CN110436408B - Two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material and preparation method thereof - Google Patents
Two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material, which is prepared from sodium aluminum hydride and two-dimensional titanium carbide Ti 2 C, mixing and mechanically milling to obtain the product; the two-dimensional titanium carbide Ti 2 And C presents a two-dimensional sheet stacking structure. The preparation method comprises the following steps: 1) Two-dimensional Ti 2 C, preparation; 2) And (3) preparing the two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material. When the doping amount of the catalyst is 1wt percent, the hydrogen release temperature of the system is reduced to 45 ℃, and the hydrogen release amount reaches 6.0 wt percent; when the doping amount of the catalyst is 9 wt%, the hydrogen release temperature of the system is reduced to 92 ℃, and the hydrogen release amount reaches 5.4 wt%. The invention has the following advantages: 1. effectively improves the hydrogen release performance of the sodium aluminum hydride, and has higher hydrogen storage capacity and hydrogen release rate under mild conditions. The initial hydrogen release temperature is reduced to 45 ℃, and the hydrogen release amount reaches 6.0 wt%; 2. ti 2 C is used as a catalyst to be more matched with the sodium aluminum hydride hydrogen storage material; 3. has the advantages of low cost, simple preparation process, controllable reaction and the like.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials of new energy materials, in particular to two-dimensional titanium carbide (Ti) 2 C) A hydrogen storage material doped with sodium aluminum hydride and a preparation method thereof.
Background
With the development of society and the progress of science and technology, energy has become one of the global focus problems facing human beings, and the search of green, efficient and renewable new energy for replacing fossil energy becomes the development target of all countries in the world, and is the key to solve the problems of energy shortage and environmental pollution. The hydrogen energy has the advantages of rich raw material sources, environment-friendly products, renewability and the like, and becomes one of the most potential alternative energy sources at present. 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.
Metal complex hydride NaAlH 4 Because of its high hydrogen storage capacity (7.5 wt%), and its mild hydrogen discharge condition, it is considered as a typical high-density solid-state hydrogen storage material, and is a very promising on-board hydrogen storage system, but the current slow hydrogen discharge power and poor cycle stability restrict practical application.
In recent years, most studies have focused on doping catalytic modification of the metal, such as various catalysts of transition metals (transition metal simple substance, hydride, oxide, halide, etc.), rare earth compounds and carbon-based materials, and reported catalysts such as Ti and TiO 2 、TiF 3 、HfCl 4 、CeCl 3 、Sm 2 O 3 、SmCl 3 Is equally directed to NaAlH 4 The hydrogen storage performance of (2) is improved to a certain extent. It was found that in NaAlH 4 In the research of catalytic hydrogen storage of coordination hydride, the titanium-based compound has the best catalytic effect for a plurality of metals and compound catalysts thereof adopted at present.
Lee et al NaAlH 4 With TiO 2 Ball milling and mixing, adding nano TiO 2 The hydrogen release amount of the particle mixed system reaches 5.1 wt percent, and the result shows that the TiO 2 Nanoparticle pair NaAlH 4 The hydrogen evolution kinetics and the cycling performance of the catalyst have good catalytic action [ Gil-Jae Lee, jae-Hyeok Shim, young broad Cho, et al 4 catalyzed with TiO 2 nanopowder. International Journal of Hydrogen Energy[J]. 2008, 33, 3748-3753.]. However, the titanium-based compound has higher initial hydrogen evolution temperature and has catalytic superiority based on two-dimensional metal carbide (MXene), so that MXene material has wider application in the catalytic field.
Transition metal carbide or nitride (MXene) is a novel two-dimensional material with a graphene-like structure, and the unique two-dimensional structure of the MXene provides a good diffusion channel for the embedding and the extraction of ions, so that the diffusion rate of the ions in the MXene is accelerated. Due to the unique two-dimensional layered structure, large specific surface area, good capacitance and hydrophilicity, the MXene material is widely applied to the fields of lithium ion batteries, supercapacitors, functional ceramics and the like. In MXene materials, ti 3 C 2 And Ti 2 C is more mature.
Ti 3 C 2 Prior art as catalysts:
all Hu Fei adopts NaAlH 4 As a hydrogen storage material, ti 3 C 2 As a catalyst; when Ti is present 3 C 2 NaAlH in an amount of 7 wt% 4 The initial hydrogen release temperature is reduced to 98 ℃, the temperature is heated to 200 ℃ along with the temperature, and the hydrogen release amount reaches 4.9 wt%; wherein, ti 3 C 2 Is prepared by etching Ti with hydrofluoric acid 3 AlC 2 The method for preparing the catalyst [ all Hu Fei, the preparation of Ti-based catalyst and the preparation of MgH 2 And NaAlH 4 Influence of Hydrogen absorption and desorption Properties of Hydrogen storage Material [ D]Zhejiang, university of Zhejiang, 2018.]。
CN109052403A discloses a two-dimensional titanium carbide doped lithium aluminum hydride hydrogen storage material and a preparation method thereof, and LiAlH is adopted 4 As a hydrogen storage material, ti 3 C 2 As a catalyst; when Ti is present 2 LiAlH when the addition amount of C is 5 wt% 4 The initial hydrogen release temperature of the reactor is 48.8 ℃; wherein, ti 3 C 2 The preparation method of (a) is the same as that of all Hu Fei.
By comparing Hu Fei and CN109052403A, naAlH 4 And LiAlH 4 Two hydrogen storage materials, using the same Ti 3 C 2 As a catalyst, however, ti is caused due to the difference in alkali metal elements 3 C 2 The catalytic effect of (a) produces a significant difference.
Ti 2 C prior art as catalyst:
li and the like are Ti 2 Using AlC as raw material and adopting etching method to prepare Ti 2 C, and MgH is adopted 2 As a hydrogen storage material, ti 2 C is used as a catalyst; when Ti is present 2 When the added amount of C is 5 wt%, mgH 2 The initial hydrogen release temperature is 423 ℃, the surface activation energy (Ea) is 157.9 kJ/mol, the total enthalpy change (delta H) is 59.5 kJ/mol, and the total enthalpy change (delta H) is respectively higher than that of pure MgH 2 The temperature is reduced by 37 ℃,36.5 percent and 11 percent; wherein, ti 2 C is prepared by etching Ti with hydrofluoric acid 2 The preparation of [ Jingxiao Li, shun Wang, yulei Du, et al, catalytic effect of Ti ] from AlC 2 C MXene on the dehydrogenation of MgH 2 [J]. International Journal of Hydrogen Energy, 2019, 44: 6787–6794.]。
To prove that the same is Ti 2 C as a catalyst, however, ti due to the difference of hydrogen storage materials 2 The catalytic effect of C produced significant differences. The invention additionally prepares LiAlH by the comparative example 2 4 As a hydrogen storage material, ti 2 C is used as hydrogen storage material of catalyst, and the hydrogen production performance is tested when Ti is used 2 LiAlH when the addition amount of C is 5 wt% 4 The initial hydrogen discharge temperature of (3) is 72 ℃, when the temperature is increased to 300 ℃, liAlH 4 The total hydrogen release amount of the titanium carbide is about 5 wt percent, and the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material prepared by the method is prepared by using NaAlH 4 As a hydrogen storage material, ti 2 C as the hydrogen storage material of the catalyst, the same Ti can be obtained by comparison 2 C as a catalyst, however, causes Ti due to the difference in alkali metal elements 2 The catalytic effect of C gave the conclusion of significant differences.
Therefore, the technical schemes of MXene material catalytic metal complex hydrides provided by the prior art all present the following technical problems: 1) The initial hydrogen release temperature is higher; 2) The hydrogen release dynamic performance is poor, and the hydrogen release amount is low.
However, the inventors have found that the root of the above technical problem is to solve the problem of matching the hydrogen storage material and the catalyst.
Disclosure of Invention
The invention aims to provide a two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material and a preparation method thereof.
The inventor researches and discovers that:
Ti 3 C 2 the adsorption energy of Na atoms in the most stable Na adsorption configuration is 1.785 eV, and the most stable adsorption sites of the Na atoms are the top positions of C atoms;
Ti 2 the adsorption energy of Na atoms in the most stable Na adsorption configuration of C is 1.830 eV, and the most stable adsorption sites of the Na atoms are hollow sites of Ti atoms on the second layer;
it is known from the common knowledge that the larger the adsorption energy, the more stable the adsorption site. Therefore, from the theoretical analysis, it is found that Ti is preferable to Ti 3 C 2 ，Ti 2 C as catalyst should be more suitable for NaAlH 4 Hydrogen storage materials, but not for LiAlH 4 A hydrogen storage material.
On the basis of the theory, the inventor adjusts the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material provided by the invention and effectively controls NaAlH 4 The hydrogen discharging process of the hydrogen storage material can simultaneously realize the following 2 technical effectsAnd (4) fruit:
1. reducing the initial hydrogen release temperature of 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 carried out at 225-275 ℃.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
two-dimensional titanium carbide Ti 2 C-doped sodium aluminum hydride hydrogen storage material, comprising sodium aluminum hydride and two-dimensional titanium carbide Ti 2 C, mixing and mechanically milling to obtain the product;
the two-dimensional titanium carbide Ti 2 The addition amount of C accounts for 1-9 wt% of the total mass;
the two-dimensional titanium carbide Ti 2 C presents a two-dimensional sheet stacking structure, which shows that hydrofluoric acid successfully etches Ti 2 AlC, the layer is obviously stripped; the two-dimensional titanium carbide Ti 2 C is Ti 2 AlC and hydrofluoric acid.
The preparation method of the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material comprises the following steps:
step 1) two-dimensional Ti 2 C preparation of Ti with a particle size of 0.1-30 μm 2 AlC ceramic powder as raw material and Ti 2 The addition amount of AlC ceramic powder is 0.05-0.1 g/ml, and Ti is added 2 Immersing AlC ceramic powder in 10-20 wt% hydrofluoric acid solution, reacting under magnetic stirring at 20-40 deg.C for 10-15 h, washing with deionized water until pH is 7, vacuum filtering, and vacuum drying at 80-100 deg.C for 8-12 h to obtain two-dimensional titanium carbide Ti 2 C；
Step 2) preparation of two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material by using two-dimensional Ti under the protection of argon 2 The mass fraction of C satisfies the condition that the addition amount accounts for 1-9 wt percent of the total mass, and the two-dimensional titanium carbide Ti obtained in the step 1 is weighed 2 C, sodium aluminum hydride in the presence of argon as a protective atmosphere, wherein the ball-to-feed ratio is (60-40): 1, ball milling at the ball milling rotating speed of 400-600 r/min for 2-4 h to obtain the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material.
In order to prove that the two-dimensional titanium carbide material is successfully prepared, an X-ray diffraction test is carried out on the two-dimensional titanium carbide material, and diffraction peaks appear at 33.7 degrees and 60.4 degrees, which indicates that the titanium carbide is successfully prepared.
In order to prove the structural characteristics of the two-dimensional titanium carbide material, the material structure prepared by the method is a two-dimensional layered stacked structure through the test of a scanning electron microscope.
In order to prove the influence of the addition of two-dimensional titanium carbide as a catalyst on the hydrogen desorption performance of sodium aluminum hydride, ti was prepared 2 The two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material has the C content of 0wt%, 1wt%, 7 wt% and 9 wt%, respectively. The temperature rise dehydrogenation test proves that the initial hydrogen release temperature of the sodium aluminum hydride hydrogen storage material added with the two-dimensional titanium carbide is 45-92 ℃, the hydrogen release temperature is reduced by 1-48 ℃ compared with that of pure sodium aluminum hydride, and the total hydrogen release amount reaches 4.9-6 wt%.
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 the sodium aluminum hydride, and has higher hydrogen storage capacity and hydrogen discharge rate under mild conditions. Titanium carbide Ti in two dimensions 2 When the doping amount of C is 1wt%, the initial hydrogen release temperature is reduced to 45 ℃, the hydrogen release amount reaches 6.0 wt%, and the hydrogen release performance is greatly improved;
2. the two-dimensional titanium carbide Ti prepared by the invention 2 The C has a two-dimensional layered structure, and can be fully combined with sodium aluminum hydride when being used as a catalyst to be compounded with the sodium aluminum hydride, so that the hydrogen release performance of the composite hydrogen storage material is improved, and the indication shows that Ti 2 C is used as a catalyst to be more matched with the sodium aluminum hydride hydrogen storage material;
3. the two-dimensional titanium carbide Ti prepared by the invention 2 The method C has the advantages of low cost, simple preparation process, controllable reaction and the like.
Drawings
FIG. 1 shows two-dimensional titanium carbide Ti prepared by etching with hydrofluoric acid according to embodiment 1 of the present invention 2 An XRD spectrum of C;
FIG. 2 is a two-dimensional etching process using hydrofluoric acid according to embodiment 1 of the present inventionTitanium carbide Ti 2 C, a field emission scanning electron microscope image;
FIG. 3 shows Ti doping in accordance with embodiments 1 to 3 of the present invention 2 NaAlH with C content of 1wt%, 7 wt% and 9 wt% 4 Dehydrogenation graph of (a);
FIG. 4 is the doping 0wt% of Ti of specific comparative example 1 of the present invention 2 NaAlH of C 4 The dehydrogenation graph of (a);
FIG. 5 is the doping 1wt% of Ti of specific comparative example 2 of the present invention 2 LiAlH of C 4 Dehydrogenation profile of (a).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material comprises the following steps:
step 1) two-dimensional Ti 2 C preparation with Ti having a particle size of 10 μm 2 AlC ceramic powder as raw material and Ti 2 The adding amount concentration of the AlC ceramic powder is 0.1 g/ml, and Ti is added 2 Immersing AlC ceramic powder in hydrofluoric acid solution with the concentration of 15 wt%, reacting under the condition of magnetic stirring reaction of 10 h at the reaction temperature of 30 ℃, washing the solution until the pH value is 7 by deionized water, performing reduced pressure suction filtration, and performing vacuum drying on 12 h at the temperature of 80 ℃ to obtain the two-dimensional titanium carbide Ti, wherein the concentration of Ti is 15 wt% 2 C；
Step 2) two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material (Ti) 2 C content of 1 wt%) is prepared by weighing 0.005 g obtained in step 1 under the protection of argon gas, and obtaining two-dimensional layered titanium carbide Ti 2 C and 0.495 g NaAlH 4 Under the protection atmosphere of argon, the ball-material ratio is 40:1, ball milling at the rotating speed of 450 r/min for 2 h to obtain the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material.
In order to prove that the two-dimensional titanium carbide material is successfully prepared, an X-ray diffraction test is carried out on the two-dimensional titanium carbide material, and the test result is shown in figure 1, and diffraction peaks appear at 33.7 degrees and 60.4 degrees, which indicates that the titanium carbide material is successfully prepared.
In order to prove the structural characteristics of the two-dimensional titanium carbide material, the structure of the material is a two-dimensional layered stacked structure as shown in fig. 2 through the test of a scanning electron microscope.
The obtained Ti 2 The sodium aluminum hydride hydrogen storage material with the C content of 1wt percent is subjected to a temperature rise dehydrogenation test, and the test method comprises the following steps: a proper amount of sample (600 mg-800 mg) is weighed, the temperature is increased to 300 ℃ at the heating rate of 3 ℃/min to test the hydrogen release performance of the hydrogen storage material, the detection result is shown in figure 3, the initial hydrogen release temperature is 45 ℃, and the hydrogen release amount is 6.0 wt% when the temperature is increased to 300 ℃.
To demonstrate the effect of the addition of two-dimensional titanium carbide as a catalyst on the hydrogen evolution performance of sodium aluminum hydride, ti was prepared by comparative example 1, examples 1, 2 and 3 2 The two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material has the C content of 0wt%, 1wt%, 7 wt% and 9 wt%. The test results are shown in fig. 3 and 4. The initial hydrogen release temperature of the sodium aluminum hydride hydrogen storage material added with the two-dimensional titanium carbide is proved to be 45-92 ℃, the initial hydrogen release temperature is reduced by 1-48 ℃ compared with that of pure sodium aluminum hydride, and the total hydrogen release amount reaches 4.9-6 wt percent.
Comparative example 1
Without adding Ti 2 Sodium aluminum hydride hydrogen storage material of C, i.e. Ti 2 The preparation method of the sodium aluminum hydride hydrogen storage material with the C content of 0wt percent has the same steps as the example 1 except that: in the step 2.1, ti is not added 2 C, respectively weighing 0 g two-dimensional titanium carbide Ti in an argon atmosphere glove box 2 C and 0.5 g NaAlH 4 。
The obtained Ti 2 The sodium aluminum hydride hydrogen storage material with the C content of 0wt percent is subjected to a temperature rise dehydrogenation test, the test method is the same as that of the example 1, the test result is shown in figure 4, the initial hydrogen release temperature is 93 ℃, and the hydrogen release amount is 4.5 wt percent when the temperature is raised to 300 ℃.
Therefore, the initial hydrogen release temperature of the sodium aluminum hydride hydrogen storage material added with the two-dimensional titanium carbide is 45-92 ℃, the initial hydrogen release temperature is reduced by 1-48 ℃ compared with that of pure sodium aluminum hydride, and the total hydrogen release amount reaches 4.9-6 wt percent, which shows that the added Ti 2 C has very good hydrogen release performance on sodium aluminum hydride hydrogen storage materialsGood catalytic action.
Comparative example 2
To study Ti 2 C on the hydrogen release performance of other light hydrogen storage materials, and the inventor also tests Ti 2 C-doped LiAlH 4 The hydrogen desorption performance of the hydrogen storage material is shown in FIG. 5, when 1wt% Ti is added 2 C, when the temperature is increased to 300 ℃, liAlH 4 The total hydrogen evolution of about 5 wt% demonstrates Ti 2 C does not have a good catalytic effect on all hydrogen storage materials.
Example 2
Two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material (Ti) 2 Preparation method of C content of 7 wt%), the steps which are not specifically described are the same as example 1, except that: in said step 2.1, ti 2 The addition amount of C is 7 wt percent, and 0.035 g two-dimensional titanium carbide Ti is respectively weighed in an argon atmosphere glove box 2 C and 0.465 g NaAlH 4 。
The obtained Ti 2 The sodium aluminum hydride hydrogen storage material with the C content of 7 wt percent is subjected to a temperature rise dehydrogenation test, the test method is the same as that of the example 1, the detection result is shown in figure 3, the initial hydrogen release temperature is 75 ℃, and the hydrogen release amount is 4.9 wt percent when the temperature is raised to 300 ℃.
Example 3
Two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material (Ti) 2 The preparation method of the C content of 9 wt%) is the same as that of the embodiment 1 except that: in said step 2.1, ti 2 The addition of C is 9 wt%, and 0.045 g two-dimensional titanium carbide Ti is weighed in an argon atmosphere glove box 2 C and 0.455 g NaAlH 4 。
The obtained Ti 2 The sodium aluminum hydride hydrogen storage material with the C content of 7 wt percent is subjected to a temperature rise dehydrogenation test, the test method is the same as that of the example 1, the detection result is shown in figure 3, the initial hydrogen release temperature is 92 ℃, and the hydrogen release amount is 5.4 wt percent when the temperature is raised to 300 ℃.
Thus, ti 2 The hydrogen release performance of the sodium aluminum hydride hydrogen storage material with the C content of 1wt percent is optimal. As shown in fig. 3, the initial hydrogen-releasing temperature is 45 ℃, which is 48 ℃ lower than that of pure sodium aluminum hydride,when the temperature is raised to 300 ℃, the hydrogen release amount is 6.0 wt percent, which is improved by 33.3 percent compared with pure sodium aluminum hydride.
Claims (3)
1. A two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material is characterized in that: from sodium aluminium hydride and two-dimensional titanium carbide Ti 2 C, mixing and mechanically milling to obtain the product;
the two-dimensional titanium carbide Ti 2 The addition amount of C accounts for 1wt percent of the total mass;
the two-dimensional titanium carbide Ti 2 C, presenting a two-dimensional sheet stacking structure;
the two-dimensional titanium carbide Ti 2 C is Ti 2 AlC and hydrofluoric acid.
2. The method for preparing a two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material as claimed in claim 1, wherein the method comprises the following steps:
step 1) two-dimensional Ti 2 C preparing Ti 2 Immersing AlC ceramic powder in hydrofluoric acid solution, reacting under certain conditions, washing, filtering and drying to obtain two-dimensional titanium carbide Ti 2 C；
Ti of said step 1) 2 The addition amount of the AlC ceramic powder material meets the requirements that the concentration is 0.05-0.1 g/ml, and the concentration of hydrofluoric acid is 10-20 wt%;
ti of said step 1) 2 The grain size of AlC ceramic powder is 0.1-30 μm;
the reaction condition of the step 1) is that the reaction is carried out at the reaction temperature of 20-40 ℃ by magnetic stirring for 10-15 h; the filtration is vacuum filtration; the drying condition is that 8-12 h is dried in vacuum at the temperature of 80-100 ℃;
step 2) preparation of the two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material, weighing the two-dimensional titanium carbide Ti obtained in the step 1) according to a certain mass fraction under the protection of argon 2 C, ball milling the mixture and sodium aluminum hydride under certain conditions to obtain a two-dimensional titanium carbide-doped sodium aluminum hydride hydrogen storage material;
said step 2) two-dimensional Ti 2 The mass fraction of C satisfies that the addition amount accounts for 1wt percent of the total mass; what is needed isThe ball milling conditions are that argon is used as protective atmosphere, the ball-to-material ratio is (60-40): 1, the ball milling rotating speed is 400-600 r/min, and the ball milling time is 2-4 h.
3. The application of the two-dimensional titanium carbide doped sodium aluminum hydride hydrogen storage material as the hydrogen storage field according to claim 1 is characterized in that: when the doping amount of the catalyst is 1wt%, the hydrogen release temperature of the system is reduced to 45 ℃, and the hydrogen release amount reaches 6.0 wt%.
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