CN112126927B - Preparation method of hydrogen storage material - Google Patents
Preparation method of hydrogen storage material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano hydrogen storage material, which comprises the following steps: 1S: carrying out ultrasonic cleaning on the porous copper; 2S: preparing copper oxide nanowires by high-temperature oxidation in an oxygen atmosphere; 3S: preparing titanium oxide-coated copper oxide nanowires by a sol-gel method; 4S: and performing magnesium deposition on the nanowire by using a magnetic filtering technology. The method is based on a super-nano composite structure which can conveniently absorb and release hydrogen by a high-temperature oxidation method, an ion implantation method, a sol-gel method and a magnetic filtration deposition method. The hydrogen absorption material prepared by the method has the characteristics of strong hydrogen absorption capacity, low hydrogen release temperature, self-cleaning and the like; the hydrogen absorption material of the invention has important application prospect in the aspect of hydrogen energy.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to a preparation method of a hydrogen storage material.
Background
With the development of industry and the improvement of people's living standard of matter, the demand of energy is increasing day by day. Since the energy used in recent decades is mainly from fossil fuels (such as coal, oil and natural gas), and its use inevitably pollutes the environment, and its reserves are limited, the search for renewable green energy is urgent. Hydrogen energy is attracting attention as a green energy source and an energy carrier with abundant reserves, wide sources and high energy density. The hydrogen energy utilization needs to solve the following 3 problems of hydrogen preparation, storage, transportation and application, and the storage and transportation of the hydrogen energy is the key of the hydrogen energy application. The hydrogen exists in a gaseous form under the common conditions and is inflammable, explosive and easy to diffuse, so that safety, high efficiency and no leakage loss in hydrogen storage and transportation are considered to be the priority in practical application, and great difficulty is brought to the storage and transportation.
Disclosure of Invention
The present invention is directed to solving the problems described above. The invention aims to provide a preparation method of a hydrogen storage material. The method can conveniently form the nano-structure material with high surface area and high hydrogen storage capacity based on high-temperature oxidation, ion implantation, sol-gel and magnetic filtration deposition methods. The material prepared by the method has the characteristics of low cost, good hydrogen storage capacity, low hydrogen release temperature, low activation energy and the like; the material of the invention has important application prospect in hydrogen storage. According to one aspect of the present invention, there is provided a method of preparing a hydrogen storage material, comprising the steps of:
1S: carrying out ultrasonic cleaning on the porous copper mesh;
2S: performing noble metal ion implantation on the porous copper mesh;
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
Wherein the content of the first and second substances,
the thickness of the porous copper net in the step 1S is 0-2mm, and the mesh number of the copper net is 600-1200 meshes.
2S: performing noble metal ion implantation on the porous copper mesh:
the implantation is performed by using metal ion source, ion beam current of 0.2-1mA, pulse width of 20-200 μ s, implantation metal of Ag, Au, Pt, etc., implantation energy of 0-4KeV, and dosage of 1 × 1015-1×1016/cm2；
3S: preparing copper oxide nanowires at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment is 400-750 ℃ during high-temperature oxidation, the gas in the vacuum chamber is oxygen gas, the pressure is 0.1-50Pa, the length of the prepared copper oxide nanowire is 30-100 mu m, and the density is 10-50/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coating film layer is 0-1 mu m.
5S: performing magnesium deposition on the nanowires by using a magnetic filtration technology:
the arcing current is 40-80A, the oxygen flow is 0-100sccm, the vacuum degree is 2 x 10-3-6×10-3Pa, depositing for 1-3 min, wherein the deposition thickness is not more than 5 nm; set the heightThe voltage of the power pulse bias is 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
The invention relates to a preparation method of a hydrogen storage material, which comprises the following steps:
1S: porous copper is used as a substrate, and 600 meshes and 1200 meshes are selected as growth matrixes of the nanowires.
In the invention, in the range of 600-1200 meshes, the growth of the nanowire can be stably realized through high-temperature oxidation, and the nanowire can not be stably grown from the copper net with too high or too low mesh number. Meanwhile, the storage of hydrogen with different volumes can be realized through the selection of the mesh number of the porous copper, and compared with the traditional storage technology, the invention has the characteristics of low cost and strong controllability.
2S: performing noble metal ion implantation on the porous copper mesh:
according to the invention, the injection of the noble metal is beneficial to forming a defect, namely a region with high surface energy, on the surface of the porous copper mesh, the growth of the copper oxide nanowire can be preferentially realized during high-temperature oxidation, the size and the length of the grown nanowire can be adjusted by the size of the defect, and the doping of the noble metal can be realized, so that the noble metal has a positive effect on the subsequent atomic conversion and adsorption of hydrogen.
3S: preparing copper oxide nanowires at high temperature in an oxygen atmosphere;
in the invention, the temperature of the vacuum equipment during high-temperature oxidation is 400-750 ℃, the atmosphere is oxygen gas, the pressure is 0.1-50Pa, and the length of the prepared copper oxide nanowire is 30-100 mu m. Compare and prepare the copper oxide nano wire under traditional atmosphere, this patent can realize the accurate control of nano wire diameter, length through the control of atmosphere under the vacuum.
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
in the invention, the copper oxide nanowires mainly have the following functions: 1) as scaffolds for high surface area nanomaterials; 2) the titanium dioxide and the subsequent titanium dioxide form a compound semiconductor, so that the hydrogen absorption efficiency is increased; the titanium dioxide is a good hydrogen absorption material, the nano titanium dioxide or the porous titanium dioxide is difficult to control the size due to the complex preparation process, and the method for regulating and controlling the titanium dioxide nano structure by taking the copper oxide as the carrier is obviously different from the traditional method.
5S: performing magnesium deposition on the nanowires by using a magnetic filtration technology:
according to the invention, the combination of the nano metal magnesium and hydrogen can be greatly improved by using the nano metal magnesium as the nano decorative substance on the surface of the titanium dioxide, the hydrogen absorption efficiency is improved, and the hydrogen desorption temperature and the related activation energy can be reduced.
Compared with the prior art, the preparation method of the hydrogen storage material has the following advantages:
1. compared with the traditional hydrogen absorption material, the copper oxide nanowire is used as the support to form the high-surface-area hydrogen absorption material, so that the repeatability is strong, the cost is low, and the industrial mass production is easier to realize;
2. compared with the traditional method, the method controls the diameter, the length and the like of the nanowire by using ion implantation, and is more controllable;
3. the preparation of the nano hydrogen storage material is an environment-friendly process, wherein the processes of high-temperature oxidation, ion implantation and magnetic filtration deposition can be accurately controlled, and the repeatability and the stability of the nano hydrogen storage material are stronger than those of the conventional method;
4. compared with the traditional hydrogen storage material, the hydrogen storage material has the advantages that the surface hydrogen absorption efficiency can be greatly improved, the hydrogen release temperature can be reduced and the like by means of titanium dioxide coating, nano-magnesium deposition and the like;
5. the nano hydrogen storage material also has a self-cleaning function, and the recycling frequency of the nano hydrogen storage material is higher than that of the traditional hydrogen storage material.
Other characteristic features and advantages of the invention will become apparent from the following description of embodiments, which is to be read in connection with the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention, in which like reference numerals are used to designate like elements, and the drawings in the following description are some, but not all embodiments of the invention, and will enable one of ordinary skill in the art to make and use the invention.
FIG. 1 shows a process flow diagram of a method for producing a hydrogen storage material according to the invention;
fig. 2 shows porous copper before and after high temperature oxidation according to the present invention;
FIG. 3 illustrates copper oxide nanowires grown after high temperature oxidation in accordance with the present invention;
FIG. 4 shows titanium dioxide and magnesium encapsulated copper oxide nanowires according to the present invention
FIG. 5 shows the self-cleaning test of the materials according to examples 1 and 2 of the present invention;
fig. 6 shows the hydrogen evolution temperature and decomposition activation energy of the materials according to examples 1 to 4 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 with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The preparation method of the hydrogen storage material comprises the following steps:
1S: carrying out ultrasonic cleaning on the porous copper mesh;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 600-
2S: performing noble metal ion implantation on the porous copper mesh;
the implantation is performed by using metal ion source, ion beam current of 0.2-1mA, pulse width of 20-200 μ s, implantation metal of Ag, Au, Pt, etc., implantation energy of 0-4KeV, and dosage of 1 × 1015-1×1016/cm2；
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment is 400-750 ℃ during high-temperature oxidation, the gas in the vacuum chamber is oxygen gas, the pressure is 0.1-50Pa, the length of the prepared copper oxide nanowire is 30-100 mu m, and the density is 10-50/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coating film layer is 0-1 mu m.
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
The arcing current is 40-80A, the oxygen flow is 0-100sccm, the vacuum degree is 2 x 10-3-6×10-3Pa, depositing for 1-3 min, wherein the deposition thickness is not more than 3 nm; the voltage of the high-power pulse bias is set to be 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
Examples
Example 1
1S: carrying out ultrasonic cleaning on the porous copper mesh;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 800 meshes
2S: performing noble metal ion implantation on the porous copper mesh;
the implantation is carried out by using metal ion source, ion beam current of 0.5mA, pulse width of 50 mus, implantation metal of Ag, implantation energy of 2KeV and dosage of 1 × 1015-1×1016/cm2；
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment during high-temperature oxidation is 650 ℃, the gas in the vacuum chamber is oxygen gas, the pressure is 10Pa, the length of the prepared copper oxide nanowire is 30 mu m, and the density is 30/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coated film layer is 100 nm.
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
The arcing current is 60A, the oxygen flow is 0-100sccm, the vacuum degree is 2 multiplied by 10-3-6×10-3Pa, depositing for 1-3 min, and depositing with the thickness of 2 nm; the voltage of the high-power pulse bias is set to be 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
Example 2
1S: carrying out ultrasonic cleaning on the porous copper mesh;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 1000 meshes
2S: performing noble metal ion implantation on the porous copper mesh;
the implantation is carried out by using metal ion source, ion beam current of 0.6mA, pulse width of 50 mus, implantation metal of Ag, implantation energy of 3KeV and dosage of 1 × 1015-1×1016/cm2；
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment during high-temperature oxidation is 700 ℃, the gas in the vacuum chamber is oxygen gas, the pressure is 20Pa, the length of the prepared copper oxide nanowire is 40 mu m, and the density is 30/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coated film layer is 200 nm.
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
The arcing current is 70A, the oxygen flow is 0-100sccm, the vacuum degree is 2 multiplied by 10-3-6×10-3Pa, depositing for 1-3 min, and depositing with the thickness of 3 nm; the voltage of the high-power pulse bias is set to be 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
Example 3
1S: carrying out ultrasonic cleaning on the porous copper mesh;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 1100 meshes
2S: performing noble metal ion implantation on the porous copper mesh;
the implantation is carried out by using metal ion source, ion beam current of 0.7mA, pulse width of 50 mus, implantation metal of Ag, implantation energy of 3KeV and dosage of 1 × 1015-1×1016/cm2；
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment during high-temperature oxidation is 750 ℃, the gas in the vacuum chamber is oxygen gas, the pressure is 30Pa, the length of the prepared copper oxide nanowire is 50 mu m, and the density is 30/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coated film layer is 300 nm.
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
The arcing current is 70A, the oxygen flow is 0-100sccm, the vacuum degree is 2 multiplied by 10-3-6×10-3Pa, depositing for 1-3 min, and depositing with the thickness of 3 nm; the voltage of the high-power pulse bias is set to be 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
Example 4
1S: carrying out ultrasonic cleaning on the porous copper mesh;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 1200 meshes
2S: performing noble metal ion implantation on the porous copper mesh;
the implantation is carried out by using metal ion source, ion beam current of 0.8mA, pulse width of 50 mus, implantation metal of Ag, implantation energy of 3KeV and dosage of 1 × 1015-1×1016/cm2；
3S, preparing the copper oxide nanowire at high temperature in an oxygen atmosphere;
the temperature of the vacuum equipment during high-temperature oxidation is 750 ℃, the gas in the vacuum chamber is oxygen gas, the pressure is 40Pa, the length of the prepared copper oxide nanowire is 50 mu m, and the density is 30/mu m2。
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
the coated titanium dioxide film is prepared by a sol-gel method, the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the coating film layer is 1 mu m.
5S: and performing magnesium deposition on the nanowires by using a magnetic filtration technology.
The arcing current is 70A, the oxygen flow is 0-100sccm, the vacuum degree is 2 multiplied by 10-3-6×10-3Pa, depositing for 1-3 min, and depositing with the thickness of 4 nm; the voltage of the high-power pulse bias is set to be 1-5 kV, the pulse width is 1-5 mus, the pulse frequency is 1-200 Hz, the duty ratio is 1/10000-1/5000, and the peak power is 1-5 MW.
FIG. 2 shows the porous copper surface before and after high temperature oxidation, and it can be clearly seen that uniform and dense black copper oxide nanowires are formed on the porous copper surface; FIG. 3 is a topographical view of copper oxide nanowires grown on a porous copper substrate, the nanowires being arranged in an array, the nanowires having a diameter of 20-80nm and a length of 30-100 μm. Fig. 4 is a surface topography after magnesium deposition by sol-gel and magnetic filtration, and it can be clearly found that after sol-gel, the surface of the nanowire forms a three-dimensional dendritic structure, which greatly increases the specific surface area of the nanowire. It can be clearly seen from fig. 6 that the increase of the specific surface has a positive effect on both the hydrogen desorption temperature (60-75 ℃) and the decomposition activation energy of the hydrogen storage material, and the hydrogen desorption temperature and the decomposition activation energy are greatly reduced. Fig. 5 shows the self-cleaning performance of the hydrogen absorption material, which can be seen clearly that the hydrogen absorption material has the self-cleaning effect, and can greatly reduce the possibility of adsorbing other pollutants in the environment where the hydrogen absorption material is located, and improve the service life of the hydrogen absorption material.
In conclusion, the preparation method of the hydrogen storage material can conveniently form the super-nano structure, greatly improve the specific surface of the material and simultaneously greatly reduce the preparation cost. The material prepared by the method has the characteristics of self-cleaning performance, high hydrogen absorption efficiency, low hydrogen release temperature and the like; the material of the invention has important application prospect in the aspect of hydrogen energy. The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. A method for preparing a hydrogen storage material, comprising the steps of:
1S: carrying out ultrasonic cleaning on the porous copper mesh;
2S: performing noble metal ion implantation on the porous copper mesh;
3S: preparing copper oxide nanowires at high temperature in an oxygen atmosphere;
4S: copper oxide nanowires wrapped with titanium oxide by a sol-gel method;
5S: performing magnesium deposition on the nanowires by using a magnetic filtration technology;
the thickness of the porous copper net is 0-2mm, and the mesh number of the copper net is 600-1200 meshes;
in the step 2S, the ion beam current of the metal ion source is 0.2-1mA, the pulse width is 20-200 mus, the implanted metal is Ag, Au or Pt, the implantation energy is 0-4keV, and the dosage is 1 multiplied by 1015-1×1016/cm2；
In the step 3S, the temperature of the vacuum equipment during high-temperature oxidation is 400-750 ℃, the gas in the vacuum chamber is oxygen, the pressure is 0.1-50Pa, the length of the prepared copper oxide nanowire is 30-100 mu m, and the density is 10-50/mu m2；
Preparing a wrapped titanium dioxide film in the step 4S by a sol-gel method, wherein the solution comprises tetrabutyl titanate, absolute ethyl alcohol, nitric acid and glacial acetic acid, and the thickness of the wrapped film layer is 0-1 mu m;
when the magnesium deposition is performed by magnetic filtration in the step 5S, the arcing current is set to be 40-80A, the oxygen flow is 0-100sccm, and the vacuum degree is 2 multiplied by 10-3-6×10-3Pa, depositing for 1-3 min, wherein the deposition thickness is not more than 5nm, and simultaneously applying high-power pulse bias composite direct-current bias to the porous copper mesh; setting the voltage of the high-power pulse bias voltage to be 1-5 kV, the pulse width to be 1-5 mus, the pulse frequency to be 1-200 Hz, the duty ratio to be 1/10000-1/5000 and the peak power to be 1-5 MW; setting the voltage of the direct current bias voltage to be 1-1000V, and setting the duty ratio to be 1-80%.
2. A method for producing a hydrogen absorbing material as claimed in claim 1, wherein the hydrogen absorbing material is produced to have a self-cleaning property and a hydrogen releasing temperature as low as 60 to 75 ℃.
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