CN112830450B - Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof - Google Patents

Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof Download PDF

Info

Publication number
CN112830450B
CN112830450B CN202110139286.1A CN202110139286A CN112830450B CN 112830450 B CN112830450 B CN 112830450B CN 202110139286 A CN202110139286 A CN 202110139286A CN 112830450 B CN112830450 B CN 112830450B
Authority
CN
China
Prior art keywords
cotio
cobalt titanate
lithium aluminum
porous
aluminum hydride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110139286.1A
Other languages
Chinese (zh)
Other versions
CN112830450A (en
Inventor
孙立贤
赵莉
徐芬
陈凯
高旭
张孝旭
鞠函宇
涂德贵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guilin University of Electronic Technology
Original Assignee
Guilin University of Electronic Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guilin University of Electronic Technology filed Critical Guilin University of Electronic Technology
Priority to CN202110139286.1A priority Critical patent/CN112830450B/en
Publication of CN112830450A publication Critical patent/CN112830450A/en
Application granted granted Critical
Publication of CN112830450B publication Critical patent/CN112830450B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Hair brushDisclosed is a porous nano-rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material, which is prepared from lithium aluminum hydride and porous nano-rod-shaped cobalt titanate CoTiO3Mixing and mechanically milling to obtain the product; a uniformly dispersed porous nanorod structure is presented; the microscopic size is 1-4 μm in length and 0.5-2 μm in width; porous nanorod-shaped cobalt titanate CoTiO3Prepared by the reaction of cobalt acetate, tetrabutyl titanate and ethylene glycol. The preparation method comprises the following steps: 1. porous nanorod-shaped cobalt titanate CoTiO3Preparing; 2. porous nanorod-shaped cobalt titanate CoTiO3And preparing the lithium aluminum hydride-doped hydrogen storage material. As an application in the field of hydrogen storage, when porous nano-rod-shaped cobalt titanate CoTiO3When the addition amount is 5 wt%, the hydrogen releasing temperature of the system is reduced to 61 ℃, and the hydrogen releasing amount reaches 8.13 wt%; when porous nano rod-shaped cobalt titanate CoTiO3When the addition amount is 10 wt%, the hydrogen releasing temperature of the system is reduced to 63 ℃, and the hydrogen releasing amount reaches 8.32 wt%. The invention has the following advantages: 1. high hydrogen release performance, high hydrogen storage capacity and high hydrogen release rate; 2. the hydrogen releasing condition is mild.

Description

Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogen storage materials of new energy materials, in particular to porous nanorod-shaped cobalt titanate (CoTiO)3) A doped lithium aluminum hydride hydrogen storage material and a preparation method thereof.
Background
With the rapid development of social economy and the rapid increase of population, the gradual shortage of resources and energy and the gradual deterioration of ecological environment become problems to be solved at present. People pay more and more attention to developing green energy and protecting ecological environment. The hydrogen energy has the advantages of abundant reserves, renewability, high efficiency, recycling and the like, and is one of the most promising choices for replacing fossil fuels in future energy systems. At present, the development and utilization of hydrogen energy mainly face three key problems of production, storage and transportation. Among them, how to safely and efficiently use hydrogen energy as vehicle-mounted storage is the research subject with the most challenging and commercial value at present. The traditional high-pressure liquid and gaseous hydrogen storage has low efficiency and low safety, and becomes an important factor restricting large-scale commercialization of vehicle-mounted hydrogen storage.
Lithium aluminum hydride (LiAlH)4) Having a higher hydrogen storage capacity (10.6 wt%) and relatively lower raw material cost is considered one of the most promising hydrogen storage materials. But the high desorption temperature and slow kinetics limit its practical application.
In recent years, to improve LiAlH4Much work has been done on the dehydrogenation performance of (1) mainly in the following areas: (1) reducing the particle size by ball milling and nano-confinement; (2) doping and catalytic modification; (3) and constructing a complex system with other metal hydrides. Among them, many studies have focused on doping catalytic modification of the metal element, such as doping metal catalysts like metal element, metal halide, metal oxide and other metal compounds. Reported as NiFe2O4、CoFe2O4、ScCl3、TiC、TiCl3、TiF3Equal pair of LiAlH4The hydrogen storage performance of (2) is improved to a certain extent.
Rafiudd et al [ Rafiudd, Qu X, Li P, et al, synthetic catalytic effects of NiCl2, TiC and TiN on hydrogen storage properties of LiAlH4. Rare Metals. 2011,30:27-34.]Mixing LiAlH4Ball milling and mixing with TiC, the hydrogen release amount of a mixing system added with nano TiC particles reaches 6.85 wt%, the hydrogen release temperature is reduced to 95 ℃, and the result shows that the TiC nano particles are matched with LiAlH4The hydrogen release kinetics and the cycle performance of the catalyst have good catalytic action. However, TiC doping catalyzes LiAlH4The initial hydrogen release temperature is still higher than the maximum working temperature of the vehicle-mounted hydrogen storage system regulated by the U.S. department of energy, namely 85 ℃, and needs to be further improved.
Huang et al [ Huang X, Xiao X, Wang X, el al. synthetic catalytic action from pore-like TMTiO3 (TM = Ni and Co) for reversible hydrogen storage of magnesium hydride[J]. The Journal of Physical Chemistry C, 2018, 122(49): 27973-27982.]Respectively using transition metal oxide NiTiO3And CoTiO3Doping with MgH2Then, doped NiTiO was found3Then, the hydrogen release temperature can be reduced to 235 ℃, and the hydrogen release amount reaches 6.9 wt%; addition of CoTiO3Can reduce MgH2The initial temperature of decomposition and the accelerated rate of desorption of hydrogen. However, inflection points still exist during dehydrogenation, and NiTiO3Bitio3Has lower initial dehydrogenation temperature and faster hydrogen desorption rate, completely eliminates discontinuity of desorption curve, and thus shows better catalysis.
Based on the above experimental results, the research of the subject group of the present inventors showed that [ Sunlixian, a nickel titanate doped lithium aluminum hydride hydrogen storage material and its preparation method, China, 201911263650.4[ P]. 2020.02.21.]With NiTiO3Doping with LiAlH4It was found that the hydrogen evolution temperature could be lowered to 73 ℃ and the hydrogen evolution reached 7.2 wt%.
Through the above transition metal carbide and oxide TiC, NiTiO3And CoTiO3The technical scheme of the hydrogen discharge performance of the catalytic hydrogen storage material is analyzed, and the common technical problems existing in the current technical scheme are as follows:
1) the initial hydrogen release temperature is higher;
2) the hydrogen release dynamic performance is poor, and the hydrogen release amount is low.
Meanwhile, by comparing Huang and Sun's technical solutions, it can be known that the hydrogen storage materials are MgH respectively due to different hydrogen storage materials2And LiAlH4Even with the same dopant NiTiO3Different laws are present. This phenomenon indicates that NiTiO3In different hydrogen storage materials, different catalytic effects are produced, i.e. it is shown that the technical features play different roles in the two technical solutions.
That is, the inventors have studied to find that there is a problem that the hydrogen storage material and the catalyst are matched with each other, namely, the above-mentionedThe root of the technical problem is to solve the matching problem of the hydrogen storage material and the catalyst. Through calculation of a first principle, CoTiO is found3Can effectively improve the LiAlH hydrogen storage material4Experiments show that the theoretical calculation result is consistent with the test result.
Disclosure of Invention
The invention aims to provide a porous nano rod-shaped cobalt titanate-doped lithium aluminum hydride hydrogen storage material and a preparation method thereof.
The inventor researches and discovers that:
the CoTiO is known through DFT calculation3For LiAlH4The effect of dehydrogenation. In this study, we constructed a cluster-surface interface model and evaluated the level of density functional theory, [ AlH ]4]-Clustered in CoTiO3Adsorption energy on the surface and how the interface weakens the adsorption [ AlH4]-Cluster Al-H bonds. Our model is based on the following considerations: (i) LiAlH4The crystal is composed of [ AlH4]-Tetrahedral and Li atomic composition, and (ii) dehydrogenation process involving drawing [ AlH ] from the crystal4]-Tetrahedra, and dissociation or recrystallization of Al-H clusters. As shown in Table 1, when [ AlH ]4]-Tetrahedral adsorption to CoTiO3On the surface of (2), the bond length of Al-H is significantly extended. Apparently, CoTiO3The surface exhibits a relatively low energy barrier, [ AlH ]4]-Tetrahedron derived from LiAlH4The Al-H bonds are pulled out of the crystal and are greatly weakened. Furthermore, charge redistribution display of the computational structure, [ AlH4]-Bond weakening of clusters is by electrons from CoTiO3Surface transfer to [ AlH4]-Cluster induced. The density of states (DOS) plot indicates that the Al 2p orbital occupies the range from LiAlH4To [ AlH4]-@CoTiO3Showing an increasing trend. Therefore, interfacial charge transfer and the decontamination of Al-H clusters promote the weakening of Al-H bonds. The theoretical calculation is CoTiO3In LiAlH4The cluster-surface interface and the catalytic mechanism in dehydrogenation reactions provide a profound explanation.
TABLE 1
LiAlH4 [AlH4]-@CoTiO3
Atom Atomic charge (e)
Al -2.11
H1 0.53 0.40
H2 0.53 0.65
H3 0.53 0.66
H4 0.53 0.71
Bond Bond length (Å)
Al-H1 1.65 1.59
Al-H2 1.65 1.79
Al-H3 1.65 1.80
Al-H4 1.65 1.90
Adsorption energy (eV)
-5.87
On the basis of the theory, the inventor adjusts the porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material provided by the invention, and effectively controls LiAlH4The hydrogen discharging process of the hydrogen storage material simultaneously realizes the following 2 technical effects:
1. reducing the initial hydrogen release temperature in the whole hydrogen release process;
2. the induction period of the second hydrogen releasing process is greatly reduced, the hydrogen releasing temperature is reduced, the two hydrogen releasing processes are coordinated, and finally, a large number of hydrogen releasing processes are realized at 90-210 ℃.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a porous nano-rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material is prepared from lithium aluminum hydride and porous nano-rod-shaped cobalt titanate CoTiO3Mixing and mechanically milling to obtain the product;
the porous nano rod-shaped cobalt titanate CoTiO3The addition amount of (B) is 5-10 wt% of the total mass;
the porous nano rod-shaped cobalt titanate CoTiO3A uniformly dispersed porous nanorod structure is presented; porous nano-rod-shaped cobalt titanate CoTiO3The microscopic size is 1-4 μm in length and 0.5-2 μm in width;
the porous nano rod-shaped cobalt titanate CoTiO3Prepared by the reaction of cobalt acetate, tetrabutyl titanate and glycol.
Porous nano-rod-shaped cobalt titanate CoTiO3The preparation method of the lithium aluminum hydride-doped hydrogen storage material comprises the following steps:
step 1, porous nano-rod-shaped cobalt titanate CoTiO3The preparation method comprises the steps of adding cobalt acetate and tetrabutyl titanate into ethylene glycol to perform mixed reaction under a certain condition, washing, filtering and drying to obtain a calcined precursor, and calcining under a certain condition to obtain the porous nano rodlike cobalt titanate CoTiO3；
The cobalt acetate and tetrabutyl titanate of the step 1 satisfy the following condition that 1:1, the ratio of the amounts of substances;
the mixing reaction in the step 1 is carried out under the conditions that cobalt acetate tetrahydrate is added into ethylene glycol to be stirred and dissolved to obtain a mixed solution, tetrabutyl titanate is slowly added into the mixed solution, and then the mixed solution is subjected to mixing reaction under the magnetic stirring condition at the reaction temperature of 20-40 ℃ for 4-6 h to obtain a purple suspension;
the washing and filtering method in the step 1 is centrifugation, the solvent used for washing is absolute ethyl alcohol, the centrifugation speed is 6000-; the drying condition of the step 1 is vacuum condition, the drying temperature is 60-80 ℃, and the drying time is 8-12 h;
the calcining conditions in the step 1 are that the heating rate is 3 ℃/min, the calcining temperature is 600 ℃, the calcining time is 1-2 h, and the calcining atmosphere is air;
step 2, porous nano-rod-shaped cobalt titanate CoTiO3Preparing hydrogen storage material doped with lithium aluminum hydride by using the porous nanorod-shaped cobalt titanate CoTiO obtained in the step 13And lithium aluminum hydride satisfy a certain mass fraction relation, and under a certain condition, the porous nano rod-shaped cobalt titanate CoTiO is subjected to reaction3Ball-milling with lithium aluminum hydride to obtain porous nanometer rod-shaped cobalt titanate CoTiO3Doping a lithium aluminum hydride hydrogen storage material;
the step 2 is to prepare porous nano rodlike cobalt titanate CoTiO3The mass fraction relation satisfied by the lithium aluminum hydride is porous nano-rod-shaped cobalt titanate CoTiO3The addition amount of (B) is 5-10 wt% of the total mass;
the grinding conditions in the step 2 are that argon is used as protective atmosphere, and the ball material ratio is (60-40): 1, the ball milling speed is 400-.
Porous nano-rod-shaped cobalt titanate CoTiO3The application of doped lithium aluminum hydride hydrogen storage material as hydrogen storage field is that when the porous nano rod-shaped cobalt titanate CoTiO3When the addition amount is 5 wt%, the hydrogen releasing temperature of the system is reduced to 61 ℃, and the hydrogen releasing amount reaches 8.13 wt%; when porous nanometer rod-shaped cobalt titanate CoTiO3When the addition amount is 10 wt%, the hydrogen releasing temperature of the system is reduced to 63 ℃, and the hydrogen releasing amount reaches 8.32 wt%.
X-ray diffraction test proves that the porous nano-rod-shaped cobalt titanate CoTiO3The material is successfully prepared.
Scanning electron microscope test and transmission electron microscope test prove that the porous nano-rod-shaped cobalt titanate CoTiO3The material is characterized by a uniformly dispersed porous nano rod-shaped structure, the length of the nano rod-shaped structure is 0.5-4 mu m, and the width of the nano rod-shaped structure is 0.1-2 mu m.
The hydrogen release performance test shows that the porous nano rod-shaped titanic acid is addedCobalt CoTiO3The initial hydrogen releasing temperature of the lithium aluminum hydride hydrogen storage material is 61-63 ℃, which is reduced by 91-93 ℃ compared with pure lithium aluminum hydride, and the total hydrogen releasing amount reaches 8.13-8.32 wt%.
The Differential Scanning Calorimetry (DSC) test and the Kissinger equation calculation result show that the activation energy of the two-step reaction is 58.09 kJ/mol and 40.49 kJ/mol respectively.
Therefore, compared with the prior art, the invention has the following advantages:
1. the hydrogen storage material prepared by the invention effectively improves the hydrogen storage performance of lithium aluminum hydride, and has higher hydrogen storage capacity and hydrogen discharge rate under mild conditions. When porous nano rod-shaped cobalt titanate CoTiO3When the doping amount of the catalyst is 5 wt%, the initial hydrogen release temperature is reduced to 61 ℃, the hydrogen release amount reaches 8.13 wt%, and the hydrogen release performance is greatly improved;
2. the porous nano rod-shaped cobalt titanate CoTiO prepared by the invention3Has a uniformly dispersed porous nano rod-shaped structure, can be fully combined with lithium aluminum hydride when being used as a catalyst to be compounded with the lithium aluminum hydride, and improves the hydrogen release performance of the composite hydrogen storage material, thereby showing that CoTiO3The catalyst is matched with the lithium aluminum hydride hydrogen storage material;
3. the porous nano rod-shaped cobalt titanate CoTiO prepared by the invention3The method has the advantages of low cost, simple preparation process, controllable reaction and the like.
Description of the drawings:
FIG. 1 shows CoTiO prepared according to embodiment 1 of the present invention3XRD pattern of (A) and CoTiO3Standard PDF card atlas;
FIG. 2 shows CoTiO prepared according to embodiment 1 of the present invention3A field emission scanning electron microscope image of (a);
FIG. 3 shows CoTiO prepared according to embodiment 1 of the present invention3Transmission electron microscopy images of;
FIG. 4 shows [ AlH4 ]]--CoTiO3The charge redistribution map of the computed structure of (1);
FIG. 5 is LiAlH4And [ AlH4]--CoTiO3Density of states (DOS) map of (a);
FIG. 6 shows CoTiO doped according to the present invention in example 1, comparative example 3, and example 23LiAlH with contents of 2 wt%, 5 wt% and 10 wt%, respectively4The dehydrogenation graph of (a);
FIG. 7 is a specific comparative example 1 of the present invention doped with 0 wt% CoTiO3LiAlH of4The dehydrogenation graph of (a);
FIG. 8 is a 5 wt% CoTiO doped sample according to example 1 of the present invention3LiAlH of4The dehydrogenation graph of (a);
FIG. 9 is a 5 wt% CoTiO doped sample according to example 1 of the present invention3LiAlH of (2)4A fitted graph of Differential Scanning Calorimetry (DSC) tests of (a);
FIG. 10 shows CoTiO prepared according to example 1 of the present invention3An X-ray photoelectron spectrum of (a).
Detailed Description
The present invention will be described in further detail by way of examples, but the present invention is not limited thereto, with reference to the accompanying drawings.
Example 1
CoTiO (cobalt-titanium oxide)3Porous nanorod-shaped cobalt titanate CoTiO with content of 5 wt%3The preparation method of the lithium aluminum hydride-doped hydrogen storage material comprises the following steps:
step 1, porous nano-rod-shaped cobalt titanate CoTiO3The preparation method comprises the steps of weighing 2.49 g of cobalt acetate tetrahydrate at the temperature of 25 ℃ by taking the cobalt acetate and tetrabutyl titanate according to the mass ratio of 1:1, adding the cobalt acetate tetrahydrate into 60 ml of glycol, stirring and dissolving, measuring 3.4 ml of tetrabutyl titanate, slowly adding the tetrabutyl titanate into the solution, magnetically stirring at the rotating speed of 100 rpm/min for 4 hours, and carrying out mixing reaction. Centrifuging and washing with anhydrous ethanol for 3 times, each time centrifuging for 5 min, vacuum drying at 70 deg.C for 10 hr, calcining at 600 deg.C in muffle furnace for 1 hr to obtain porous nanometer rod-shaped cobalt titanate CoTiO3；
Step 2, porous nano-rod-shaped cobalt titanate CoTiO3Preparing hydrogen storage material doped with lithium aluminum hydride by using the porous nanorod-shaped cobalt titanate CoTiO obtained in the step 13And hydrogenThe lithium aluminum oxide satisfies the mass fraction relation of 1:19, and 0.025 g of the porous nano-rod-shaped cobalt titanate CoTiO obtained in the step 1 is weighed under the protection of argon3And 0.475 g of lithium aluminum hydride, at a pellet to feed ratio of 40: 1, ball milling is carried out under the conditions that the ball milling rotating speed is 450 r/min and the ball milling time is 2 hours, and then the porous nano rodlike cobalt titanate CoTiO is obtained3Doped lithium aluminum hydride hydrogen storage materials.
To prove that the porous nanorod-shaped cobalt titanate CoTiO3The material is successfully prepared, X-ray diffraction test is carried out on the material, the test result is shown in figure 1, and the obtained diffraction spectrum can be matched with CoTiO3The standard PDF card corresponds to the standard PDF card, which shows that the cobalt titanate CoTiO is successfully prepared3。
To prove that the porous nanorod-shaped cobalt titanate CoTiO3The structural characteristics of the material are tested by a scanning electron microscope, and the test result is shown in figure 2, and the material has a porous nanorod structure with uniformly dispersed appearance; the microscopic dimensions of the material, as measured by scanning electron microscopy, are 0.5-4 μm long and 0.1-2 μm wide, as shown in FIG. 3.
To prove that the porous nanorod-shaped cobalt titanate CoTiO3The influence of the material on the hydrogen desorption performance of the lithium aluminum hydride is calculated by the charge redistribution of the structure, and the calculation result is shown in figure 4, [ AlH4]-Bond weakening of clusters is by electrons from CoTiO3Surface transfer to [ AlH4]-Cluster induced. Through the calculation of the state Density (DOS), the calculation result is shown in figure 5, and the interface charge transfer and the impurity removal of the Al-H cluster promote the weakening of the Al-H bond and are beneficial to the release of hydrogen.
To prove that the porous nanorod-shaped cobalt titanate CoTiO3As the influence of the catalyst on the hydrogen release performance of lithium aluminum hydride, CoTiO is prepared3Porous nanorod-shaped cobalt titanate CoTiO with content of 5 wt%3Doped lithium aluminum hydride hydrogen storage materials. The test result of the temperature rise dehydrogenation test is shown in fig. 8. Confirms that the porous nano-rod-shaped cobalt titanate CoTiO is added3The initial hydrogen releasing temperature of the lithium aluminum hydride hydrogen storage material is 61 ℃, and the total hydrogen releasing amount reaches 8.13 wt%.
To prove that the porous nanorod-shaped cobalt titanateCoTiO3Influence of the material on the hydrogen evolution kinetic performance of lithium aluminum hydride on CoTiO3The lithium aluminum hydride hydrogen storage material with the content of 5 wt% is subjected to Differential Scanning Calorimetry (DSC) test, and the Kissinger equation is applied to fit the test data, so that the activation energy is finally calculated, and the fitting result is shown in FIG. 9. Confirming the addition of CoTiO3The activation energies of the first two steps of the reaction of the lithium aluminum hydride hydrogen storage material with the content of 5 wt% are 58.09 kJ/mol and 40.49 kJ/mol respectively, which are reduced by 58.11 kJ/mol and 92.51 kJ/mol respectively compared with pure lithium aluminum hydride.
To prove the porous nanorod cobalt titanate CoTiO3The material is successfully prepared, X-ray photoelectron spectroscopy is carried out on the material, the test result is shown in figure 10, and the sample really contains Co, Ti and O elements, which indicates that the cobalt titanate CoTiO is successfully prepared3。
To prove that the porous nanorod-shaped cobalt titanate CoTiO3LiAlH was calculated as the effect of the catalyst on the hydrogen evolution performance of lithium aluminum hydride4And [ AlH4]--CoTiO3The bond length and adsorption energy of (b) are calculated and shown in table 1. When [ AlH ] is4]-Tetrahedral adsorption to CoTiO3When on the surface of (2), the bond length of Al-H is prolonged remarkably, promoting the breakage of Al-H bond, and facilitating the release of hydrogen.
To prove CoTiO3The effect on the hydrogen evolution behavior of lithium aluminum hydride hydrogen storage materials was compared to comparative example 1, i.e., no CoTiO addition3The lithium aluminum hydride hydrogen storage material of (1).
Comparative example 1
Without adding CoTiO3Of lithium aluminum hydride hydrogen storage material, i.e. CoTiO3A process for the preparation of a 0 wt% lithium aluminum hydride hydrogen storage material, the steps not specifically illustrated being the same as in example 1, except that: in the step 1, no CoTiO is added3In an argon atmosphere glove box, only 0.5 g of LiAlH was weighed4。
The obtained CoTiO3A temperature-rising dehydrogenation test was carried out on a lithium aluminum hydride hydrogen storage material having a content of 0 wt% in the same manner as in example 1, and the results are shown in FIG. 7, in which the initial hydrogen-evolving temperature was 154 ℃ and the hydrogen-evolving amount at the time of temperature rise to 300 ℃ was set to7.21 wt%。
Thus, adding porous nanorod cobalt titanate CoTiO3The initial hydrogen release temperature of the lithium aluminum hydride hydrogen storage material is 61 ℃, the initial hydrogen release temperature is reduced by 93 ℃ compared with that of pure lithium aluminum hydride, the total hydrogen release amount reaches 8.13 wt percent and is improved by 12.8 percent compared with that of pure lithium aluminum hydride, and the addition of CoTiO is shown3Has good catalytic action on the hydrogen release performance of the lithium aluminum hydride hydrogen storage material.
To demonstrate the calcination temperature vs. CoTiO3Influence of preparation comparative example 2, i.e. porous nanorod-shaped cobalt titanate CoTiO prepared at a calcination temperature of 400 deg.C3。
Comparative example 2
Porous nano-rod-shaped cobalt titanate CoTiO3The same procedure as in example 1 except that: in the step 1, the calcination temperature is 400 ℃.
The obtained CoTiO3The X-ray diffraction test is carried out, the test method is the same as that of the example 1, and the obtained diffraction spectrum cannot be similar to that of CoTiO3The standard PDF card corresponds to the standard PDF card, and shows that when the muffle furnace calcining temperature is 400 ℃, the cobalt titanate CoTiO can not be successfully prepared3。
Thus, the calcination temperature is relative to the CoTiO produced3The component (A) has an influence of CoTiO3Important factors for the success of the preparation.
To prove CoTiO3Comparative example 3 and example 2, i.e., CoTiO, were performed to determine the effect of doping levels on the hydrogen evolution performance of lithium aluminum hydride hydrogen storage materials3The doping amount of (A) is 2 wt% and 10 wt%.
Comparative example 3
Preparation method of porous nano rodlike cobalt titanate doped lithium aluminum hydride hydrogen storage material (CoTiO)3 Content 2 wt%), the procedure not specified was the same as in example 1 except that: in the step 2, CoTiO3The doping amount of (2 wt%) was measured in an argon atmosphere glove box, and 0.01 g of porous nanorod cobalt titanate CoTiO was weighed out3And 0.49 gLiAlH4。
The obtained CoTiO3Heating up and removing lithium aluminum hydride hydrogen storage material with content of 2 wt%The hydrogen test, which was performed in the same manner as in example 1, showed the results shown in FIG. 6, wherein the initial hydrogen discharge temperature was 94 ℃ and the hydrogen discharge amount was 7.21 wt% when the temperature was raised to 300 ℃.
Example 2
Preparation method of porous nano rodlike cobalt titanate doped lithium aluminum hydride hydrogen storage material (CoTiO)3 Content 10 wt%), the procedure not specifically described was the same as in example 1 except that: in the step 2, CoTiO3The doping amount of (2) is 10 wt%, 0.05 g of porous nano-rod cobalt titanate CoTiO is weighed in an argon atmosphere glove box3And 0.45 g of LiAlH4。
The obtained CoTiO3The temperature-rising dehydrogenation test was carried out on the lithium aluminum hydride hydrogen storage material with the content of 10 wt%, the test method was the same as that of example 1, and the test result is shown in fig. 6, in which the initial hydrogen-releasing temperature was 63 ℃ and the hydrogen-releasing amount was 8.32 wt% when the temperature was raised to 300 ℃.
Thus, CoTiO3The lithium aluminum hydride hydrogen storage material with the content of 5 wt% has the best hydrogen discharge performance. As shown in FIG. 3, the initial hydrogen release temperature is 61 ℃, which is 93 ℃ lower than that of pure lithium aluminum hydride, and the hydrogen release amount is 8.13 wt% when the temperature is raised to 300 ℃, which is 12.8% higher than that of pure lithium aluminum hydride.

Claims (10)

1. A porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material is characterized in that: lithium aluminum hydride and porous nanorod cobalt titanate CoTiO3Mixing and mechanically milling to obtain the product; the porous nano rod-shaped cobalt titanate CoTiO3The addition amount of (B) is 5-10 wt% of the total mass.
2. The porous nanorod cobalt titanate CoTiO as in claim 13A lithium aluminum hydride doped hydrogen storage material, characterized in that: the porous nano rod-shaped cobalt titanate CoTiO3A uniformly dispersed porous nanorod structure is presented; porous nanorod-shaped cobalt titanate CoTiO3The microscopic size is 1-4 μm in length and 0.5-2 μm in width.
3. The porous nanorod titanic acid of claim 2Cobalt CoTiO3A lithium aluminum hydride doped hydrogen storage material, characterized in that: the porous nano rod-shaped cobalt titanate CoTiO3Prepared by the reaction of cobalt acetate, tetrabutyl titanate and ethylene glycol.
4. The porous nanorod cobalt titanate CoTiO as in claim 13The preparation method of the lithium aluminum hydride-doped hydrogen storage material is characterized by comprising the following steps:
step 1, porous nano-rod-shaped cobalt titanate CoTiO3The preparation method comprises the steps of adding cobalt acetate and tetrabutyl titanate into ethylene glycol to perform mixed reaction under a certain condition, washing, filtering and drying to obtain a calcined precursor, and calcining under a certain condition to obtain the porous nano rodlike cobalt titanate CoTiO3；
The cobalt acetate and tetrabutyl titanate of the step 1 satisfy the following condition that 1:1, the ratio of the amounts of substances;
step 2, porous nano-rod-shaped cobalt titanate CoTiO3Preparing hydrogen storage material doped with lithium aluminum hydride by using the porous nanorod-shaped cobalt titanate CoTiO obtained in the step 13And lithium aluminum hydride satisfy a certain mass fraction relation, and under a certain condition, the porous nano rod-shaped cobalt titanate CoTiO is subjected to reaction3Ball-milling with lithium aluminum hydride to obtain porous nanometer rodlike cobalt titanate CoTiO3Doped lithium aluminum hydride hydrogen storage materials.
5. The method of claim 4, wherein: the condition of the mixing reaction in the step 1 is that cobalt acetate tetrahydrate is added into ethylene glycol to be stirred and dissolved to obtain a mixed solution, tetrabutyl titanate is slowly added into the mixed solution, and then the mixed reaction is carried out under the condition of magnetic stirring at the reaction temperature of 20-40 ℃ for 4-6 h to obtain purple suspension.
6. The method of claim 4, wherein: the washing and filtering method in the step 1 is centrifugation, the solvent used for washing is absolute ethyl alcohol, the centrifugation speed is 6000-8000 rpm, and the centrifugation time is 10-15 min; the drying condition of the step 1 is vacuum condition, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
7. The method of claim 4, wherein: the calcination conditions in the step 1 are that the heating rate is 3 ℃/min, the calcination temperature is 600 ℃, the calcination time is 1-2 h, and the calcination atmosphere is air.
8. The method of claim 4, wherein: the step 2 is to prepare porous nano rod-shaped cobalt titanate CoTiO3The mass fraction relation satisfied by the lithium aluminum hydride is porous nano-rod-shaped cobalt titanate CoTiO3The addition amount of (B) is 5-10 wt% of the total mass.
9. The method of claim 4, wherein: the grinding conditions in the step 2 are that argon is used as protective atmosphere, and the ball material ratio is (60-40): 1, the ball milling speed is 400-.
10. The porous nanorod cobalt titanate CoTiO as in claim 13The application of the doped lithium aluminum hydride hydrogen storage material as the hydrogen storage field is characterized in that: when porous nano rod-shaped cobalt titanate CoTiO3When the addition amount is 5 wt%, the hydrogen releasing temperature of the system is reduced to 61 ℃, and the hydrogen releasing amount reaches 8.13 wt%; when porous nano rod-shaped cobalt titanate CoTiO3When the addition amount is 10 wt%, the hydrogen releasing temperature of the system is reduced to 63 ℃, and the hydrogen releasing amount reaches 8.32 wt%.
CN202110139286.1A 2021-02-02 2021-02-02 Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof Active CN112830450B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110139286.1A CN112830450B (en) 2021-02-02 2021-02-02 Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110139286.1A CN112830450B (en) 2021-02-02 2021-02-02 Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112830450A CN112830450A (en) 2021-05-25
CN112830450B true CN112830450B (en) 2022-06-07

Family

ID=75931427

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110139286.1A Active CN112830450B (en) 2021-02-02 2021-02-02 Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112830450B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130266878A1 (en) * 2012-04-04 2013-10-10 GM Global Technology Operations LLC Hydrogen storage system including a lithium conductor
CN110817791B (en) * 2019-12-11 2023-02-28 桂林电子科技大学 Nickel titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof

Also Published As

Publication number Publication date
CN112830450A (en) 2021-05-25

Similar Documents

Publication Publication Date Title
CN110116990B (en) In-situ preparation method of nano magnesium hydride
Song et al. Constructing graphene nanosheet-supported FeOOH nanodots for hydrogen storage of MgH2
Xia et al. Dehybridization effect in improved dehydrogenation of LiAlH4 by doping with two-dimensional Ti3C2
CN110817791B (en) Nickel titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof
CN103840176B (en) Three-dimensional grapheme based combined electrode of a kind of area load Au nano particle and its preparation method and application
CN110707301A (en) Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof
Yuan et al. N-doped carbon coated Ti3C2 MXene as a high-efficiency catalyst for improving hydrogen storage kinetics and stability of NaAlH4
CN108658038B (en) Based on LiAlH4Hydrogen storage material and method for producing the same
Wei et al. Multielement synergetic effect of NiFe 2 O 4 and h-BN for improving the dehydrogenation properties of LiAlH 4
CN109012664B (en) Amorphous carbon supported nano metal particle catalyst and preparation method and application thereof
Guemou et al. Graphene-anchored Ni6MnO8 nanoparticles with steady catalytic action to accelerate the hydrogen storage kinetics of MgH2
CN109052403B (en) Two-dimensional titanium carbide-doped lithium aluminum hydride hydrogen storage material and preparation method thereof
Zhang et al. Constructing Mg 2 Co–Mg 2 CoH 5 nano hydrogen pumps from LiCoO 2 nanosheets for boosting the hydrogen storage property of MgH 2
Chen et al. Core-shell structured Si@ Cu nanoparticles segregated in graphene-carbon nanotube networks enable high reversible capacity and rate capability of anode for lithium-ion batteries
CN113148956B (en) Preparation method of graphene-loaded nano flaky transition metal hydride and hydrogen storage material
Yan et al. Enhanced hydrogen storage properties of magnesium hydride by multifunctional carbon-based materials: a review
CN112830450B (en) Porous nano rod-shaped cobalt titanate doped lithium aluminum hydride hydrogen storage material and preparation method thereof
Luo et al. BiPO4 is embedded in reduced graphene oxide as an anode for potassium ion batteries
CN111515380B (en) High-capacity magnesium-based composite hydrogen storage material and preparation method thereof
CN112717966A (en) Two-dimensional black phosphorus-MoO3-xComposite material, preparation method and application thereof
CN108091838B (en) Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step
CN114590774A (en) Magnesium hydride hydrogen storage material based on hierarchical porous microspheres Ti-Nb-O and preparation method thereof
CN100338798C (en) Magnesium and multi-wall nano carbon tube composite hydrogen storage material and process for preparing same
CN116706168B (en) Nickel/nickel boron/hexagonal boron nitride composite material and preparation method and application thereof
CN117899884B (en) Catalyst for enhancing performance of composite hydrogen storage material, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant