CN107188121A - A kind of improved LiNH2LiH composite hydrogen storage materials and the method for improving hydrogen storage property - Google Patents
A kind of improved LiNH2LiH composite hydrogen storage materials and the method for improving hydrogen storage property Download PDFInfo
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- CN107188121A CN107188121A CN201710458743.7A CN201710458743A CN107188121A CN 107188121 A CN107188121 A CN 107188121A CN 201710458743 A CN201710458743 A CN 201710458743A CN 107188121 A CN107188121 A CN 107188121A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The present invention relates to a kind of improved LiNH2LiH composite hydrogen storage materials and the method for improving hydrogen storage property, belong to the technical field of solid-state hydrogen storage during hydrogen energy source is developed.The improved LiNH2LiH composite hydrogen storage materials, are doping K2TiF6LiNH2LiH composite hydrogen storage materials.Alkali metal light metal hydride (LiH LiNH2) solid-state hydrogen storage material has the advantages that high-performance, low-density, the present invention is by ball action by K+、Ti+、F‑Ion is doped to LiH LiNH simultaneously2In mixture so that the dehydrogenation initial temperature of the compound substantially reduces (124 DEG C of reduction), and the compound speed is significantly improved, the Reversible Cycle of compound system, which is inhaled, puts stabilized hydrogen raising.In catalyst K2TiF6In the presence of, Li N H system performances are improved, the inventive method is safe efficient so that the practical application of hydrogen car and fuel cell is further.
Description
Technical field
The invention belongs to lightweight alkali metal solid state chemistry hydrogen storage technology field, more particularly to LiNH2- LiH system hydrogen storages
Exploration, the research for the effective catalyst that can improve.
Background technology
In the last few years, the eco-friendly power source talked about extensively by people --- hydrogen, is considered as following most promising fuel, but
It is that we want the utilization of Hydrogen Energy to come true to also need to solve many problems, especially in terms of hydrogen storage.Due to hydrogen
Danger is higher and volume energy density is relatively low, and traditional storage of higher pressures and low-temperature storage are for transport applications in practice
It is not best bet.At present, the appearance of solid-state hydrogen storage technology, improves current situation.Solid-state hydrogen storage (utilizes hydrogen and material
A kind of chemical hydrogen storage mode of material reaction generation hydride) advantage is had more in terms of security and economy, especially for light
Prime element hydrogen storage system, realizes the safe hydrogen storage of the solid-state of high weight and high volume density.
In hydrogen storage field, metal hydride storage hydrogen is a kind of wider hydrogen storage method of current application, still,
The hydrogen storage content of most metal hydrides is only 1wt%~3wt%, and experiment proof can not meet the vehicle-mounted storage of business well
The need for hydrogen.Therefore, people start to turn to some light-weight metals of research, such as alkali metal lithium, the compound of sodium or potassium.Since
The nitride and amides that Chen Ping in 2002 et al. has delivered lithium metal first on Nature can be in relatively low temperature
Reversibly inhale for about 320 DEG C and put hydrogen capacity and reach 11.5wt%, subsequent LiNH2- LiH systems are also used as a kind of solid-state hydrogen storage system
System is suggested.LiNH2Can be in 200~300 DEG C of reversible hydrogen adsorption and desorptions after-LiH mixing, the temperature section is for practical application
Still it is higher, it is impossible to the requirement with the commercial hydrogen storage of modernization to be met, in order to improve LiNH2The suction of-LiH systems/put hydrogen
Can, someone's research adds TiCl in the Li-N-H systems3, KH, KX (wherein X be F, Cl or Br) compound etc., find plus
Enter these catalyst has preferable catalytic effect for improving suction/hydrogen desorption kineticses performance of Li-N-H systems, can significantly change
Kind LiNH2The hydrogen storage property of-LiH systems.But tri- kinds of ions of K+, Ti-, F- are acted on into some hydrogen storage system simultaneously simultaneously
Relevant report is simultaneously few, currently without document report by K2TiF6Into Li-N-H hydrogen storage systems, the research is to these three ions
It is added to one in Li-N-H hydrogen storage systems research simultaneously, by the synergy of three to expect that hydrogen storage property can be improved.
The content of the invention
Present invention aims at propose a kind of LiNH that can effectively improve hydrogen storage property2The preparation side of-LiH hydrogen storage materials
Method.
The technical scheme is that：By K2TiF6The LiNH of doping2Ball is carried out under an atmosphere of hydrogen with LiH mixture
Mill processing, acquirement contains K2TiF6LiNH2- LiH composite hydrogen storage materials.
The K that the present invention is added2TiF6LiNH is substantially improved as catalyst2The hydrogen desorption performance of-LiH systems, is obtained
Relatively low puts hydrogen peak temperature with putting hydrogen initial temperature, and hydrogen discharging rate is improved, also, K2TiF6Doping make LiNH2- LiH systems
Inhale the cyclical stability raising for putting hydrogen.
The present invention has obtained doping K of the size up to Nano grade by ball grinding method in a hydrogen atmosphere2TiF6's
LiNH2The crystal grain of-LiH composites so that the K of doping2TiF6LiNH can be preferably distributed to2With in LiH samples,
Give full play to K+、Ti+、F-Ion acts synergistically, so as to significantly improve LiNH2- LiH system hydrogen storage properties.
Further, K of the present invention2TiF6Doping account for 1~5mol% of the mixture.The different doping of addition
The K of amount2TiF6LiNH can be reduced to varying degrees2- LiH system desorption temperatures, improve dehydrogenation rate.Improving LiNH2-LiH
System hydrogen storage property and on the basis of ensureing its hydrogen storage ability, selects K2TiF6Doping in the range of 1~5mol%, pass through
Experimental studies have found that, non-impurity-doped K2TiF6LiNH2The dehydrogenation initial temperature of-LiH samples is 199 DEG C, in comparison, K2TiF6
LiNH when doping reaches 1mol%2- LiH composite sample system dehydrogenations initial temperature is 92 DEG C, reduces about 107 DEG C；K2TiF6Doping
Amount is 85 DEG C up to 3mol% dehydrogenations initial temperature, reduces about 114 DEG C；K2TiF6It is 75 that doping, which reaches 5mol% dehydrogenations initial temperature,
DEG C, reduce about 124 DEG C.As can be seen that with K2TiF6The desorption temperature of increase system of doping decline accordingly.Work as work
Make temperature from when being heated to 150 DEG C for 50 DEG C, within the range LiNH2The hydrogen desorption capacity of-LiH samples and doping K2TiF6Sample is put
Hydrogen amount is compared to fewer, doping 1mol%, 3mol% and 5mol%K2TiF6The hydrogen desorption capacity of sample be respectively 0.680wt%,
1.478wt% and 2.496wt%, and LiNH2The hydrogen desorption capacity of-LiH samples is only 0.651wt%.From the above with data point
From the point of view of analysis, K2TiF6Doping improve LiNH to a certain extent2The hydrogen storage property of-LiH systems, reduces the starting temperature of dehydrogenation
Degree so that the composite above has some superiority in the development and utilization of Hydrogen Energy.
It is highly preferred that by Experimental comparison, and data analysis, we select K2TiF6Doping account for the mixture
5mol% be used as best research analysis object.In doping 5mol%K2TiF6Under conditions of, obtain the de- starting of relatively low hydrogen attached
Temperature (75 DEG C) and dehydrogenation peak temperature (233 DEG C), meanwhile, have preferable hydrogen discharging rate under the doping, operating temperature from
When room temperature is heated to 250 DEG C, adulterate 5mol%K2TiF6LiNH2The hydrogen discharging rate of-LiH composite hydrogen storage materials be 4.33wt%/
H, and LiNH2The hydrogen discharging rate of-LiH hydrogen storage materials is only 2.83wt%/h.In addition, with doping 1mol%, 3mol%K2TiF6Phase
Compare, adulterate 5mol%K2TiF6Suction can be more promoted to put stabilized hydrogen circulation, it is 250 DEG C to inhale hydrogen operating temperature, puts hydrogen operating temperature
For 300 DEG C, carry out circulation suction and put hydrogen experiment.Adulterate 5mol%K2TiF6LiNH2- LiH composite hydrogen storage materials can carry out reversible follow
Ring 5 times, and LiNH2- LiH hydrogen storage materials can only be carried out 2 times.
The LiNH2Mixing quality ratio with LiH is 1: 1.Li is reported first from Chen Ping in 2002 et al.3N can be according to side
Since journey (1) reversibly carries out 2 steps storage hydrogen, hereafter Li-N-H systems hydrogen storage material is received significant attention：
AndReaction system due to its of a relatively high hydrogen storage content (6.5wt%) and compared with
Low reaction activity turns into one of popular hydrogen storage material.Such as equation (2)
Therefore, from 1:1 LiNH2LiNH is studied with LiH mixture2The hydrogen storage property of-LiH systems.
The atmosphere of hydrogen condition is 0.6MPa.In order to suppress LiNH2Generation Li is reacted during ball milling with LiH2NH
And H2, pouring for another aspect high pressure hydrogen preferably carry out ball-milling treatment.Selection is under higher hydrogen (0.6MPa) pressure
Carry out ball milling pretreatment.
With LiNH2- LiH hydrogen storage materials are compared, and the present invention contains K2TiF6LiNH2- LiH composite hydrogen storage materials put hydrogen
Initial temperature, put hydrogen peak temperature reduction, hydrogen discharging rate improve, circulation hydrogen storage property be improved significantly.
Brief description of the drawings
Fig. 1 is LiNH2- LiH doping different proportions K2TiF6The thermal desorption mass spectrogram of sample after ball milling.
Fig. 2 is LiNH2- LiH doping different proportions K2TiF6The weight-loss curve figure of sample after ball milling.
Fig. 3 is LiNH2- LiH non-impurity-dopeds, doping 5mol%K2TiF6Sample milled sample puts hydrogen cyclic curve at 300 DEG C
Figure.
Fig. 4 is LiNH2- LiH non-impurity-dopeds, doping 5mol%K2TiF6Sample milled sample is respectively at 200 DEG C, 250 DEG C, 300 DEG C
Under isothermal dehydrogenation follow figure.
Fig. 5 is LiNH2- LiH non-impurity-dopeds, doping 10mol%KF, doping 5mol%TiF4And doping 5mol%K2TiF6
Milled sample thermal desorption mass spectrogram.
Embodiment
First, embodiment 1：
1st, ball milling LiNH2With LiH (1：1) biased sample：In argon gas glove box, weigh by LiNH2With LiH crystal with 1: 1
The sample 0.3g of mass ratio mixing composition is fitted into the ball grinder containing 20 stainless steel steel balls.Ball grinder is taken out, is filled with
0.6MPa hydrogen, and ball grinder is symmetrically arranged in planetary ball mill, ball-milling treatment 2 is small under 450 revs/min of rotating speed
When.
2nd, LiNH after ball milling2- LiH biased samples carry out hydrogen thermal desorption test：In argon gas glove box, reclaim after ball milling
LiNH2With LiH biased samples, LiNH after 13mg ball millings is taken2- LiH biased samples, pass through caloic combined instrument carry out hydrogen desorption survey
Examination, gas signal is detected as H2, condition is that (flow velocity is 20ml min to argon gas atmosphere-1), 50~600 DEG C, heating rate is 10k/
min.Non-impurity-doped LiNH can be obtained2The hydrogen of putting of-LiH systems is originated and peak temperature, and bent in the weight loss of the temperature section
Line.
3rd, LiNH after ball milling2- LiH biased samples carry out hydrogen desorption kineticses test：In argon gas glove box, 150mg is weighed
LiNH after ball milling2- LiH biased samples pass through PCT (gases at high pressure adsorption instrument) progress etc. at 200 DEG C, 250 DEG C, 300 DEG C respectively
Warm hydrogen desorption experiment.LiNH can be obtained2The isothermal dehydrogenation of-LiH biased samples respectively at 200 DEG C, 250 DEG C, 300 DEG C is bent
Line.In addition, in argon gas glove box, weighing LiNH after 150mg ball millings2By PCT, (gases at high pressure are adsorbed-LiH biased samples
Instrument) set operating temperature to inhale hydrogen and 300 DEG C of dehydrogenations for 250 DEG C, non-impurity-doped LiNH can be obtained2- LiH systems are at 200 DEG C and 300
Hydrogen discharging rate at DEG C and put hydrogen cyclic curve.
2nd, embodiment 2：
1st, with 1: 1 mass ratio by LiNH2First mixed with LiH, then the 1mol%K that adulterates respectively2TiF6, 3mol%K2TiF6
And 3mol%K2TiF6Obtain K2TiF6The LiNH of doping2With LiH mixed crystals.
Adulterate K2TiF6LiNH2With LiH mixed crystals：In argon gas glove box, 0.3g doping K is weighed2TiF6LiNH2
It is fitted into LiH mixed crystals in the ball grinder containing 20 stainless steel steel balls.Then ball grinder is taken out from glove box, is filled with
0.6MPa hydrogen, and ball grinder is symmetrically arranged in planetary ball mill, ball-milling treatment 2 is small under 450 revs/min of rotating speed
When.
2nd, after ball milling adulterate different content K2TiF6LiNH2- LiH biased samples carry out hydrogen thermal desorption test：In argon
In gas glove box, the different amounts of K that adulterated after ball milling is reclaimed2TiF6LiNH2- LiH biased samples, mix after 13mg ball millings are taken respectively
Miscellaneous 1mol%, 3mol% and 5mol%K2TiF6LiNH2- LiH biased samples carry out hydrogen desorption survey by caloic combined instrument
Examination, gas signal is detected as H2, condition is that (flow velocity is 20ml min to argon gas atmosphere-1), 50~600 DEG C, heating rate is 10k/
min.Adulterate 1mol%, 3mol% and 5mol%K can be obtained2TiF6LiNH2The hydrogen of putting of-LiH biased samples is originated and peak value
Temperature, and in the weight loss curve of the temperature section.
3rd, after ball milling adulterate different content K2TiF6LiNH2- LiH aggregate samples carry out hydrogen desorption kineticses test：In argon gas
In glove box, 150mg doping 1mol%, 3mol% and 5mol%K are weighed respectively2TiF6LiNH2- LiH composite samples pass through
PCT (gases at high pressure adsorption instrument) carries out isothermal hydrogen desorption experiment at 200 DEG C, 250 DEG C, 300 DEG C respectively.It can be adulterated
1mol%, 3mol% and 5mol%K2TiF6LiNH2The isothermal dehydrogenation of-LiH composite samples at 200 DEG C, 250 DEG C, 300 DEG C
Curve.In addition, in argon gas glove box, 150mg doping 1mol%, 3mol% and 5mol%K are weighed respectively2TiF6LiNH2-
LiH composite samples set operating temperature to be 200 DEG C of suction hydrogen and 300 DEG C of dehydrogenations by PCT (gases at high pressure adsorption instrument), can obtain
150mg doping 1mol%, 3mol% and 5mol%K are weighed respectively2TiF6LiNH2At 250 DEG C and 300 DEG C of-LiH composite samples
Hydrogen discharging rate and put hydrogen cyclic curve.
3rd, embodiment 3：
1st, with 1: 1 mass ratio by LiNH2First mixed with LiH, then the 5mol%TiF4 that adulterates, obtain doping TiF4's
LiNH2With LiH mixed crystals.
Doping 5mol%TiF4 LiNH2With LiH mixed crystals：In argon gas glove box, 0.3g doping 5mol% is weighed
TiF4 LiNH2It is fitted into LiH mixed crystals in the ball grinder containing 20 stainless steel steel balls.Then ball is taken out from glove box
Grinding jar, is filled with 0.6MPa hydrogen, and ball grinder is symmetrically arranged in planetary ball mill, the ball under 450 revs/min of rotating speed
Mill processing 2 hours.
2nd, sample carries out hydrogen desorption test after ball milling：In argon gas glove box, the 5mol%TiF4 that adulterated after ball milling is reclaimed
LiNH2With LiH biased samples, the LiNH for the 5mol%TiF4 that adulterated after 13mg ball millings is taken2Joined with LiH biased samples by caloic
Hydrogen desorption test is carried out with instrument, gas signal is detected as H2, condition is that (flow velocity is 20ml min to argon gas atmosphere-1), 50~600
DEG C, heating rate is 10k/min.The 5mol%TiF that adulterates can be obtained4LiNH2The hydrogen of putting of-LiH biased samples is originated and peak value
Temperature.
4th, embodiment 4：
1st, with 1: 1 mass ratio by LiNH2First mixed with LiH, then the 10mol%KF that adulterates, obtain doping KF LiNH2
With LiH mixed crystals.
Doping 10mol%KF LiNH2With LiH mixed crystals：In argon gas glove box, 0.3g doping 10mol% is weighed
KF LiNH2It is fitted into LiH mixed crystals in the ball grinder containing 20 stainless steel steel balls.Then ball milling is taken out from glove box
Tank, is filled with 0.6MPa hydrogen, and ball grinder is symmetrically arranged in planetary ball mill, the ball milling under 450 revs/min of rotating speed
Processing 2 hours.
2nd, sample carries out hydrogen desorption test after ball milling：In argon gas glove box, doping 10mol%KF after ball milling is reclaimed
LiNH2With LiH biased samples, the LiNH for the 10mol%KF that adulterated after 13mg ball millings is taken2Pass through caloic combined instrument with LiH biased samples
Hydrogen desorption test is carried out, gas signal is detected as H2, condition is that (flow velocity is 20ml min to argon gas atmosphere-1), 50~600 DEG C,
Heating rate is 10k/min.The 5mol%TiF that adulterates can be obtained4LiNH2The hydrogen of putting of-LiH biased samples is originated and peak value temperature
Degree.
5th, test result analysis：
Fig. 1 is LiNH2- LiH doping different proportions K2TiF6Composite sample ball milling after thermal desorption mass spectrum comparison diagram, lead to
The hydrogen signal curve for contrasting several materials is crossed, is found with K2TiF6The increase of percentage is added, the span at dehydrogenation peak reduces peak
Intensity increase.Meanwhile, dehydrogenation initial temperature lower, from undoped 199 DEG C to doping 5mol%K2TiF6Composite sample in
75 DEG C of desorption temperature, reduces about 125 DEG C.Dehydrogenation peak temperature has obvious reduction, compared with undoped, be doped with
K2TiF6Composite sample dehydrogenation peak temperature all than relatively low, wherein 5mol%K2TiF6Composite sample it is minimum (be 233
℃)。
Fig. 2 is LiNH2- LiH doping different proportions K2TiF6Composite sample ball milling after the weightless comparison diagram of thermal desorption, such as
Shown in figure, the LiNH not adulterated2- LiH samples do not occur platform between 50 DEG C -400 DEG C, and the K that adulterates2TiF6Answer
Condensation material all goes out dehydrogenation platform in the temperature section, illustrates the K that adulterates2TiF6Composite dehydrogenation rate improve.On the other hand,
Operating temperature is in 200 DEG C, 5mol%K2TiF6Compound sample hydrogen desorption capacity it is most.
Fig. 3 is LiNH2- LiH non-impurity-dopeds, doping 5mol%K2TiF6Composite sample puts hydrogen at 250 DEG C of suction hydrogen, 300 DEG C
Cyclic curve figure, adulterate 5mol%K2TiF6Sample is carried out after circulation puts hydrogen 5 times can stablize, and hydrogen desorption capacity is still in 1.7wt%
Left and right, and preceding 4 circulations hydrogen desorption capacity changes little exist.And, undoped sample, after circulate twice, hydrogen desorption capacity
It is decreased obviously, second of circulation hydrogen desorption capacity is only about 0.5wt%.
Fig. 4 is LiNH2- LiH non-impurity-dopeds, doping 5mol%K2TiF6Composite sample is respectively at 200 DEG C, 250 DEG C, 300 DEG C
Isothermal dehydrogenation figure.It can be seen that at 300 DEG C, LiNH2- LiH non-impurity-dopeds sample and doping 5mol%K2TiF6Compound sample
Product hydrogen desorption capacity is more or less the same, but doping 5mol%K2TiF6Composite sample can just reach in 0.5h puts hydrogen platform, and LiNH2-
LiH non-impurity-doped samples need 1h.At 250 DEG C, adulterate 5mol%K2TiF6Composite sample hydrogen desorption capacity (2.6wt%) substantially compares
LiNH2- LiH non-impurity-dopeds sample (1.7wt%) is more, and the 5mol%K that adulterates2TiF6Composite sample reaches that putting hydrogen puts down in 0.6h
Platform, hydrogen discharging rate is 4.33wt%/h.At 200 DEG C, adulterate 5mol%K2TiF6Composite sample hydrogen desorption capacity is 0.54wt%,
LiNH2- LiH non-impurity-doped sample hydrogen desorption capacities 0.28wt%.As can be seen here, K2TiF6Addition can greatly improve LiNH2- LiH's
Hydrogen discharging rate.
Fig. 5 is LiNH2- LiH non-impurity-dopeds, doping 10mol%KF, doping 5mol%TiF4And doping 5mol%K2TiF6
Milled sample thermal desorption mass spectrogram.Found by the contrast of several different materials, KF, TiF4And K2TiF6To LiNH2- LiH has
Certain catalytic effect, all causes LiNH2- LiH initial dehydrogenated temperature and dehydrogenation peak temperature reduction, but work as K+、Ti+、
F-When ion acts synergistically, improvement is more obvious.Doping 5mol%K can be seen that by dehydrogenation peak temperature2TiF6Ball
The dehydrogenation peak temperature of grind away product is minimum.
K+、Ti+、F-Ion synergy can give full play to the effect of these three ions, work as 5mol%K2TiF6It is doped to
LiNH2Hydrogen storage property is greatly improved during-LiH, either on hydrogen storage content, desorption temperature or dehydrogenation rate.Other are outstanding
Catalyst compares (KF, TiF4Deng), we obtain it is minimum put hydrogen peak temperature and put hydrogen initial temperature, be more nearly 2015 years
The hydrogen storage standard that International Energy Agency is formulated, the business application apart from solid-state hydrogen storage is closer to a step.
Claims (6)
1. a kind of improved LiNH2- LiH composite hydrogen storage materials, it is characterised in that be doping K2TiF6LiNH2The compound storages of-LiH
Hydrogen material.
2. improved LiNH according to claim 12- LiH composite hydrogen storage materials, it is characterised in that K2TiF6Doping
Amount accounts for LiNH21~5mol% of-LiH mixtures, LiNH2LiNH in-LiH mixtures2It is 1 with LiH mass ratioes:1.
3. doping K according to claim 1 or 22TiF6LiNH2- LiH composite hydrogen storage materials, it is characterised in that K+、
Ti-、F-Three kinds of ions act synergistically on LiNH2In-LiH hydrogen storage systems, starting hydrogen discharging temperature is less than 100 DEG C, peak value hydrogen discharging temperature
Less than 260 DEG C.
4. a kind of improved LiNH2The preparation method of-LiH composite hydrogen storage materials, it is characterised in that entered using planetary type ball-milling instrument
Prepared by row mechanical ball mill, step is as follows：
1) under an argon atmosphere, by the K of different mol ratio2TiF6It is placed in and has been loaded with LiNH2The stainless steel jar mill of-LiH mixtures
In, and add ball-milling medium.
2) 0.6MPa hydrogen is filled with into ball grinder as protection gas, under the conditions of rotating speed is 450 rev/min, ball milling 2h, you can
Doping K is made2TiF6LiNH2- LiH composite hydrogen storage materials.
5. preparation method according to claim 4, it is characterised in that step 1) in, in ball-milling treatment, ball-milling medium with
Quality of material ratio is 90: 1.
6. preparation method according to claim 4, it is characterised in that step 1) in, ball-milling medium is 20 steel balls.
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| CN117772259B (en) * | 2024-02-26 | 2024-07-02 | 山东海化集团有限公司 | Double-active-center ammonia synthesis catalyst and preparation method and application thereof |
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| CN112079331B (en) * | 2020-08-20 | 2022-06-03 | 浙江工业大学 | Synthesis method of metal-nitrogen-hydrogen system hydrogen storage material |
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