CN106430097B - Composite hydrogen storage material and preparation method thereof - Google Patents
Composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN106430097B CN106430097B CN201610796014.8A CN201610796014A CN106430097B CN 106430097 B CN106430097 B CN 106430097B CN 201610796014 A CN201610796014 A CN 201610796014A CN 106430097 B CN106430097 B CN 106430097B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
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- 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
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Abstract
The present invention relates to hydrogen storage material fields, and in particular, to a kind of composite hydrogen storage material and preparation method thereof.The composite hydrogen storage material contains the boron hydride of the first metallic element doped with the second metallic element, wherein first metallic element is Li, Na or K；Second metallic element is one of Rb, Cs, group iia element, Group IIIB element, group ivb element, Group VB element, group VIB element, V Group IIB element, group VIII element, group ib element, group iib element and group III A metallic element or a variety of.Composite hydrogen storage material provided by the invention makes in common light metal boron hydride doped with the second metallic element, the boron hydride of first metallic element doped with the second metallic element is non-solvent compound, so as to release the more pure hydrogen of safer and atmosphere.
Description
Technical field
The present invention relates to hydrogen storage material fields, and in particular, to a kind of composite hydrogen storage material and preparation method thereof.
Background technique
Hydrogen is element generally existing in universe, what tellurian substance 66% was made of hydrogen, as a kind of completely clear
The advantages that clean new and renewable energy, Hydrogen Energy is with rich reserves, and light weight, energy density is high, environmentally protective, are considered
It is following one of the new energy for being most hopeful to substitute traditional fossil energy.Under normal temperature and pressure, hydrogen exists in a gaseous form, easily
Characteristics, the storage and transport to hydrogen such as diffusion, inflammable, explosive bring very big difficulty.Therefore hydrogen is safe and efficient
Storing technology limits the scale of Hydrogen Energy, practical utilization.
Solid-state hydrogen storage in practical applications with the obvious advantage, hydrogen-storage density is big, and highly-safe, hydrogen storage is at low cost, is convenient for
Storage and transport.In current solid-state hydrogen storage research field, coordinating metal hydride is mainly made of light metal and hydrogen, can be with
A greater amount of hydrogen is stored, there is high hydrogen storage capability.
With LiBH4For the light metal boron hydride of representative, theoretical hydrogen storage capability is up to 18.4%, has good reversible
Property and cyclical stability, it is considered to be most promising hydrogen storage material.However, due to LiBH4Belong to rhombic system, wherein B
Atom is combined to form [BH in the form of covalent bond with 4 H atoms of surrounding4]-Tetrahedron, then Li is combined in the form of ionic bond+It is formed
LiBH4Crystal, steric configuration are stable tetrahedral structures, have strong chemical bonding effect between element, so that with LiBH4For
The alkali metal boronhydride of representative is faced with thermodynamics, the dynamics problem of serious suction/hydrogen release.Its hydrogen discharging temperature is high, puts
Hydrogen rate is low and hydrogen desorption capacity is lower.
Summary of the invention
The purpose of the present invention is be that high for existing light metal boron hydride hydrogen discharging temperature, hydrogen desorption capacity is more low to lack
It falls into, provides that a kind of hydrogen discharging temperature is low and higher composite hydrogen storage material of hydrogen desorption capacity and preparation method thereof.
To achieve the goals above, the present invention provides a kind of composite hydrogen storage material, which contains doped with the second metal
The boron hydride of first metallic element of element, wherein first metallic element is Li, Na or K；Second metallic element
For Rb, Cs, group iia element, Group IIIB element, group ivb element, Group VB element, group VIB element, V Group IIB
Element, group VIII element, group ib element, group iib element and group III A one of metallic element or a variety of.
The present invention also provides a kind of preparation methods of composite hydrogen storage material, this method comprises:
(1) in an inert atmosphere, in the presence of liquid phase protective agent, by the boron hydride of the first metallic element and the second metal
The halide of element carries out ball milling；The liquid phase protective agent is hexamethylene and/or heptane；
(2) ball milling products therefrom is subjected to desolvation processing；
Wherein, first metallic element is Li, Na or K；Second metallic element be Rb, Cs, group iia element,
Group IIIB element, group ivb element, Group VB element, group VIB element, V Group IIB element, group VIII element,
One of IB race element, group iib element and group III A metallic element are a variety of.
The present invention also provides composite hydrogen storage materials prepared by the above method.
Composite hydrogen storage material provided by the invention makes in common light metal boron hydride doped with the second metallic element,
The boron hydride of first metallic element doped with the second metallic element is non-solvent compound, so as to release it is safer and
The more pure hydrogen of atmosphere.
Also, it is the same as be described hereinafter, it also have the advantage that
1, composite hydrogen storage material preparation process of the present invention is very simple, it is only necessary to which liquid phase ball milling at room temperature is not necessarily to
Specific catalyst is added, and does not need to carry out cumbersome purification step after ball milling.
2, the hydroboration containing the first metallic element doped with the second metallic element will be made by means of the present invention
The composite hydrogen storage material of object, which has lower hydrogen discharging temperature and higher hydrogen desorption capacity, such as starts largely to release hydrogen
When temperature all at 400 DEG C hereinafter, hydrogen desorption capacity is closer to theoretical hydrogen storage content.Significantly improve its thermodynamics and kinetics performance.
3, raw material sources are extensive, at low cost.Reaction generate chemical property vivaciously and not yet commercialized compound hydroboration
Object hydrogen storage material, the material simultaneously do not contain solvate.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD spectrum of composite hydrogen storage material of the invention, wherein Fig. 1 (a) is the resulting composite hydrogen occluding of embodiment 1
The XRD spectrum of materials A 1, Fig. 1 (b) are the XRD spectrums of the resulting composite hydrogen storage material A3 of embodiment 3, and Fig. 1 (c) is embodiment 6
The XRD spectrum of resulting composite hydrogen storage material A6.
Fig. 2 is the XRD spectrum of composite hydrogen storage material of the invention, wherein Fig. 2 (a) is the resulting composite hydrogen occluding of embodiment 2
The XRD spectrum of materials A 2, Fig. 2 (b) are the XRD spectrums of the resulting composite hydrogen storage material A4 of embodiment 4, and Fig. 2 (c) is embodiment 5
The XRD spectrum of resulting composite hydrogen storage material A5.
Fig. 3 is the thermogravimetric curve of composite hydrogen storage material of the invention, wherein Fig. 3 (a) is the heat of composite hydrogen storage material A1
Weight-loss curve, Fig. 3 (b) are the thermogravimetric curves of composite hydrogen storage material A3, and Fig. 3 (c) is that the thermal weight loss of composite hydrogen storage material A6 is bent
Line.
Fig. 4 is the thermogravimetric curve of composite hydrogen storage material of the invention, wherein Fig. 4 (a) is the heat of composite hydrogen storage material A2
Weight-loss curve, Fig. 4 (b) are the thermogravimetric curves of composite hydrogen storage material A4, and Fig. 4 (c) is that the thermal weight loss of composite hydrogen storage material A5 is bent
Line.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of composite hydrogen storage material, which contains the first metallic element doped with the second metallic element
Boron hydride, wherein first metallic element be Li, Na or K；Second metallic element is Rb, Cs, group iia is first
Element, Group IIIB element, group ivb element, Group VB element, group VIB element, V Group IIB element, group VIII element,
One of metallic element of group ib element, group iib element and group III A is a variety of.
According to the present invention, the boron hydride of first metallic element doped with the second metallic element can be understood as
The first metallic element of part in the boron hydride of one metallic element is replaced by the second metallic element, to be formed in the lattice of part
The doped products with lattice defect replaced by the second metallic element of the first metallic element.
According to the present invention, the specific example as the group iia element of the second metallic element includes: Mg, Ca, Sr etc..
The specific example of Group IIIB element as the second metallic element includes: Sc, Y, La, Ce etc..
The specific example of group ivb element as the second metallic element includes: Ti, Zr etc..
The specific example of Group VB element as the second metallic element includes: V etc..
The specific example of group VIB element as the second metallic element includes: Cr etc..
The specific example of V Group IIB element as the second metallic element includes: Mn etc..
The specific example of group VIII element as the second metallic element includes: Fe, Co, Ni etc..
The specific example of group ib element as the second metallic element includes: Cu etc..
The specific example of group iib element as the second metallic element includes: Zn etc..
The specific example of group III A metallic element as the second metallic element includes: Al etc..
Preferably, the second metallic element is Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, La
With one of Ce or a variety of.
It is resulting doped with for example, by using Li as the first metallic element and in the case that Ca is as the second metallic element
The boron hydride of first metallic element of two metallic elements can be LiCa (BH4)3。
It is resulting doped with for example, by using Li as the first metallic element and in the case that Mg is as the second metallic element
The boron hydride of first metallic element of two metallic elements can be LiMg (BH4)3。
According to the present invention, although there is no particular limitation by the present invention, under normal conditions, which also contains the first gold medal
Belong to element halide and the second metallic element halide, the halide for example can for fluoride, chloride, bromide,
Iodide etc..Preferably, in the composite hydrogen storage material, the boron hydrogen of first metallic element doped with the second metallic element
The content of compound is 5-15 weight %, more preferably 7-9 weight %.And composite hydrogen storage material of the invention does not contain solvation
Object, component are substantially non-solvent compound.
Wherein, the halide of the first metallic element can be for example LiCl, NaCl etc..
Wherein, the halide of the second metallic element for example can be CaCl2、MgCl2Deng.
In the composite hydrogen storage material, in addition to having halide and second metal member of the boron hydride also containing the first metallic element
The halide of element, it is preferable that the molar ratio of the first metallic element and the second metallic element is 1-10:1 in the material, more preferably
4-6:1.
The present invention also provides a kind of preparation methods of composite hydrogen storage material, this method comprises:
(1) in an inert atmosphere, in the presence of liquid phase protective agent, by the boron hydride of the first metallic element and the second metal
The halide of element carries out ball milling；The liquid phase protective agent is hexamethylene and/or heptane；
(2) ball milling products therefrom is subjected to desolvation processing；
Wherein, first metallic element is Li, Na or K；Second metallic element be Rb, Cs, group iia element,
Group IIIB element, group ivb element, Group VB element, group VIB element, V Group IIB element, group VIII element,
One of IB race element, group iib element and group III A metallic element are a variety of.
According to the present invention, first metallic element and the second metallic element are as described above, no longer superfluous herein
It states.
Wherein, the boron hydride of the first metallic element is LiBH4、NaBH4And KBH4In it is one or more.
Wherein, the halide of second metallic element for example can be fluoride, the second metal of the second metallic element
One of iodide of the chloride of element, the bromide of the second metallic element and the second metallic element are a variety of.This is described
The specific example of the halide of second metallic element for example can be with are as follows: MgCl2、MgF2、AlCl3、CaCl2、ScCl3、TiCl3、
TiF3、VCl3、CrCl3、MnCl2、FeCl2、CoCl2、NiCl2、CuCl2、ZnF2、SrCl2、YCl3、ZrCl4、LaCl3And CeCl3In
It is one or more.
According to the present invention, the dosage of the halide of the boron hydride and the second metallic element of first metallic element can be with
It changes in a wider range, but in order to obtain the more excellent composite hydrogen storage material of performance, it is preferable that the first metal member
The dosage of the halide of the boron hydride and the second metallic element of element makes mole of the first metallic element and the second metallic element
Than for 1-10:1, preferably 4-6:1, for example, 5-6:1.
According to the present invention, the inert atmosphere in step (1) for example can be by the inert gas offer of this field routine
The inert atmosphere that one of inert atmosphere, for example, helium, neon, argon gas etc. or a variety of inert gases provide.
According to the present invention, the liquid phase protective agent can aid in method of the invention obtain non-solvent compound doped with
The boron hydride of first metallic element of the second metallic element, the present inventor is it has been unexpectedly found that work as the liquid phase
Protective agent is that above-mentioned non-solvent compound can be made in hexamethylene and/or heptane, so that resulting composite hydrogen storage material can
Obtain more pure hydrogen.
Wherein, the protectant dosage of the liquid phase can change in a wider range, for the ease of the composite hydrogen-storage material
The preparation of material, it is preferable that the halide of the boron hydride and the second metallic element of the first metallic element relative to 100g it is total
Weight, the protectant dosage of liquid phase are 100-600mL, preferably 400-500mL.
It according to the present invention, as described above, will be so that the second metallic element be doped by the mechanical milling process of step (1)
In the boron hydride of first metallic element, the boron hydride containing the first metallic element doped with the second metallic element is formed
Composite hydrogen storage material.That is, the mechanical milling process will make the ionic portions of the second metallic element replace the first metallic element
Boron hydride the first metallic element of center, to obtain the hydroboration of the first metallic element doped with the second metallic element
Object, while generating the halide of the first metallic element of by-product.Ideally, it is believed that the halide of the second metallic element
The second metallic element provided it is fully doped enter the first metallic element boron hydride, however be usually unable to enough react completely,
Therefore, the resulting product of ball milling may be considered by the first metallic element doped with the second metallic element boron hydride,
The composite hydrogen-storage material feed composition of the halide of the halide of one metallic element and the second metallic element composition.Wherein, although ball
It grinds in product, the halide mode presence that the halide of the second metallic element can be with independent second metallic element, still
The present invention also measures the halide of the second metallic element under this form into the first metal doped with the second metallic element
In the boron hydride form of element.
In the case of, according to the invention it is preferred to, the condition of the ball milling include: ball material mass ratio be 10-120:1 (preferably
10-20:1), revolving speed be 250-600rpm (preferably 300-400rpm), temperature be 10-30 DEG C, the time be 0.5-30h (preferably
For 5-24h, more preferably 10-20h).It is highly preferred that the ball milling is by the way of positive and negative alternate operation, such as every 20-60min
Just antiport.Above-mentioned ball milling is carried out for example, by using planetary ball mill.
In the case of, according to the invention it is preferred to, in step (2), the condition of the desolvation processing includes: vacuum pressure
For -100KPa to -1KPa, temperature is 10-30 DEG C, and the time is 1-5h (preferably 2-4h).
The present invention also provides composite hydrogen storage materials prepared by the above method.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example:
XRD spectrum is measured using Rigaku Rigaku DMAX2400 type X-ray diffractometer.
Thermogravimetric curve is measured using Germany's Nai Chi company STA449F3 type synchronous solving.
The temperature stage of main dehydrogenation refers to that system releases the temperature range of a large amount of hydrogen.
Total weight loss refers to hundred of the original matter gross mass in the quality and reaction system of the substance reduction in reaction system
Divide weight ratio, is equivalent to practical hydrogen storage content.
Theoretical hydrogen storage content refers in reaction system raw material by LiBH4The quality for the protium that equal boron hydrides provide with react
The percent by weight ratio of system total mass of raw material.
Embodiment 1
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
(1) in the glove box for being filled with argon gas, by the LiBH of 11.256mmol4With the MgCl of 1.876mmol2It is added not
In steel ball grinding jar of becoming rusty (ball material mass ratio is 20:1, and steel ball sphere diameter is 8mm), and 1.7mL hexamethylene is added, ball milling is sealed
Tank simultaneously takes out glove box.Ball milling is carried out on planetary ball mill, ball milling condition includes: the revolving speed 300rpm at 25 DEG C, just
The mode (after every operation 1h of short duration pause 0.2h, then antiport) of anti-alternate run, effective Ball-milling Time are 20h.
(2) by the product after ball milling at vacuum pressure -100KPa in 25 DEG C of dry 4h, obtain composite hydrogen storage material A1.
Through XRD spectrum detection (its map is shown in shown in Fig. 1 (a)), the composite hydrogen storage material is in addition to there is original matter MgCl2With
LiBH4Except, LiCl and novel substance are also generated, which is the LiBH doped with Mg4, it is represented by LiMg (BH4)3, i.e.,
Ball milling product is by MgCl2、LiBH4、LiCl、Mg(BH4)2With LiMg (BH4)3The mixture of composition, LiMg (BH4)3Content about
For 9 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates composite material cyclohexane
It is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Embodiment 2
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
(1) in the glove box for being filled with argon gas, by the LiBH of 19.270mmol4With the CaCl of 3.854mmol2It is added not
In steel ball grinding jar of becoming rusty (ball material mass ratio is 10:1, and steel ball sphere diameter is 8mm), and 4.2mL hexamethylene is added, ball milling is sealed
Tank simultaneously takes out glove box.Ball milling is carried out on planetary ball mill, ball milling condition includes: the revolving speed 400rpm at 25 DEG C, just
The mode (after every operation 1h of short duration pause 0.2h, then antiport) of anti-alternate run, effective Ball-milling Time are 10h.
(2) by the product after ball milling at vacuum pressure -100KPa in 25 DEG C of dry 2h, obtain composite hydrogen storage material A2.
Through XRD spectrum detection (its map is shown in shown in Fig. 2 (a)), the composite hydrogen storage material is in addition to there is original matter CaCl2With
LiBH4Except, also generate LiCl, Ca (BH4)2And novel substance, the novel substance are the LiBH doped with Ca4, it is represented by LiCa
(BH4)3, i.e. ball milling product is by CaCl2、LiBH4、LiCl、Ca(BH4)2With LiCa (BH4)3The mixture of composition, LiCa
(BH4)3Content be about 7 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates compound
Material cyclohexane is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Embodiment 3
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
(1) in the glove box for being filled with argon gas, by the LiBH of 12.396mmol4With the MgCl of 3.099mmol2It is added not
In steel ball grinding jar of becoming rusty (ball material mass ratio is 15:1, and steel ball sphere diameter is 8mm), and 2.5mL hexamethylene is added, ball milling is sealed
Tank simultaneously takes out glove box.Ball milling is carried out on planetary ball mill, ball milling condition includes: the revolving speed 350rpm at 25 DEG C, just
The mode (after every operation 1h of short duration pause 0.2h, then antiport) of anti-alternate run, effective Ball-milling Time are 16h.
(2) by the product after ball milling at vacuum pressure -100KPa in 25 DEG C of dry 3h, obtain composite hydrogen storage material A3.
Through XRD spectrum detection (its map is shown in shown in Fig. 1 (b)), the composite hydrogen storage material is in addition to there is original matter MgCl2With
LiBH4Except, LiCl and novel substance are also generated, which is the LiBH doped with Mg4, it is represented by LiMg (BH4)3, i.e.,
Ball milling product is by MgCl2、LiBH4、LiCl、Mg(BH4)2With LiMg (BH4)3The mixture of composition, LiMg (BH4)3Content about
For 9 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates composite material cyclohexane
It is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Embodiment 4
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
(1) in the glove box for being filled with argon gas, by the LiBH of 8.556mmol4With the CaCl of 2.139mmol2It is added stainless
In steel ball grinding jar (ball material mass ratio is 20:1, and steel ball sphere diameter is 8mm), and 1.5mL hexamethylene is added, ball grinder is sealed
And take out glove box.Carry out ball milling on planetary ball mill, ball milling condition includes: the revolving speed 300rpm at 25 DEG C, positive and negative
The mode (after every operation 1h of short duration pause 0.2h, then antiport) of alternate run, effective Ball-milling Time are 10h.
(2) by the product after ball milling at vacuum pressure -100KPa in 25 DEG C of dry 2h, obtain composite hydrogen storage material A4.
Through XRD spectrum detection (its map is shown in shown in Fig. 2 (b)), the composite hydrogen storage material is in addition to there is original matter CaCl2With
LiBH4Except, also generate LiCl, Ca (BH4)2And novel substance, the novel substance are the LiBH doped with Ca4, it is represented by LiCa
(BH4)3, i.e. ball milling product is by CaCl2、LiBH4、LiCl、Ca(BH4)2With LiCa (BH4)3The mixture of composition, LiCa
(BH4)3Content be about 7 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates compound
Material cyclohexane is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Embodiment 5
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
According to method as described in example 4, unlike, in step (1), wherein LiBH4For 5.484mmol, CaCl2For
2.742mmol.To finally obtain composite hydrogen storage material A5 by subsequent step.
Through XRD spectrum detection (its map is shown in shown in Fig. 2 (c)), the composite hydrogen storage material is in addition to there is original matter CaCl2With
LiBH4Except, also generate LiCl, Ca (BH4)2And novel substance, the novel substance are the LiBH doped with Ca4, it is represented by LiCa
(BH4)3, i.e. ball milling product is by CaCl2、LiBH4、LiCl、Ca(BH4)2With LiCa (BH4)3The mixture of composition, LiCa
(BH4)3Content be about 7 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates compound
Material cyclohexane is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Embodiment 6
The present embodiment is for illustrating composite hydrogen storage material and preparation method thereof of the invention.
According to method as described in example 4, the difference is that, in step (1), using MgCl2Replace CaCl2, wherein LiBH4
For 6.108mmol, MgCl2For 3.054mmol.To finally obtain composite hydrogen storage material A6 by subsequent step.
Through XRD spectrum detection (its map is shown in shown in Fig. 1 (c)), the composite hydrogen storage material is in addition to there is original matter MgCl2With
LiBH4Except, LiCl and novel substance are also generated, which is the LiBH doped with Mg4, it is represented by LiMg (BH4)3, i.e.,
Ball milling product is by MgCl2、LiBH4、LiCl、Mg(BH4)2With LiMg (BH4)3The mixture of composition, LiMg (BH4)3Content about
For 9 weight %.Infrared detection product has no the C-H stretching vibration characteristic peak of cyclohexane solvent, illustrates composite material cyclohexane
It is completely removed, thus resulting composite hydrogen storage material and non-solvent compound.
Comparative example 1
By pure LiBH4As hydrogen storage material DA1.
Comparative example 2
According to method described in embodiment 1, the difference is that, hexamethylene is replaced using tetrahydrofuran, to obtain compound storage
Hydrogen material DA2.
Through infrared detection, there are the characteristic peaks of tetrahydrofuran solvent, so that resulting composite hydrogen storage material is solvate,
It has obtained containing LiCa (BH4)3·THF、Ca(BH4)2·THF、CaCl2、LiBH4, LiCl composite hydrogen storage material.
Test case 1
Under the conditions of argon gas, 600 DEG C are heated to from 50 DEG C with the heating rate of 10 DEG C/min, measures above-mentioned composite hydrogen-storage material
The thermogravimetric curve for expecting A1-A6 and hydrogen storage material DA1-DA2, obtains hydrogen discharging temperature and hydrogen desorption capacity, the results are shown in Table 1.
Table 1
| Hydrogen storage material | The temperature stage of main dehydrogenation | Total weight loss/% | Theoretical hydrogen storage content/% |
| A1 | 80℃-360℃ | 9.61% | 10.71% |
| A2 | 100℃-300℃ | 8.86% | 9.17% |
| A3 | 135℃-370℃ | 8.78% | 8.84% |
| A4 | 150℃-330℃ | 7.86% | 8.14% |
| A5 | 180℃-350℃ | 5.12% | 5.22% |
| A6 | 100℃-350℃ | 5.01% | 5.81% |
| DA1 | 400℃-520℃ | 9.03% | 18.5% |
| DA2 | 300℃-520℃ | 9.17% | 5.22% |
By upper table can be seen that composite hydrogen storage material of the invention can since at lower temperature can quickly put
Hydrogen, and total hydrogen desorption capacity is relatively high.Composite hydrogen storage material A1-A6 is compared, is considered for thermodynamics and kinetics performance, A1,
A2 and A3 material is more highly preferred to.
Wherein, the thermogravimetric curve of composite hydrogen storage material A1, A3 and A6 is shown in Fig. 3 (a)-(c) respectively, can be seen by Fig. 3
Out, composite hydrogen storage material A1 has reached 8.10% in 360 DEG C of weight loss, is basically completed hydrogen release, especially 180-300 DEG C it
Between hydrogen discharging rate it is most fast, hydrogen desorption capacity reaches 4.23% in the section；Composite hydrogen storage material A3 has reached in 370 DEG C of weight loss
8.77%, it is basically completed hydrogen release, the hydrogen discharging rate especially between 135-370 DEG C is most fast, and hydrogen desorption capacity reaches in the section
7.06%；Composite hydrogen storage material A6 has reached 4.49% in 350 DEG C of weight loss, is basically completed hydrogen release.
The thermogravimetric curve of composite hydrogen storage material A2, A4 and A5 are shown in Fig. 4 (a)-(c) respectively, as seen in Figure 4, multiple
It closes hydrogen storage material A2 and has reached 6.90% in 300 DEG C of weight loss, hydrogen release is basically completed, especially between 150-300 DEG C
Hydrogen discharging rate is most fast, and hydrogen desorption capacity reaches 5.28% in the section；Composite hydrogen storage material A4 has reached in 370 DEG C of weight loss
6.70%, it is basically completed hydrogen release；Composite hydrogen storage material A5 has reached 4.02% in 350 DEG C of weight loss, is basically completed hydrogen release.
It is noted that the main hydrogen release section of the composite hydrogen storage material DA2 of comparison is 300-520 DEG C.But this is compound
Object has the defect that a large amount of tetrahydrofurans are released during low-temperature heat, so that total weight loss is much larger than its theoretical hydrogen storage
Amount, and nonideal hydrogen storage material.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (1)
1. a kind of preparation method of composite hydrogen storage material, which is characterized in that this method comprises:
(1) in an inert atmosphere, in the presence of liquid phase protective agent, lithium borohydride and magnesium chloride are subjected to ball milling；The liquid phase is protected
Protecting agent is hexamethylene and/or heptane, and the molar ratio of lithium borohydride and magnesium chloride is 6:1, wherein the condition of the ball milling includes:
Ball material mass ratio is 10-20:1, and revolving speed 300-400rpm, temperature is 10-30 DEG C, time 10-20h, and ball milling is using positive and negative
The mode of alternate run, every 20-60min just antiport；
(2) ball milling products therefrom is subjected to desolvation processing, the condition of desolvation processing include: vacuum pressure be-
100KPa to -1KPa, temperature are 10-30 DEG C, time 1-5h；
Wherein, the total weight relative to the lithium borohydride of 100g and magnesium chloride, the protectant dosage of liquid phase are 400-
500mL。
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