CN110482488B - Composite hydrogen storage material, preparation method and application thereof - Google Patents
Composite hydrogen storage material, preparation method and application thereof Download PDFInfo
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
The invention discloses a composite hydrogen storage material, a preparation method and application thereof. The invention adopts a unique high-temperature reduction carbon coating method to form an even amorphous carbon layer with through 3D pore channels on the surface of the hydrogen storage material particles, thereby not only ensuring the normal input and output paths of hydrogen, but also greatly improving the heat conduction performance of the hydrogen storage material due to the close contact between the carbon layer and the hydrogen storage material particles.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite hydrogen storage material, a preparation method and application thereof.
Background
Hydrogen storage materials (hydrogen storage materials) are a class of materials that can reversibly absorb and release hydrogen gas. Hydrogen storage alloys refer to intermetallic compounds that reversibly absorb, store, and release hydrogen in large quantities at a certain temperature and hydrogen pressure. However, the thermal conductivity of the existing hydrogen storage alloy has a great problem, so that when the alloy is filled into a hydrogen storage device, the problems of local sintering, pulverization, insufficient hydrogen absorption and desorption of materials and the like are caused because heat cannot be transferred into or out of the system in time, and the hydrogen storage dynamic performance and the service life of the system are influenced.
For this reason, some methods for improving the thermal conductivity of the material have been proposed, but the thermal conductivity is still poor.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composite hydrogen storage material, a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a composite hydrogen storage material, where the composite hydrogen storage material includes a hydrogen storage material, and a porous heat-conducting amorphous carbon layer coated on a surface of the hydrogen storage material and a heat-conducting material doped in the porous heat-conducting amorphous carbon layer.
At present, in order to improve the thermal conductivity of the material, it is studied to incorporate the material with higher thermal conductivity such as carbon nanotube and aluminum powder into the hydrogen storage alloy by mechanical mixing method, so as to improve the overall thermal conductivity of the hydrogen storage alloy. However, research shows that although the method of mixing the high-thermal-conductivity material by a mechanical method can improve the overall thermal conductivity of the hydrogen storage alloy to a certain extent, the mixed material and the hydrogen storage alloy still have considerable gaps, so that the heat transfer efficiency between interfaces is low, and the further improvement of the thermal conductivity of a composite system is limited.
Therefore, in order to solve the difficulty in this practical aspect, embodiments of the present invention provide a composite hydrogen storage material, where the composite hydrogen storage material includes a hydrogen storage material, and a porous heat-conducting amorphous carbon layer coated on a surface of the hydrogen storage material and a heat-conducting material doped in the porous heat-conducting amorphous carbon layer. Therefore, the composite hydrogen storage material provided by the embodiment of the invention is different from the existing mechanically mixed composite hydrogen storage material, and the hydrogen storage material is coated in the porous heat-conducting amorphous carbon layer, so that the combination between the hydrogen storage material and the porous heat-conducting amorphous carbon layer coated on the surface of the hydrogen storage material is firmer, the interface contact is better, and the heat-conducting property is stronger. Meanwhile, the carbon layer is also doped with heat conducting materials, so that the heat conducting performance of the whole composite hydrogen storage material is further improved.
In an alternative embodiment, the hydrogen storage material is a hydrogen storage alloy;
preferably, the hydrogen storage alloy is a titanium-based hydrogen storage alloy;
preferably, the particle size of the hydrogen storage material is 150-300 mesh.
The hydrogen storage material in the embodiment of the invention is selected from hydrogen storage alloy, more preferably titanium-based hydrogen storage alloy, because the titanium-based hydrogen storage alloy has high hydrogen storage capacity and high hydrogen discharge platform, the invention has a good application prospect in the field of solid hydrogen storage. The powder is crushed to the particle size of 150-300 meshes in the using process, which is beneficial to coating the surface layer.
In an alternative embodiment, the thermally conductive material comprises a fibrous thermally conductive material;
preferably, the fibrous heat conducting material comprises at least one of PAN-based carbon fiber, glass fiber, graphene fiber and carbon nanotube, and more preferably, the fibrous heat conducting material is selected from carbon nanotube;
preferably, the heat conducting material further comprises metal powder, the metal powder comprises at least one of Au, Ag, Al, Cu and Ti powder, more preferably, the metal powder is selected from the Ti powder, and more preferably, the particle size of the metal powder is less than 500 nm;
more preferably, the fibrous heat conducting material or the metal powder is used in an amount of 0.05 to 1 wt% based on the total amount of the raw materials of the composite hydrogen storage material.
According to the composite hydrogen storage material provided by the embodiment of the invention, the porous heat-conducting amorphous carbon layer is also doped with the heat-conducting material, and the fibrous heat-conducting material can enhance the heat-conducting property and toughness of the carbon layer, so that the coated carbon layer is prevented from being broken when the coated carbon layer is subjected to severe volume change in the hydrogen absorption and desorption process of the hydrogen storage alloy, and the metal powder can further enhance the heat and mass transfer effects of the coated carbon layer. Therefore, the aim of inhibiting the pulverization of the hydrogen storage material in the cyclic hydrogen absorption and desorption process is fulfilled by limiting the volume change rate of the particles in the hydrogen absorption and desorption process.
In an optional embodiment, the porous heat-conducting amorphous carbon layer is a porous heat-conducting amorphous carbon layer with a 3D pore channel structure penetrating through the surface and the interior of the amorphous carbon layer;
preferably, the thickness of the porous heat-conducting amorphous carbon layer is 10nm-100 nm.
According to the composite hydrogen storage material provided by the embodiment of the invention, the porous heat-conducting amorphous carbon layer coated on the surface of the hydrogen storage material is a compact amorphous carbon layer with 3D through holes, so that an effective hydrogen diffusion channel is provided for the composite hydrogen storage material, meanwhile, the agglomeration of alloy in a hydrogen absorption and desorption process is avoided, the carbon layer and hydrogen storage alloy particles maintain good interface contact, and the heat conductivity of the material is increased.
In a second aspect, an embodiment of the present invention provides a preparation method of the above composite hydrogen storage material, including the following steps: and carrying out a carbonization-reduction reaction on the uniform mixture of the carbon source precursor, the hydrogen storage material and the heat conduction material so as to coat the surface of the hydrogen storage material to form the porous heat conduction amorphous carbon layer.
The embodiment of the invention provides a preparation method of a composite hydrogen storage material, which comprises the following steps: and carrying out a carbonization-reduction reaction on the uniform mixture of the carbon source precursor, the hydrogen storage material and the heat conduction material so as to coat the surface of the hydrogen storage material to form the porous heat conduction amorphous carbon layer. The method adopts a unique high-temperature carbon coating method to coat the hydrogen storage material, reduces the expansion and contraction of the hydrogen storage material in the hydrogen charging and discharging process, and achieves the effect of prolonging the service life. On one hand, the carbon material coated on the surface has good heat conductivity, so that the heat conductivity of the alloy can be improved. On the other hand, more importantly, the carbon source precursor and the heat conducting material in the embodiment of the invention adopt an in-situ reaction method of high-temperature carbonization to coat the surface of the hydrogen storage material to form a carbon layer, and the reaction is not simply mechanically mixed but generated in situ on the surface of the hydrogen storage material. Therefore, the hydrogen storage material and the carbon layer coated on the surface of the hydrogen storage material are combined more firmly, the interface contact is better, the heat conducting property is stronger, and meanwhile, the carbon layer is also doped with the heat conducting material, so that the heat conducting property of the whole composite hydrogen storage material is greatly improved.
In an alternative embodiment, the carbon source precursor is a carbon-containing substance;
preferably, the carbon source precursor comprises at least one of styrene butadiene rubber, asphalt, glucose, sucrose and phenolic resin;
preferably, the particle size of the carbon source precursor is 200-300 mesh.
The carbon source precursor in the embodiment of the invention is a carbon-containing substance, the carbon-containing substance can generate a carbonization reduction reaction at high temperature, a porous heat-conducting amorphous carbon layer is coated on the surface of the hydrogen storage alloy, the particle size of the carbon source precursor is controlled to be 200-300 meshes, so that the carbon source precursor can better generate the carbonization reduction reaction to generate a coating layer, the particle size is too small, the generated coating carbon layer can be caused to generate a compact non-porous layer to block a transmission channel of hydrogen, the coating carbon layer is broken when the volume of the carbon source precursor is changed violently in the hydrogen absorption and desorption process of the hydrogen storage material, the particle size is too large, the carbonization reaction at high temperature is possibly insufficient and only exists as a carbon material and the hydrogen storage material in a mechanical mixing mode, and the heat conductivity of the composite hydrogen storage material is reduced.
In an optional embodiment, the reaction temperature of the carbonization reduction is 600-800 ℃, and the time is 1-2 h; preferably, the carbonization-reduction reaction is carried out under the protection of an inert gas selected from argon.
The carbonization-reduction reaction in the embodiment of the invention is carried out under the protection of inert gas to prevent the material from being oxidized, the temperature of the carbonization-reduction is 600-800 ℃, and the time is 1-2h, because on one hand, a porous heat-conducting amorphous carbon layer can be formed on the surface of the hydrogen storage alloy in the temperature and the time, the temperature is further increased or the time is prolonged, the heat conductivity coefficient of the prepared composite hydrogen storage material is not obviously increased, or because the carbon layer accounts for too much, the effective hydrogen storage quantity is lost too much, therefore, the temperature of the carbonization-reduction reaction is 600-800 ℃, and the time is 1-2h, which is most beneficial for preparing the composite hydrogen storage material with proper heat conductivity, and meanwhile, proper redox agents and catalysts can be added in the reaction process to shorten the reaction time.
In an alternative embodiment, the method further comprises: carrying out secondary coating on the surface of the composite hydrogen storage material coated with the porous heat-conducting amorphous carbon layer;
preferably, the secondary coated carbon source precursor is different from the primary coated carbon source precursor.
In the preparation process of the composite hydrogen storage material provided by the embodiment of the invention, secondary coating can be carried out after primary coating is carried out on the surface of the hydrogen storage material according to the required heat-conducting property. Preferably, the carbon source precursor coated twice is different from the carbon source precursor coated once, because the carbon source precursors coated twice are different, a more compact coating layer cannot be generated on the surface of the carbon coating layer coated once in the secondary coating process, so that a transmission channel of hydrogen is not blocked.
In an alternative embodiment, the preparation of the composite hydrogen storage material comprises the steps of: under the protection of argon, mixing titanium-based hydrogen storage alloy with styrene-butadiene rubber, performing primary coating on the surface of the titanium-based hydrogen storage alloy through a carbonization-reduction reaction to form a porous heat-conducting amorphous carbon layer, then mixing the primary coated titanium-based hydrogen storage alloy with asphalt, performing secondary coating on the surface of the porous heat-conducting amorphous carbon layer formed through the primary coating through a carbonization-reduction reaction,
preferably, the heat conduction material is doped in the process of primary coating and/or secondary coating;
preferably, the heat conducting material comprises a fibrous heat conducting material, and more preferably, the heat conducting material further comprises metal powder;
more preferably, the fibrous heat conducting material or the metal powder is used in an amount of 0.05 to 1 wt% based on the total amount of the raw materials of the composite hydrogen storage material.
The embodiment of the invention provides a preparation method of a composite hydrogen storage material, which coats a porous heat-conducting amorphous carbon layer on the surface of the hydrogen storage material by a high-temperature carbonization reduction method, and as an alternative embodiment, in order to increase the thickness of the porous heat-conducting amorphous carbon layer, secondary coating can be performed on the porous heat-conducting amorphous carbon layer, in the process, as a preferred embodiment, a heat-conducting material can be doped in the process of primary coating or the process of secondary coating, as another preferred embodiment, the heat-conducting material can be doped in the process of primary coating and the process of secondary coating, in the above preferred embodiment, the doped heat-conducting material comprises a fibrous heat-conducting material, more preferably, the heat-conducting material also comprises metal powder, and as a preferred embodiment, the doped amount of the heat-conducting material can be adjusted in the primary coating or the secondary coating, more preferably, the heat conductive material such as fibrous heat conductive material or metal powder is incorporated in an amount of 0.05 to 1 wt% based on the total amount of raw materials used for the composite hydrogen storage material.
The embodiment of the invention provides a preparation method of a composite hydrogen storage material, which is characterized in that a compact amorphous carbon layer with a 3D through pipeline is formed on the surface of a titanium-based hydrogen storage alloy by a high-temperature carbonization reduction method, an effective hydrogen diffusion channel is provided for the hydrogen storage material, meanwhile, the agglomeration of the alloy in the hydrogen absorption and desorption process is avoided, the carbon layer and hydrogen storage alloy particles maintain good interface contact, and the heat conductivity of the material is increased. On the basis, the heat conductivity and toughness of the film layer are enhanced through the carbon nano tube, and the film layer is prevented from cracking when violent volume change occurs in the hydrogen absorbing and releasing process of the hydrogen storage alloy. And the high heat conduction metal powder doped in the carbon layer further enhances the heat and mass transfer effects of the film layer. The fiber-reinforced metal-doped amorphous carbon layer coating process can keep the structural stability of the metal hydrogen storage alloy and improve the dynamic performance of the hydrogen storage material.
In a third aspect, embodiments of the present invention provide a composite hydrogen storage material prepared according to the preparation method of any one of the preceding embodiments and use of the composite hydrogen storage material of any one of the preceding embodiments for hydrogen supply in a fuel cell system.
The invention has the following beneficial effects:
the invention provides a composite hydrogen storage material, a preparation method and an application thereof, the composite hydrogen storage material comprises a hydrogen storage material, a porous heat-conducting amorphous carbon layer coated on the surface of the hydrogen storage material and a heat-conducting material doped in the porous heat-conducting amorphous carbon layer, the hydrogen storage material is coated in the porous heat-conducting amorphous carbon layer, a pore channel in the amorphous carbon layer provides an effective hydrogen diffusion channel for the hydrogen storage material, avoiding the agglomeration of the alloy in the hydrogen absorbing and releasing process, maintaining good interface contact between the amorphous carbon layer and the hydrogen storage alloy particles, increasing the thermal conductivity of the material, on the basis, the heat conducting performance of the composite hydrogen storage material is further improved by adding the heat conducting material, thereby obtaining the high-thermal-conductivity composite hydrogen storage material, the high-thermal-conductivity composite hydrogen storage material keeps the stability in the structure, meanwhile, the dynamic performance of the hydrogen storage material can be improved, and the hydrogen storage material can be used as a hydrogen supply material of a fuel cell system.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM image of a composite hydrogen storage material prepared in an example of the invention;
FIG. 2 is a TEM image of a composite hydrogen storage material prepared in an example of the present invention;
FIG. 3 is a TEM image of a composite hydrogen storage material prepared in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Examples 1 to 10
One-step coated high-thermal-conductivity Ti-Fe-Mn series composite hydrogen storage alloy
The hydrogen occluding alloys of examples 1 to 10 were all Ti-Fe-Mn based composite hydrogen occluding alloys, and the preparation of the Ti-Fe-Mn based composite hydrogen occluding alloys included the following steps: pure metals Ti, Fe and Mn are used as smelting raw materials, and the raw materials are TiFe0.8Mn0.2Proportionally smelting and throwing to obtain an alloy sheet with the thickness of 0.3 mm. The flakes were crushed to a fine powder having an average particle size of 300 mesh.
Mixing the prepared alloy powder with a carbon source precursor and a heat conduction material for 12 hours until the mixture is uniform, then putting the mixture into a vacuum heat treatment furnace, heating the mixture to 750 ℃ under the protection of argon, preserving the heat for 5 hours, and then cooling the mixture to room temperature along with the furnace, wherein the mixture is obtained by the steps of mixing the alloy powder, the carbon source precursor and the heat conduction material. The precursor is nitrile butadiene rubber slurry, the heat conducting material can be at least one of multi-wall carbon nanotubes and metal powder, and the proportion (the proportion is a mass ratio) of the alloy powder, the carbon source precursor and the heat conducting material in the embodiments 1 to 10 is shown in the following table 1.
The heat conductivity coefficient, hydrogen storage density and hydrogen absorption and desorption cycle life of each composite hydrogen storage material are respectively measured.
See table 1 below for specific results:
TABLE 1
As can be seen from the data of example 1 in Table 1 above, in the absence of TiFe as a hydrogen storage alloy0.8Mn0.2Before modification, the intrinsic hydrogen storage capacity of the hydrogen storage alloy reaches 1.78 wt%, and the heat conductivity coefficient is only 1.121W/(m.K).
From the data of examples 2 to 4, it is understood that the thermal conductivity of the alloy rapidly increased to 6W/(m.K) or more after the surface of the hydrogen absorbing alloy was coated with the porous heat-conductive amorphous carbon layer, but the hydrogen absorbing capacity of the alloy decreased. After comprehensively considering and balancing the loss of the performance, the formula with the carbon source precursor accounting for 0.01 wt% is selected as the preferable condition for further modification. At this time, the thermal conductivity of the hydrogen storage alloy is 6.036W/(m.K), and the hydrogen storage capacity is 1.75 wt%.
From the data of examples 5 to 7, it can be seen that the addition of carbon nanotubes to the amorphous carbon layer of the hydrogen storage alloy can further improve the thermal conductivity, and at the same time, enhance the toughness of the carbon layer, and the enhanced carbon layer can prolong the hydrogen absorption and desorption cycle life of the composite hydrogen storage material. As can be seen from the data in Table 1, when the amount of carbon nanotubes added is 1%, the thermal conductivity of the composite hydrogen storage material is 10.323W/(m.K), and the hydrogen storage capacity is reduced to 1.71 wt%. Further increasing the addition of the carbon nanotubes and decreasing the thermal conductivity of the composite hydrogen storage material. Therefore, the addition amount of the carbon nanotubes is not more than 1%.
From the data of examples 8-10, it can be seen that, in the case where the addition ratio of the fixed carbon nanotubes is 1%, Ti powder is added to the composite hydrogen storage material to prepare a composite hydrogen storage material system doped with fiber toughening, metal powder heat conduction enhancement and 3D pore amorphous carbon layer coating. As the addition amount of Ti powder is increased from 0.1% to 5%, the thermal conductivity of the composite hydrogen storage material is increased from 12.301W/(mK) to 18.552W/(mK), but the hydrogen storage amount of the composite hydrogen storage material is greatly reduced from 1.73 wt% to 1.63 wt%.
Thus, in this example, the carbon source precursor in the composite hydrogen storage material with the best overall performance (suitable thermal conductivity and hydrogen storage capacity): carbon nanotube: the metal powder ratio is 97.9: 1: 1: 0.1.
the morphology of the sample is detected, referring to fig. 1, and as can be seen from the SEM image, a carbon coating layer is formed on the surface of the hydrogen storage alloy particles, and meanwhile, the particulate matter in the coating layer is metal powder or carbon nanotubes.
Referring to fig. 2, it can be seen from the TEM image that a carbon coating layer is formed on the surface of the hydrogen storage alloy particles, and the particulate matter in the coating layer is the metal powder or the carbon nanotubes.
Referring to FIG. 3, it can be seen from the TEM image that a dense, uniform, porous carbon coating layer is formed on the surface of the hydrogen occluding alloy particles.
Examples 11 to 13:
secondary coated high-thermal-conductivity Ti-Zr-Mn series composite hydrogen storage alloy
The hydrogen occluding alloys of examples 11 to 13 were each a Ti-Zr-Mn based composite hydrogen occluding alloy, and the preparation of the Ti-Zr-Mn based composite hydrogen occluding alloy included the steps of: pure metals Ti, Zr, Cr, Fe, Mn and Al are used as smelting raw materials, and Ti is used as raw material0.83Zr0.17Cr1.30Fe0.3Mn0.35Al0.05Proportionally smelting, and throwing to obtain alloy sheet with thickness of 0.3 mm. The alloy flakes were crushed to a fine powder having an average particle size of 400 mesh.
Mixing the alloy powder, a carbon source precursor (butadiene-acrylonitrile rubber slurry) and a fibrous heat conduction material (multi-walled carbon nanotube) according to a mass ratio of 99: 1, mixing for 12 hours until the mixture is uniform, then putting the mixture into a vacuum heat treatment furnace, heating the mixture to 750 ℃ under the protection of argon, preserving the heat for 5 hours, and then cooling the mixture to room temperature along with the furnace.
And mixing the prepared primary coating composite material with asphalt again according to the mass ratio of 99.5: 0.05, mixing for 6 hours until the mixture is uniform, then putting the mixture into a vacuum heat treatment furnace, heating the mixture to 800 ℃ under the protection of argon, preserving the heat for 3 hours, and then cooling the mixture to room temperature along with the furnace.
The thermal conductivity, hydrogen storage density and hydrogen absorption and desorption cycle life of the hydrogen storage material before and after coating are respectively measured.
See table 2 below for specific results:
TABLE 2
As can be seen from Table 2, the thermal conductivity of the uncoated hydrogen storage alloy in example 11 was 1.086W/(m.K), the hydrogen storage capacity was 1.75 wt%, and the cycle life was 458 times, while the hydrogen storage capacity of the hydrogen storage alloy coated once in example 12 remained substantially unchanged without significant decrease, while both the thermal conductivity and the cycle life showed fold increase, the thermal conductivity was about 6 times that of the uncoated hydrogen storage alloy, and the cycle life was 2 times that of the uncoated hydrogen storage alloy, indicating that the hydrogen storage material coated was a high hydrogen storage and thermal conductivity material, the cycle life was improved, and further, the thermal conductivity of the alloy was further enhanced by the secondary coating process in example 13, but the hydrogen storage capacity was slightly decreased and lost. The primary and secondary coating effectively improve the hydrogen absorption and desorption cycle life of the hydrogen storage alloy, which is attributed to the fact that the uniform coating of the porous heat-conducting amorphous carbon layer inhibits the pulverization phenomenon during the hydrogen absorption and desorption process of the alloy.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. A composite hydrogen storage material is characterized in that the composite hydrogen storage material is obtained by coating a porous heat-conducting amorphous carbon layer on the surface of a hydrogen storage material by using a high-temperature carbonization in-situ reaction of a uniform mixture of a carbon source precursor, the hydrogen storage material and a heat-conducting material, wherein the porous heat-conducting amorphous carbon layer coated on the surface of the hydrogen storage material and the heat-conducting material doped in the porous heat-conducting amorphous carbon layer are used as the heat-conducting materials,
the hydrogen storage material is a hydrogen storage alloy, the particle size of the hydrogen storage material is 150-300 meshes,
the porous heat-conducting amorphous carbon layer is a porous heat-conducting amorphous carbon layer with a 3D pore channel structure penetrating through the surface and the inside, the thickness of the porous heat-conducting amorphous carbon layer is 10nm-100nm,
the carbon source precursor accounts for 1-5% of the total raw material consumption of the composite hydrogen storage material, the heat conduction material comprises fibrous heat conduction materials and metal powder, the particle size of the metal powder is less than 500nm, the metal powder accounts for 0.1-1 wt% of the total raw material consumption of the composite hydrogen storage material, and the fibrous heat conduction materials accounts for 0.5-1 wt% of the total raw material consumption of the composite hydrogen storage material.
2. The composite hydrogen storage material of claim 1, wherein the hydrogen storage alloy is a titanium-based hydrogen storage alloy.
3. The composite hydrogen storage material of claim 1, wherein the fibrous thermally conductive material comprises at least one of PAN-based carbon fibers, graphene fibers, and carbon nanotubes.
4. The composite hydrogen storage material of claim 3, wherein the fibrous thermally conductive material is selected from carbon nanotubes.
5. The composite hydrogen storage material of claim 1, wherein the metal powder comprises at least one of Au, Ag, Al, Cu, and Ti powder.
6. The composite hydrogen storage material of claim 5, wherein the metal powder is selected from Ti powders.
7. A method of preparing a composite hydrogen storage material according to any one of claims 1-6, comprising the steps of: and carrying out a carbonization-reduction reaction on the uniform mixture of the carbon source precursor, the hydrogen storage material and the heat conduction material to coat the surface of the hydrogen storage material to form a porous heat conduction amorphous carbon layer, wherein the particle size of the carbon source precursor is 200-300 meshes.
8. The production method according to claim 7, wherein the carbon source precursor is a carbon-containing substance.
9. The method according to claim 8, wherein the carbon source precursor includes at least one of styrene-butadiene rubber, pitch, glucose, sucrose, and phenol resin.
10. The method as claimed in claim 7, wherein the reaction temperature of the carbonization reduction is 600 ℃ and 800 ℃ for 1-2 h.
11. The method according to claim 10, wherein the carbonization-reduction reaction is performed under protection of an inert gas selected from argon.
12. The method of manufacturing according to claim 7, further comprising: and performing secondary coating on the surface of the composite hydrogen storage material coated with the porous heat-conducting amorphous carbon layer.
13. The method of claim 12, wherein the secondary coated carbon source precursor is different from the primary coated carbon source precursor.
14. The method of claim 12, comprising the steps of: under the protection of argon, mixing titanium-based hydrogen storage alloy with styrene-butadiene rubber, performing primary coating on the surface of the titanium-based hydrogen storage alloy through a carbonization-reduction reaction to form a porous heat-conducting amorphous carbon layer, then mixing the primary coated titanium-based hydrogen storage alloy with asphalt, and performing secondary coating on the surface of the porous heat-conducting amorphous carbon layer formed through the primary coating through a carbonization-reduction reaction.
15. The method of claim 14, wherein a thermally conductive material is incorporated during the primary coating and/or the secondary coating.
16. The method of claim 15, wherein the thermally conductive material comprises a fibrous thermally conductive material.
17. The method of claim 15, wherein the thermally conductive material further comprises a metal powder.
18. The method of claim 16, wherein the fibrous thermal conductive material is used in an amount of 0.5 to 1 wt% based on the total amount of raw materials of the composite hydrogen storage material.
19. The method of claim 17, wherein the metal powder is used in an amount of 0.1-1 wt% based on the total amount of raw materials of the composite hydrogen storage material.
20. Use of the composite hydrogen storage material prepared by the preparation method according to any one of claims 7 to 19 in a hydrogen donor material for a fuel cell system.
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