation method of described composite hydrogen storage material:
Light metal boron hydride is mixed with ammonium salt, carries out mixing and ball milling, ratio of grinding media to material under an ar atmosphere
Being 10～120:1, rotational speed of ball-mill is 200～500 revs/min, and Ball-milling Time is 4～12h.
As preferably, ball grinding method includes planetary type ball-milling, horizontal ball milling or vibration type ball milling.Abrading-ball
Stainless steel ball, agate ball or ceramic/metal composite materials abrading-ball can be used.
As preferably, ball milling temperature is room temperature.
As preferably, mechanical milling process uses both forward and reverse directions alternate run, runs 0.2～0.5h, suspends
0.05～0.2h or without stop, rerun the most in the opposite direction.This method of operation can improve ball
Mill efficiency, makes material mixing uniform, and reaction is fully.
Compared with prior art, present invention have the advantage that
1, use the ball grinding method of the present invention, Ca (BH can be made4)2、LiBH4With Mg (BH4)2Light metal
Boron hydride the most just can generate a kind of hydrogen storage containing B-N-H key with ammonia salt generation chemical reaction
Material；Preparation method technique is simple, effective, low cost and environmentally safe.
2, the ammonium salt used in this hydrogen storage material has synthesis technique simply, nothing cheap, nontoxic
The advantages such as pollution, but up to the present have the ammonium salt of more than 95% to be all used only as agricultural nitrogenous fertilizer, exploitation
Its application in terms of hydrogen storage material is significant.
3, use said method prepare by Ca (BH4)2、LiBH4With Mg (BH4)2Compound with ammonia salt
Containing the composite hydrogen storage material of B-N-H key, hydrogen storage capability is high, and hydrogen discharging temperature is low, and hydrogen discharging rate is high, puts
The hydrogen purity gone out is high.
4, prepared hydrogen storage material system great prospect of the application in fuel cell hydrogen source；Used
Ammonium salt low price, environmentally safe.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates (a) and the Fourier of the composite hydrogen storage material of embodiment 1 preparation
Infrared (FTIR) collection of illustrative plates (b), provides the Ca (BH after ball milling the most respectively in figure (a)4)2And NH4The XRD of Cl
Collection of illustrative plates is as a comparison；
Fig. 2 is the volume Hydrogen desorption isotherms of composite hydrogen storage material of embodiment 1 preparation, and provides comparative example 1 and prepare
Ball milling product as a comparison；
Fig. 3 is thermogravimetric (TG)-mass spectrum (MS) curve of the composite hydrogen storage material of embodiment 1 preparation；
Fig. 4 is that the composite hydrogen storage material of embodiment 1 preparation is at the isothermal dehydrogenation curve of 140 DEG C；
Fig. 5 is that the composite hydrogen storage material of embodiment 1 preparation is at the isothermal dehydrogenation curve of 190 DEG C；
Fig. 6 is the TG-MS curve of the ball milling product of comparative example 2 preparation；
Fig. 7 is XRD figure spectrum (a) and FTIR collection of illustrative plates (b) of the ball milling product of comparative example 2 preparation, also divides in figure (a)
Do not provide the Ca (BH after ball milling4)2And NH4The XRD figure of Cl is composed as a comparison；
Fig. 8 is XRD figure spectrum (a) and FTIR collection of illustrative plates (b) of the composite hydrogen storage material of embodiment 2 preparation, in figure (a)
Provide the Mg (BH after ball milling the most respectively4)2And NH4The XRD figure of Br is composed as a comparison；
Fig. 9 is the volume Hydrogen desorption isotherms of the composite hydrogen storage material of embodiment 2 preparation；
Figure 10 is the TG-MS curve of the composite hydrogen storage material of embodiment 2 preparation；
Figure 11 is XRD figure spectrum (a) and FTIR collection of illustrative plates (b) of the composite hydrogen storage material of embodiment 3 preparation, schemes (a)
In provide the Mg (BH after ball milling the most respectively4)2And NH4The XRD figure of Br is composed as a comparison；
Figure 12 is the volume Hydrogen desorption isotherms of the composite hydrogen storage material of embodiment 3 preparation；
Figure 13 is the TG-MS curve of the composite hydrogen storage material of embodiment 3 preparation；
Figure 14 is XRD figure spectrum (a) and FTIR collection of illustrative plates (b) of the composite hydrogen storage material of embodiment 4 preparation, schemes (a)
In provide the LiBH after ball milling the most respectively4With (NH4)2SO4XRD figure compose as a comparison；
Figure 15 is the volume Hydrogen desorption isotherms of the composite hydrogen storage material of embodiment 4 preparation；
Figure 16 is the TG-MS curve of the composite hydrogen storage material of embodiment 4 preparation.
Detailed description of the invention
Embodiment 1
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2With NH4Cl with mol ratio is
1:1.5 mixes, and loads in stainless cylinder of steel, puts into the rustless steel abrading-ball that ratio of grinding media to material is 100:1, close
Blocking grinding jar, is Ar gas atmosphere in making tank.Rotational speed of ball-mill is 300 revs/min, and Ball-milling Time is 10 hours.
Often run 0.5 hour, suspend 0.1 hour, rerun the most in the opposite direction.Mechanical milling process terminates
After, it is thus achieved that composite hydrogen storage material.
Composite hydrogen storage material that in Fig. 1, (a) is obtained after giving the present embodiment ball milling and
Ca(BH4)2With NH4XRD figure spectrum after Cl original material ball milling respectively.From Fig. 1, (a) understands, ball milling
Ca (BH in the composite obtained4)2With NH4The diffraction maximum of Cl is all wholly absent, raw after ball milling is described
Become a kind of amorphous composite.In Fig. 1, (b) is the FTIR figure of the composite that ball milling obtains
Spectrum, is positioned at 3274 and 3150cm-1The stretching vibration that two absworption peaks are N-H key at place；Be positioned at 2466,
2290 and 2225cm-1The stretching vibration that absworption peak is B-H key at place；At 1404cm-1The absworption peak at place
Bending vibration for N-H key；And 1185 and 1106cm-1Two peaks at place then derive from the curved of B-H key
Qu Zhendong；At 1020cm-1Place occurs in that the absworption peak of a B-N key, illustrates in mechanical milling process
Ca(BH4)2With NH4There is chemical reaction in Cl, generates a kind of hydrogen storage material containing B-N-H key.
In conjunction with to Ca (BH4)2And NH4The mass spectrum (MS) releasing gas in Cl mixture mechanical milling process is analyzed
The mutation analysis of pressure in rear ball grinder is terminated, it is known that in mechanical milling process, release a small amount of hydrogen with ball milling
Gas.According to the change calculations mechanical milling process of gas pressure in ball grinder before and after ball milling is released amounts of hydrogen,
The name composition deriving the composite hydrogen storage material containing B-N-H key prepared by the present embodiment should be
CaB2N1.5H12Cl1.5。
Fig. 2 is the volume Hydrogen desorption isotherms of B-N-H composite hydrogen storage material prepared by the present embodiment.Can from figure
To find out, after ball milling, the initial hydrogen discharging temperature of resulting materials is only 60 DEG C, relatively pure through corresponding ball milling
Ca(BH4)2Reduce about 300 DEG C.Composite is heated to 150 DEG C, releasably goes out about 4.5wt% (weight
Amount percentage ratio) hydrogen, and through the Ca (BH of corresponding technique ball milling4)2Basic no hydrogen is put at such a temperature
Go out.
It is gentle that Fig. 3 is that the present embodiment ball milling gained composite hydrogen storage material puts thermogravimetric (TG) curve of hydrogen process
Body constitution spectrum (MS) curve.Visible, put and hydrogen product is mostly hydrogen, only the NH containing denier3,
It is practically free of BH3And B2H6.In conjunction with Fig. 2 and Fig. 3, synthesized composite hydrogen storage material can be obtained and exist
Heating process is released the purity of hydrogen in gas and is more than 99mol% (molar percentage).
Fig. 4 and Fig. 5 is respectively the present embodiment ball milling gained composite hydrogen storage material 140 DEG C and 190 DEG C of temperature
The volume Hydrogen desorption isotherms of degree lower constant temperature release gas, can be seen that prepared by the present embodiment from Fig. 4 and Fig. 5
B-N-H system 140 DEG C of constant temperature dehydrogenations, in 15 minutes, amount of dehydrogenation is about 4.4 percentage by weights,
190 DEG C of constant temperature dehydrogenations, in 10 minutes, amount of dehydrogenation is about 4.7 percentage by weights.Composite hydrogen storage material has
Having high dehydrogenation rate, hydrogen desorption kinetics performance is good.
Comparative example 1
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2Load in stainless cylinder of steel, ball milling
Technique is identical with embodiment 1.
Comparative example 2
In the glove box of argon gas atmosphere, by Ca (BH4)2With NH4Cl mixes with mol ratio for 1:1.5
Close, load in the stainless cylinder of steel being placed with abrading-ball, use argon shield to carry out solid-state ball milling.Ratio of grinding media to material is
100:1, rotational speed of ball-mill is 150 revs/min, and Ball-milling Time is 3 hours.
Fig. 6 is the TG-MS curve of the hydrogen process of putting of this comparative example gained ball milling product.From figure,
Ball milling product releases larger amount of ammonia in heating process, releases the purity of hydrogen in gas low.Can
See the Ca (BH in same ratio4)2And NH4Under the conditions of Cl, as used relatively low ballmilling energy (low
Rotational speed of ball-mill and short Ball-milling Time), Ca (BH4)2And NH4Cl is the most reactionless, it is impossible to hydrogen is put in synthesis
The composite hydrogen storage material that purity is high.
In Fig. 7, (a) and (b) is respectively XRD and the FTIR figure of ball milling product prepared by this comparative example
Spectrum.From figure, (a) is it will be seen that Ca (BH in ball milling product4)2And NH4The diffraction maximum of Cl is obvious.
FTIR analyzes and does not finds B-N-H key.
Embodiment 2
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Mg (BH4)2With NH4Br with mol ratio is
1:1.5 mixes, and loads in the stainless steel jar mill being placed with rustless steel abrading-ball, ball sealer grinding jar.Enter
Row solid-state ball milling.Ratio of grinding media to material is 80:1, and rotational speed of ball-mill is 400 revs/min, and Ball-milling Time is 5 hours.Ball
Composite hydrogen storage material is obtained after mill.
In Fig. 8, (a) gives the composite hydrogen storage material of the present embodiment ball milling acquisition and through corresponding technological ball
Mg (the BH of mill4)2With NH4The X-ray collection of illustrative plates of Br.Mg (BH in the composite that ball milling obtains4)2
With NH4The diffraction maximum of Br is wholly absent, and generates a kind of amorphous composite after ball milling is described.
The FTIR collection of illustrative plates of composite after (b) is ball milling in Fig. 8,3025,3184,3261 and 3333cm-1
The stretching vibration that INFRARED ABSORPTION peak-to-peak is N-H key at place；It is positioned at 2205,2287 and 2343cm-1Place
Peak is the stretching vibration absworption peak of B-H key；It is positioned at 1401cm-1The bending that absworption peak is N-H key at place
Vibration；And it is positioned at 1162,1558 and 1270cm-1The peak-to-peak that absorbs at place then derives from the bending of B-H key
Vibration；At 1065cm-1Place occurs in that the absworption peak of a B-N key, illustrates in mechanical milling process
Mg(BH4)2With NH4Br occurs chemical reaction to generate a kind of hydrogen storage material containing B-N-H key.
In conjunction with to Mg (BH4)2And NH4Br mixture mechanical milling process is released the mass spectrum (MS) point of gas
Analysis and ball milling terminate the mutation analysis of pressure in rear ball grinder, it is known that, release a small amount of in mechanical milling process
Hydrogen.According to the change of gas pressure in ball grinder before and after ball milling, calculate in mechanical milling process and release
The amount of hydrogen, derives the name composition of the composite hydrogen storage material containing B-N-H key prepared by the present embodiment
Should be MgB2N1.5H12Br1.5。
Fig. 9 is the volume Hydrogen desorption isotherms of the hydrogen storage material containing B-N-H key prepared by the present embodiment.From volume
It can be seen that after ball milling the initial hydrogen discharging temperature of gained composite hydrogen storage material is as little as in Hydrogen desorption isotherms figure
75 DEG C, purer Mg (BH4)2(through corresponding ball-milling technology) reduces about 220 DEG C.Composite hydrogen-storage material
Material is heated to 250 DEG C of hydrogen the most releasably going out about 5.0wt%, and Mg (BH4)2(through corresponding ball milling work
Skill) basic no hydrogen releasing at such a temperature.
Figure 10 is the TG-MS curve of the hydrogen process of putting of the present embodiment ball milling gained composite hydrogen storage material.
Visible, the gas released is mainly H2, other B containing only trace2H6.In conjunction with Fig. 9 and Figure 10,
Can obtaining synthesized composite hydrogen storage material, to release the purity of hydrogen in gas in heating process big
In 92mol%.
Embodiment 3
In the glove box of argon gas atmosphere, by Mg (BH4)2With NH4Br mixes with mol ratio for 1:2
Close, load in the stainless cylinder of steel being placed with abrading-ball, ball sealer grinding jar.Carry out solid-state ball milling.Ratio of grinding media to material is
100:1, rotational speed of ball-mill is 250 revs/min, and Ball-milling Time is 10 hours.Obtain composite hydrogen storage material.
In Figure 11, (a) gives the present embodiment ball milling gained composite hydrogen storage material and Mg (BH4)2With
NH4Br X-ray collection of illustrative plates after corresponding technique ball milling.Mg (BH in composite after ball milling4)2With
NH4The diffraction maximum of Br is wholly absent, and generates a kind of amorphous material after ball milling is described.In Figure 11
B () is the FTIR collection of illustrative plates of composite, be positioned at 3031,3174 and 3261cm-1The infrared absorption peak at place
Peak is the stretching vibration of N-H key；2287 and 2343cm-1The stretching vibration that peak is B-H key at place is inhaled
Receive peak；It is positioned at 1401cm-1The bending vibration that absworption peak is N-H key at place；And 1162 and 1246cm-1
The peak-to-peak that absorbs at place then derives from the bending vibration of B-H key；At 1065cm-1Place occurs in that a B-N
The absworption peak of key, illustrates Mg (BH in mechanical milling process4)2With NH4Br occurs chemical reaction to generate one
The complicated compound containing B-N-H key.
In conjunction with to Mg (BH4)2And NH4Br mixture mechanical milling process is released the mass spectrum (MS) point of gas
Analysis and ball milling terminate the mutation analysis of pressure in rear ball grinder and understand, and release a small amount of in mechanical milling process
Hydrogen.Releasing hydrogen in mechanical milling process is gone out according to the change calculations of gas pressure in ball grinder before and after ball milling
Amount, the composite hydrogen storage material containing B-N-H key prepared by the present embodiment name composition should be
MgB2N2H12Br2。
Figure 12 is that the volume containing the composite hydrogen storage material of B-N-H system prepared by the present embodiment puts hydrogen song
Line.The initial hydrogen discharging temperature of gained composite from volume Hydrogen desorption isotherms figure it can be seen that after ball milling
As little as 75 DEG C, the purer Mg (BH through corresponding technique ball milling4)2Reduce about 220 DEG C.Compound storage
Hydrogen material is heated to 300 DEG C of hydrogen the most releasably going out about 4.5wt%, and Mg (BH4)2At such a temperature
Basic no hydrogen is released.
Figure 13 is the TG-MS curve of the hydrogen process of putting of the present embodiment gained composite, it is seen then that put
The gas gone out is mainly H2, other B containing only trace2H6.In conjunction with Figure 12 and Figure 13, institute can be obtained
The composite hydrogen storage material of synthesis is released the purity of hydrogen in gas in heating process and is more than 92mol%.
Embodiment 4
In the glove box of argon gas atmosphere, by LiBH4With (NH4)2SO4Carry out with mol ratio for 1:0.375
Mixing, loads in the stainless cylinder of steel being placed with 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, and Ball-milling Time is 8 hours.Composite hydrogen storage material is obtained after ball milling.
In Figure 14, (a) gives the obtained composite hydrogen storage material of the present embodiment ball milling and LiBH4With
(NH4)2SO4Original material X-ray figure after corresponding technique ball milling.After in Figure 14, (b) is ball milling again
Fourier infrared (FTIR) collection of illustrative plates of condensation material.LiBH in composite after ball milling4With (NH4)2SO4's
Diffraction maximum is wholly absent, and generates a kind of amorphous state hydrogen storage material containing B-N-H key after ball milling is described.
Figure 15 is the volume Hydrogen desorption isotherms of the B-N-H system hydrogen storage material prepared by the present embodiment.From body
Accumulate in hydrogen curve chart it can be seen that after ball milling the initial hydrogen discharging temperature of gained composite hydrogen storage material is as little as
50 DEG C, relatively through the pure LiBH of corresponding technique ball milling4Sample reduces about 350 DEG C.Composite hydrogen-storage material
Material is heated to 150 DEG C of hydrogen that just can discharge about 4.5wt%, and LiBH4Do not put
Hydrogen.
Figure 16 is the TG-MS curve of the hydrogen process of putting of the present embodiment gained composite.In conjunction with Figure 15
And Figure 16, synthesized composite hydrogen storage material can be obtained in heating process, release hydrogen in gas
Purity is more than 90mol%.
Embodiment 5
In the glove box of argon gas atmosphere (1 atmospheric pressure), by Ca (BH4)2With NH4Cl with mol ratio is
1:1.5 mixes, and loads in stainless cylinder of steel, puts into the rustless steel abrading-ball that ratio of grinding media to material is 100:1, close
Blocking grinding jar, is Ar gas atmosphere in making tank.Mixture is carried out solid-phase ball milling, and rotational speed of ball-mill is 500
Rev/min, Ball-milling Time is 8 hours.Often run 0.5 hour, suspend 0.1 hour, the most in the opposite direction
Rerun.
Ca (BH in composite after XRD analysis, ball milling4)2With NH4The diffraction maximum of Cl is wholly absent,
A kind of amorphous composite is generated after ball milling is described.In conjunction with to mechanical milling process is released gas
Mass spectrum (MS) is analyzed and ball milling terminates the mutation analysis of pressure in rear ball grinder and understands, Ca (BH4)2With
NH4Cl releases a small amount of hydrogen in mechanical milling process.According to gas pressure in ball grinder before and after ball milling
Change calculations goes out to release in mechanical milling process the amount of hydrogen, being combined containing B-N-H key prepared by the present embodiment
The name composition of hydrogen storage material should be CaB2N1.5H12Cl1.5。
B-N-H composite hydrogen storage material prepared by the present embodiment, after ball milling, the initial of gained sample puts hydrogen
Temperature is only 60 DEG C, purer Ca (BH4)2Reduce about 300 DEG C.Composite hydrogen storage material is heated to 150 DEG C
Just discharge the hydrogen of 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 mol ratio as 1:2
Mix, load in stainless cylinder of steel, put into the rustless steel abrading-ball that ratio of grinding media to material is 120:1, seal ball milling
Tank.Carrying out solid-state ball milling, rotational speed of ball-mill is 400 revs/min, and Ball-milling Time is 6 hours.Often run 0.5
Hour, suspend 0.1 hour, rerun the most in the opposite direction.
Ca (the BH of composite after XRD analysis, ball milling4)2With NH4The diffraction maximum of Cl is wholly absent,
A kind of amorphous composite is generated after ball milling is described.In conjunction with to Mg (BH4)2And NH4Br mixes
Mass spectrum (MS) analysis and the ball milling of releasing gas in thing mechanical milling process terminate the change of pressure in rear ball grinder
Fractional analysis understands, and releases a small amount of hydrogen in mechanical milling process.According to gas in ball grinder before and after ball milling
The change calculations of pressure goes out to release in mechanical milling process the amount of hydrogen, the present embodiment prepare containing B-N-H key
Composite hydrogen storage material name composition should be CaB2N2H12Cl2。
B-N-H composite hydrogen storage material prepared by the present embodiment, after ball milling, the initial of gained sample puts hydrogen temperature
Degree is only 50 DEG C, relatively through the pure Ca (BH of corresponding technique ball milling4)2Reduce about 300 DEG C.Composite hydrogen occluding
Material is heated to 200 DEG C of hydrogen just discharging about 3.8wt%, and Ca (BH4)2The most basic
No hydrogen is released.
Claims (8)
1. a composite hydrogen storage material, it is characterised in that:
Being composited with ammonium salt by light metal boron hydride, described light metal boron hydride includes
Ca(BH4)2、LiBH4Or Mg (BH4)2, ammonium salt includes NH4F、NH4Cl、NH4Br、NH4NO3、
(NH4)2CO3、NH4HCO3、(NH4)2SO4、NH4HSO4In at least one；
Described light metal boron hydride and the mol ratio of ammonium salt are 1:0.375～2.
Composite hydrogen storage material the most according to claim 1, it is characterised in that: described ammonium salt
Selected from NH4Cl、NH4Br、(NH4)2CO3Or (NH4)2SO4。
Composite hydrogen storage material the most according to claim 2, it is characterised in that: described is compound
Hydrogen storage material is by Ca (BH4)2With NH4Cl is composited；
Or it is by Mg (BH4)2With NH4Br is composited；
Or it is by LiBH4With (NH4)2SO4It is composited.
Composite hydrogen storage material the most according to claim 3, it is characterised in that: described Ca (BH4)2
With NH4The mol ratio of Cl is 1:1.5～2；
Described Mg (BH4)2With NH4The mol ratio of Br is 1:1.5～2；
Described LiBH4With (NH4)2SO4Mol ratio be 1:0.375.
5. the preparation according to the composite hydrogen storage material described in Claims 1 to 4 any claim
Method, it is characterised in that: light metal boron hydride is mixed with ammonium salt, mixes under an ar atmosphere
Closing ball milling, ratio of grinding media to material is 10～120:1, and rotational speed of ball-mill is 200～500 revs/min, and Ball-milling Time is
4～12h.
The preparation method of composite hydrogen storage material the most according to claim 5, it is characterised in that:
Ball grinding method includes planetary type ball-milling, horizontal ball milling or vibration type ball milling.
The preparation method of composite hydrogen storage material the most according to claim 5, it is characterised in that:
Ball milling temperature is room temperature.
The preparation method of composite hydrogen storage material the most according to claim 5, it is characterised in that:
Mechanical milling process uses both forward and reverse directions alternate run, runs 0.2～0.5h, suspends 0.05～0.2h or without stopping
Stay, rerun the most in the opposite direction.
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| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| 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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| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| 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 |
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