A catalyst and a preparation method thereof, and a hydrogen storage material containing the catalyst and a preparation method thereof
By introducing TiO2-based catalysts into magnesium hydride-based hydrogen storage materials, the problem of poor hydrogen absorption and discharge performance is solved, and room temperature hydrogen absorption, low temperature dehydrogenation and good cycle stability are achieved, which is suitable for large-scale production.
Patent Information
- Application Number
- CN202111176011.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-10-09
- Publication Date
- 2025-05-23
- Estimated Expiration
- 2041-10-09
AI Technical Summary
The thermodynamic and kinetic properties of existing magnesium hydride-based hydrogen storage materials are poor, resulting in limited use progress, especially the high dehydrogenation reaction temperature and cyclic stability deviation.
The TiO2-based catalyst is used to combine the elemental materials, hydrides or borohydrides of metal M (such as Li, Na, K) with TiO2 to form an X-TiO2 catalyst, and prepare it by solid phase ball milling or plasma treatment, to improve the hydrogen absorption and discharge performance of magnesium-based hydrogen storage materials.
The excellent hydrogen absorption capacity of magnesium-based hydrogen storage materials at room temperature and near room temperature is achieved, the cycle temperature of absorption and dehydrogenation is reduced, the rapid hydrogen absorption and discharge speed and good cycle stability are maintained, and the hydrogen storage capacity is maintained above 3.5 wt%, which is suitable for large-scale production.
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Abstract
Description
Technical Field
[0001] The present application relates to a catalyst and a preparation method thereof, and a hydrogen storage material containing the catalyst and a preparation method thereof, and belongs to the technical field of hydrogen storage materials and hydrogen storage applications. Background Art
[0002] With the depletion of fossil energy and the gradual strengthening of human environmental awareness, the development of new energy has become a topic of common concern around the world. Hydrogen energy is a new energy source with abundant reserves, clean and pollution-free, high mass energy density, and various forms of utilization. The large-scale application of hydrogen energy will have a significant impact on human society. However, the efficient and safe storage of hydrogen has always been the main technical bottleneck restricting the development of hydrogen energy.
[0003] Since the introduction of hydrogen storage materials in the 1960s, they have been a hot topic in the energy field. 2 ) has attracted worldwide attention. Mg is an element with abundant reserves (the content of Mg in the earth is about 2.5wt.%). It has high mass hydrogen storage density (7.6wt.%), volume hydrogen storage density (110kg / m 3 ) and low raw material prices. MgH 2 It is recognized as one of the most promising hydrogen storage materials, but its thermodynamic and kinetic properties of hydrogen absorption and desorption are poor (generally, the operating temperature of pure magnesium hydride for hydrogen absorption and desorption must be higher than 350°C, and the temperature for releasing 0.1MPa equilibrium hydrogen pressure must be higher than 300°C), which seriously hinders its application progress.
[0004] Catalyst modification is to improve Mg / MgH 2 The addition of a small amount of catalyst can not only maintain a high hydrogen storage capacity, but also effectively improve its hydrogen storage kinetics and cycle stability. Dehouche (Z. Dehouche et al. J Alloy Compd. 2002, 347, 319-323), Barkhordarian (G. Barkhordarian et al. J Alloy Compd. 2004, 364, 242-246) and others used high energy ball milling to prepare MgH 2 The system is doped with transition metal oxide Cr 2 O 3 and Nb 2 O 5 , the system's absorption and dehydrogenation temperatures were reduced to 300°C and 250°C, respectively, and showed good cycle stability. Bormann (Bormann, R. et al. J. Alloys Compd. 2001, 315, 237-242.) and others systematically investigated the effects of a series of metal oxides on MgH2 The influence of metal oxides on hydrogen storage performance was found to significantly accelerate the rate of hydrogen absorption and desorption of magnesium hydride hydrogen storage materials. 2 The dehydrogenation rate of the doped system exceeds 20 kW / kg and can reduce the dehydrogenation activation energy of the material.
[0005] Although the catalysts reported so far are 2 The hydrogen storage performance has been improved to varying degrees, but there are widespread problems of high dehydrogenation reaction temperature and cycle stability deviation, which hinders its further promotion and development. The development of new and efficient magnesium hydride-based hydrogen storage material catalysts and preparation methods has important development prospects and practical value. Summary of the invention
[0006] According to this application, we provide a TiO 2 A magnesium-based catalyst and a preparation method thereof, and a modified magnesium-based hydrogen storage material containing the catalyst and a preparation method thereof. The hydrogen storage material has room temperature and near room temperature hydrogen absorption capacity, a lower hydrogen absorption and dehydrogenation cycle temperature, and can maintain a faster hydrogen absorption and desorption rate, better cycle stability and a higher hydrogen storage capacity. In particular, the preparation process is simple and suitable for large-scale production, and has a good development prospect and practical application value.
[0007] According to one aspect of the present application, a catalyst is provided, wherein the catalyst contains component X and TiO 2 ;
[0008] The component X is selected from a metal M element, a hydride of M or a borohydride of M;
[0009] The metal M is selected from at least one of Li, Na, K and Rb;
[0010] The component X and TiO 2 The mass ratio is 1:100~10:1.
[0011] The TiO 2 The configuration is at least one of a rutile structure or anatase structure.
[0012] According to another aspect of the present application, a method for preparing the above-mentioned catalyst is provided, comprising the following steps:
[0013] The mixture containing component X and TiO 2 Mixing or compounding the raw materials to obtain the catalyst;
[0014] The mixing is solid phase ball milling I;
[0015] The compounding is selected from one of plasma treatment and microwave treatment.
[0016] The mixed and compounded atmosphere includes at least one of an inert gas or hydrogen; the inert gas includes argon and / or helium;
[0017] Optionally, the mixing and compounding are performed under vacuum conditions.
[0018] The conditions of the solid phase ball milling I are:
[0019] Atmosphere pressure is 0.1-10MPa; temperature is 10-100℃; ball-to-material ratio is between 20:1 and 120:1; rotation speed is 50-600 rpm; time is 0.5-60 hours;
[0020] The plasma treatment comprises the following steps: 1) loading samples under an inert gas protection atmosphere; 2) connecting a reactor and a plasma instrument under a protective gas or vacuum condition; 3) plasma treatment after argon purging; and 4) recovering catalysts from samples under an inert gas protection atmosphere.
[0021] The specific process is as follows: load the sample in an argon-protected glove box (the sample volume is less than 1 / 3 of the volume of the sample tube / reactor), seal the inlet and outlet of the sample tube and connect it to the plasma reactor, purge the reactor and plasma instrument pipelines with argon gas, apply plasma for a certain time after the gas is stable, and after the plasma treatment is completed, seal the inlet and outlet of the sample tube and move it into the glove box for sampling.
[0022] The conditions of the plasma treatment are: atmosphere pressure less than 0.2 MPa; temperature of 20 to 300° C., plasma generator power of 4 to 50 watts, and time of 0.1 to 5 hours;
[0023] The microwave treatment comprises the following steps: 1) loading samples under an inert gas protection atmosphere; 2) connecting a reactor and a microwave generating reactor under a protective gas or vacuum condition; 3) microwave reaction treatment after argon purging; and 4) sample recovery under an inert gas protection atmosphere.
[0024] The specific process is as follows: a sample volume less than 1 / 4 of the sample tube / reactor volume is loaded into an argon-protected glove box, the inlet and outlet of the sample tube are sealed and connected to the microwave reactor, argon is purged into the reactor and microwave reactor pipelines, and microwave treatment is applied after the airflow is stable. After a period of microwave treatment, the inlet and outlet of the sample tube are sealed and moved into the glove box for sampling.
[0025] The microwave treatment conditions are as follows: atmosphere pressure of 0.1-2 MPa, temperature of 30-600° C., microwave power of 100-1000 watts, time of 0.1-4 hours, and argon gas flow rate of less than 200 ml / min.
[0026] According to another aspect of the present application, there is provided a use of the above catalyst or the catalyst prepared by the above preparation method in a hydrogen storage reaction.
[0027] According to another aspect of the present application, a hydrogen storage material is provided, the hydrogen storage material comprising a magnesium material and a catalyst;
[0028] The catalyst is the above catalyst or a catalyst prepared by the above preparation method.
[0029] The magnesium material is selected from MgH 2 , magnesium powder or magnesium alloy;
[0030] The magnesium alloy also contains at least one metal element selected from the group consisting of Li, Al, Zn, Ni, La, Y, Nd, Ce, Dy, and Gd; the magnesium content in the magnesium alloy is not less than 45%, calculated by weight of the metal element.
[0031] The initial dehydrogenation temperature of the hydrogen storage material is 120-200° C.; the maximum dehydrogenation rate is reached at 210-280° C.; and the hydrogen absorption capacity is >3.5wt% at 25-75° C.
[0032] According to another aspect of the present application, a method for preparing the above-mentioned hydrogen storage material is provided, comprising the following steps:
[0033] Stirring and ball-milling the raw materials containing magnesium material and catalyst II to obtain the hydrogen storage material;
[0034] The mass ratio of the magnesium material to the catalyst is 100:1 to 1:1.
[0035] The stirring conditions are: inert gas or hydrogen atmosphere; the inert gas includes argon and / or helium; the atmosphere pressure is 0.1-10 MPa; the temperature is 10-100° C.; the rotation speed is 2000-10000 rpm; the time is 0.5-40 hours;
[0036] The conditions of ball milling II are: inert gas or hydrogen atmosphere; the inert gas includes argon and / or helium; the atmosphere pressure is 0.1-10 MPa; the temperature is 10-100° C.; the ball-to-material ratio is 10-150; the rotation speed is 50-600 rpm; and the time is 0.5-60 hours.
[0037] The ball milling II includes wet ball milling and dry ball milling;
[0038] In the stirring or wet ball milling, the raw material includes a solvent, and the volume of the solvent is 10% to 1000% of the total volume of the hydrogen storage material;
[0039] The solvent is selected from at least one of methanol, ethanol, pentane, cyclohexane, THF, and toluene;
[0040] Optionally, the wet ball milling conditions include: under inert protective gas or hydrogen reaction gas conditions, a temperature of 10 to 100° C., a rotation speed of 50 to 600 rpm, and a time of 0.5 to 40 hours;
[0041] The conditions of the dry ball milling include: a ball-to-material ratio of 10 to 150:1, a rotation speed of 50 to 600 rpm, and a time of 0.5 to 60 hours;
[0042] Optionally, the conditions for dry ball milling include: under an inert protective gas or hydrogen reaction, a pressure of 0.1 to 10 MPa and a temperature of 10 to 100° C.
[0043] Furthermore, the method for preparing the hydrogen storage material further comprises: 2 The raw materials are mixed and stirred, and ball milled II to obtain the hydrogen storage material.
[0044] The beneficial effects of this application include:
[0045] The hydrogen storage material provided by the present invention is obtained by introducing X-TiO into the magnesium-based hydrogen storage material. 2 The catalyst enables the material to have excellent catalytic activity, low hydrogen absorption and desorption temperature, can absorb hydrogen at room temperature, and significantly improves the kinetic performance of hydrogen absorption and desorption; the initial hydrogen absorption and desorption does not require activation, not only maintaining a faster hydrogen absorption and desorption speed, but also having good cycle stability, and the hydrogen storage capacity is maintained at above 3.5wt%; the preparation process is simple and easy, and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0046] Figure 1 The Na-TiO prepared in Example 1 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Programmed temperature dehydrogenation mass spectrum curve.
[0047] Figure 2 The NaH-TiO prepared in Example 2 2 XRD patterns of the catalysts.
[0048] Figure 3 The NaH-TiO prepared in Example 2 2 XPS pattern of the catalyst.
[0049] Figure 4 The NaH-TiO prepared in Example 2 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Programmed temperature dehydrogenation mass spectrum curve.
[0050] Figure 5 The NaH-TiO prepared in Example 2 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Volumetric dehydrogenation curve of .
[0051] Figure 6 The NaH-TiO prepared in Example 2 2 Catalyst added MgH 2 Isothermal dehydrogenation curve at 290 °C.
[0052] Figure 7 The NaH-TiO prepared in Example 2 2 Catalyst added MgH 2 Hydrogen absorption curves at different hydrogen pressures at room temperature.
[0053] Figure 8 The NaH-TiO prepared in Example 2 2 Catalyst added MgH 2 Cyclic absorption and dehydrogenation curve under 300℃ conditions.
[0054] Fig. 9 The NaH-TiO prepared in Example 3 2 -MgH 2 Room temperature hydrogen absorption curve of hydrogen storage materials.
[0055] Fig.10 KH-TiO prepared in Example 4 2 XRD patterns of the catalysts.
[0056] Fig.11 KH-TiO prepared in Example 4 2 XPS pattern of the catalyst.
[0057] Fig.12 Preparation of KH-TiO for Example 4 2 Morphological structure analysis of the samples, (a) is commercial TiO 2 SEM images of (b, c) KH-TiO 2 SEM images of the samples, (d, e) are KH-TiO 2 TEM images of the samples; (f, g, h, i) are KH-TiO 2 EDS spectrum of the sample.
[0058] Fig.13 KH-TiO prepared in Example 4 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Programmed temperature dehydrogenation mass spectrum curve.
[0059] Fig.14 KH-TiO prepared in Example 4 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Dehydrogenation curve diagram.
[0060] Fig.15 KH-TiO prepared in Example 4 2 Catalyst added MgH 2 Hydrogen absorption curve at room temperature and 3MPa hydrogen pressure.
[0061] Fig.16 The NaBH prepared in Example 5 4 -TiO 2 Catalyst added MgH 2 and without catalyst addition of MgH 2 Programmed temperature dehydrogenation mass spectrum curve. DETAILED DESCRIPTION
[0062] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0063] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.
[0064] The room temperature described in this application is 25°C.
[0065] The analysis method in the examples of this application is as follows:
[0066] The starting temperature and peak temperature of sample dehydrogenation were tracked by programmed temperature dehydrogenation combined with mass spectrometry detection; the amount of hydrogen adsorption and dehydrogenation and related hydrogen storage performance of the hydrogen storage material were tested by Sievert's method.
[0067] Example 1
[0068] In an argon protection glove box, weigh 5 g of metallic sodium particles and TiO at a mass ratio of 15:85. 2 The mixture was put into a ball mill. Ball milling process: the ball-to-material ratio was 30:1, at 60°C, 0.1 MPa argon atmosphere, ball milling for 10 hours, the rotation speed was 100 rpm, and the product was obtained, which was recorded as Na-TiO 2 catalyst;
[0069] In an argon protection glove box, weigh Na-TiO at a mass ratio of 5:95. 2 and MgH 22 g of the mixture was put into a ball mill. Ball milling process: the ball-to-material ratio was 40:1, and the ball milling was performed at room temperature, 0.1 MPa argon atmosphere, and the rotation speed was 200 rpm for 12 hours to obtain Na-TiO 2 Add MgH 2 Hydrogen storage materials.
[0070] Characterization: Programmed temperature dehydrogenation mass spectrometry curves such as Figure 1 , indicating that Na-TiO2 catalyst can significantly reduce the initial and peak dehydrogenation temperatures of MgH2 hydrogen storage materials.
[0071] Example 2
[0072] In an argon-protected glove box, weigh 3 g of NaH and TiO in a mass ratio of 40:60. 2 The powder was put into a ball mill. Ball milling process: the ball-to-material ratio was 30:1, at room temperature, 0.1 MPa argon atmosphere, ball milling for 10 hours, the rotation speed was 100 rpm, and the product was obtained, which was recorded as NaH-TiO 2 catalyst;
[0073] In an argon protection glove box, weigh NaH-TiO at a mass ratio of 5:95. 2 and MgH 2 A total of 2 grams were loaded into the ball mill. Ball milling process: the ball-to-material ratio was 40:1, and the ball milling was performed at room temperature, 0.1 MPa argon atmosphere, and the rotation speed was 200 rpm for 12 hours to obtain NaH-TiO 2 Add MgH 2 Hydrogen storage materials.
[0074] Figure 2 For the preparation of NaH-TiO 2 XRD pattern of the catalyst; it can be seen from the figure that the phase structure is different from that of pure TiO 2 The sample contains NaH;
[0075] Figure 3 For the preparation of NaH-TiO 2 The signal of Ti element in the XPS spectrum of the catalyst clearly shows that Ti 3+ , Ti 2+ and Ti 0 signal, indicating that TiO2 is reduced;
[0076] Figure 4 To prepare NaH-TiO 2 Catalyst MgH 2 Hydrogen storage materials and pure MgH 2 Comparison of the programmed temperature dehydrogenation mass spectrometry curves of pure MgH 2 Materials, after NaH-TiO2 The dehydrogenation performance of catalyst-modified magnesium hydride was significantly improved, the initial dehydrogenation temperature dropped to about 190°C, and the maximum dehydrogenation rate was reached at 245°C.
[0077] Figure 5 To prepare NaH-TiO 2 Catalyst MgH 2 and pure MgH 2 The dehydrogenation curve results of (without catalyst addition) are compared; it can be seen from the figure that after NaH-TiO 2 The dehydrogenation performance of catalyst-modified magnesium hydride was significantly improved, the initial dehydrogenation temperature dropped to about 190°C, and the dehydrogenation reached 7.1wt% at 270°C;
[0078] Figure 6 To prepare NaH-TiO 2 Catalyst MgH 2 The dehydrogenation curve at isothermal temperature of 290 °C; it can be seen from the figure that after NaH-TiO 2 Catalyst-modified magnesium hydride can release 7.1 wt% hydrogen in 20 minutes;
[0079] Figure 7 To prepare NaH-TiO 2 Catalyst MgH 2 The hydrogen absorption curves of NaH-TiO at room temperature and different pressures. 2 Catalyst-modified magnesium hydride can rapidly absorb up to 5.5 wt% hydrogen at room temperature under 1 to 5 MPa.
[0080] Figure 8 To prepare NaH-TiO 2 Catalyst MgH 2 The absorption and desorption curve of NaH-TiO at 300℃. 2 The catalyst-modified magnesium hydride can stably absorb more than 6.0 wt% of hydrogen.
[0081] Example 3
[0082] In an argon protection glove box, weigh 2 g of NaH and TiO in a mass ratio of 5:5:90. 2 and MgH 2 The ball milling process: the ball-to-material ratio is 40:1, and the ball milling is carried out for 12 hours at room temperature, 0.1MPa argon atmosphere, and the rotation speed is 200 rpm to obtain NaH-TiO 2 -MgH 2 Hydrogen storage materials.
[0083] Fig. 9For the preparation of NaH-TiO 2 -MgH 2 Room temperature hydrogen absorption curve of hydrogen storage material; it can be seen from the figure that the modified MgH2 can quickly absorb up to nearly 6wt% hydrogen at room temperature.
[0084] Example 4
[0085] In an argon protection glove box, weigh potassium hydride powder and TiO in a mass ratio of 30:70. 2 A total of 3 grams were loaded into the ball mill. Ball milling process: the ball-to-material ratio was 30:1, at room temperature, 0.1 MPa argon atmosphere, ball milling for 10 hours, the rotation speed was 100 rpm, and the product was obtained, which was recorded as KH-TiO 2 catalyst;
[0086] In an argon protection glove box, weigh KH-TiO at a mass ratio of 5:95. 2 and MgH 2 A total of 2 grams were loaded into the ball mill. Ball milling process: the ball-to-material ratio was 40:1, and the ball milling was performed for 12 hours at room temperature in an argon atmosphere of 0.1 MPa and a rotation speed of 200 rpm to obtain KH-TiO 2 Add MgH 2 Hydrogen storage materials.
[0087] Fig.10 For the preparation of KH-TiO 2 XRD pattern of the catalyst; it can be seen from the figure that KH-TiO 2 Different from the pure KH sample, the sample signal is significantly reduced, tending to be amorphous.
[0088] Fig.11 For the preparation of KH-TiO 2 XPS graph of the catalyst. It can be clearly seen from the figure that KH-TiO 2 There are many Ti 3+ Species;
[0089] Fig.12 For the preparation of KH-TiO 2 Catalyst morphology and structure analysis, (a) is commercial TiO 2 SEM images of (b, c) KH-TiO 2 SEM images of the samples, (d, e) are KH-TiO 2 TEM images of the samples; (f, g, h, i) are KH-TiO 2 EDS spectrum of the sample; it can be seen from the figure that there are many porous structures in the sample, and TiO 2 The surface of the sample is covered with a layer of KH, and there is K-TiO 2-x species, all samples were evenly distributed.
[0090] Fig.13 To prepare KH-TiO 2 Catalyst MgH 2 and pure MgH 2 The programmed temperature dehydrogenation mass spectrometry curve results (without catalyst addition) are compared with pure MgH 2 Materials, after KH-TiO 2 The dehydrogenation performance of catalyst-modified magnesium hydride was significantly improved, the initial dehydrogenation temperature dropped to about 195°C, and the maximum dehydrogenation rate was reached at 250°C.
[0091] Fig.14 To prepare KH-TiO 2 Catalyst MgH 2 and pure MgH 2 Dehydrogenation curve of (without catalyst addition); it can be seen from the figure that after KH-TiO 2 The hydrogen absorption and dehydrogenation performance of the catalyst-modified magnesium hydride is significantly improved, the dehydrogenation temperature of the sample is significantly reduced, and more than 6.5wt% of hydrogen can be released at 290℃.
[0092] Fig.15 To prepare KH-TiO 2 Catalyst MgH 2 Hydrogen absorption curve at room temperature and 3MPa hydrogen pressure; it can be seen from the figure that the sample can absorb more than 6.0wt% of hydrogen within 2 hours.
[0093] Example 5
[0094] In an argon-protected glove box, weigh NaBH at a mass ratio of 30:70. 4 Powder and TiO 2 A total of 2 grams were loaded into the ball mill. Ball milling process: the ball-to-material ratio was 20:1, at room temperature, 0.1 MPa argon atmosphere, ball milling for 10 hours, the rotation speed was 100 rpm, and the product was obtained, recorded as NaBH 4 -TiO 2 catalyst;
[0095] In an argon protection glove box, weigh NaBH at a mass ratio of 10:90. 4 -TiO 2 and MgH 2 The ball milling process: the ball-to-material ratio is 40:1, and the ball milling is carried out for 12 hours at room temperature, 0.1MPa argon atmosphere, and the rotation speed is 200 rpm to obtain NaBH 4 -TiO 2 Add MgH 2 Hydrogen storage materials.
[0096] Fig.16 For the prepared NaBH 4 -TiO 2 catalyst-doped MgH 2 and pure MgH 2 (without catalyst addition), the results of the temperature-programmed dehydrogenation mass spectrometry curves show that, compared with pure MgH 2 material, the hydrogen absorption and desorption performance of magnesium hydride modified by NaBH 4 -TiO 2 catalyst is significantly improved. The initial dehydrogenation temperature drops to about 190 °C, and the maximum dehydrogenation rate is reached at 245 °C;
[0097] Example 6
[0098] In an argon-protected glove box, a total of 2 g of NaBH 4 , TiO 2 and MgH 2 are weighed in a mass ratio of 5:5:90 and loaded into a ball milling jar. Ball milling process: The ball-to-material ratio is 40:1. Under an argon atmosphere at room temperature and 0.1 MPa, ball milling is carried out for 12 hours at a rotation speed of 200 revolutions per minute to obtain NaBH 4 -TiO 2 -MgH 2 hydrogen storage material.
[0099] Example 7
[0100] In an argon-protected glove box, 2 g of sodium hydride powder and TiO 2 are weighed in a mass ratio of 40:60 and loaded into a quartz tube. Plasma process treatment: The hydrogen flow rate is 30 ml / min. At 150 °C, the plasma power is 30 W, and plasma treatment is carried out for 10 minutes to obtain a product, denoted as Plasma-NaH-TiO 2 catalyst;
[0101] In an argon-protected glove box, Plasma-NaH-TiO 2 and MgH 2 are weighed in a mass ratio of 10:90, with a total of 2 g, and loaded into a ball milling jar. Ball milling process: The ball-to-material ratio is 40:1. Under an argon atmosphere at room temperature and 0.1 MPa, ball milling is carried out for 12 hours at a rotation speed of 200 revolutions per minute to obtain Plasma-NaH-TiO 2 -added MgH 2 hydrogen storage material.
[0102] Example 8
[0103] In an argon-protected glove box, 2 g of sodium hydride NaH powder and TiO 2Microwave treatment: hydrogen flow rate 30 ml / min, microwave power 600 watts, microwave time 30 min at room temperature, to obtain the product, recorded as W-NaH-TiO 2 catalyst;
[0104] In an argon protection glove box, weigh W-NaH-TiO at a mass ratio of 10:90. 2 and MgH 2 A total of 2 grams were loaded into the ball mill. Ball milling process: the ball-to-material ratio was 40:1, and the ball milling was performed for 12 hours at room temperature in an argon atmosphere of 0.1 MPa and a rotation speed of 200 rpm to obtain W-NaH-TiO 2 Add MgH 2 Hydrogen storage materials.
[0105] Example 9
[0106] In an argon-protected glove box, weigh 3 g of metallic lithium particles and TiO at a mass ratio of 50:50. 2 The mixture was loaded into a ball mill. The mixture was ball milled for 12 hours at 50°C under 0.1 MPa hydrogen pressure, with a ball-to-material ratio of 30:1 and a ball milling speed of 150 rpm to obtain the product, which was recorded as Li-TiO 2 catalyst;
[0107] In an argon protection glove box, weigh 2 g of Li-TiO at a mass ratio of 10:90. 2 and MgH 2 The ball milling process: the ball-to-material ratio is 40:1, and the ball milling is performed for 20 hours at room temperature, 1MPa hydrogen atmosphere, and the rotation speed is 250 rpm to obtain Li-TiO 2 Add MgH 2 Hydrogen storage materials.
[0108] Example 10
[0109] In an argon protection glove box, weigh sodium hydride NaH powder and TiO in a mass ratio of 20:80. 2 A total of 3 g of powder was put into a ball mill. Ball milling process: the ball-to-material ratio was 30:1, at room temperature, 0.1 MPa argon atmosphere, ball milling for 10 hours, the rotation speed was 100 rpm, and the product was obtained, which was recorded as NaH-TiO 2 catalyst;
[0110] In an argon protection glove box, weigh NaH-TiO at a mass ratio of 10:90. 22 g of Mg powder (300 mesh) and metal Mg powder (300 mesh) were put into a ball mill. Ball milling process: the ball-to-material ratio was 40:1, and the ball milling was performed at room temperature, 5 MPa hydrogen atmosphere, and the rotation speed was 200 rpm for 24 hours to obtain NaH-TiO 2 Added Mg-based hydrogen storage materials.
[0111] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A hydrogen storage material, It is characterized in that The hydrogen storage material includes a magnesium material and a catalyst; The magnesium material is selected from MgH 2 , magnesium powder or magnesium alloy; The magnesium alloy further contains at least one metal element selected from the group consisting of Li, Al, Zn, Ni, La, Y, Nd, Ce, Dy, and Gd; the magnesium content in the magnesium alloy is greater than 45% by weight of the metal element; The catalyst contains component X and TiO 2 ; The component X is selected from a metal M or a hydride of M; The metal M is selected from at least one of Li, Na, K and Rb; The component X and TiO 2 The mass ratio is 1:100~10:1; The initial dehydrogenation temperature of the hydrogen storage material is 120-200°C; the maximum dehydrogenation rate is reached at 210-280°C; the hydrogen absorption amount is >3.5wt% at 25-75°C; The method for preparing the catalyst comprises the following steps: The mixture containing component X and TiO 2 Mixing or compounding the raw materials to obtain the catalyst; The mixing is solid phase ball milling I; The compounding is selected from one of plasma treatment or microwave treatment; The mass ratio of the magnesium material to the catalyst is 100:1 to 1:
1.
2. The hydrogen storage material according to claim 1, It is characterized in that The TiO 2 The configuration is at least one of a rutile structure or anatase structure.
3. The hydrogen storage material according to claim 1, It is characterized in that The mixed and compounded atmosphere includes at least one of an inert gas or hydrogen; the inert gas includes argon and / or helium.
4. The hydrogen storage material according to claim 1, It is characterized in that The conditions of the solid phase ball milling I are: Atmosphere pressure is 0.1~10MPa; temperature is 10~100℃; ball-to-material ratio is between 20:1 and 120:1; speed is 50~600 rpm; time is 0.5~60 hours; The conditions of the plasma treatment are: atmosphere pressure less than 0.2 MPa; temperature of 20-300° C.; plasma generator power of 4-50 watts; time of 0.1-5 hours; The microwave treatment conditions are as follows: atmosphere pressure is 0.1-2 MPa; temperature is 30-600° C.; microwave power is 100-1000 watts; and time is 0.1-4 hours.
5. A method for preparing the hydrogen storage material according to claim 1, It is characterized in that The following steps are involved: Stirring and ball-milling the raw materials containing magnesium material and catalyst II to obtain the hydrogen storage material; The mass ratio of the magnesium material to the catalyst is 100:1 to 1:
1.
6. The preparation method according to claim 5, It is characterized in that The stirring conditions are: inert gas or hydrogen atmosphere; the inert gas includes argon and / or helium; the atmosphere pressure is 0.1-10 MPa; the temperature is 10-100° C.; the rotation speed is 2000-10000 rpm; the time is 0.5-40 hours; The conditions of ball milling II are: inert gas or hydrogen atmosphere; the inert gas includes argon and / or helium; the atmosphere pressure is 0.1-10 MPa; the temperature is 10-100° C.; the ball-to-material ratio is 10-150; the rotation speed is 50-600 rpm; and the time is 0.5-60 hours.