CN115109983B - Laser rapid hardening high-entropy hydrogen storage alloy and preparation method and application thereof - Google Patents
Laser rapid hardening high-entropy hydrogen storage alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a laser rapid hardening high-entropy hydrogen storage alloy, a preparation method and application thereof, wherein the hydrogen storage alloy comprises the following components (Ti) a Zr b Mn c M d ） x （RE e V f Fe g ） y A is more than or equal to 5 and less than or equal to 30 at%, b is more than or equal to 5 and less than or equal to 30 at%, c is more than or equal to 5 and less than or equal to 30 at%, d is more than or equal to 5 and less than or equal to 30 at%, a+b+c+d=x, x is more than or equal to 20 and less than or equal to 90 at%, and M is any one of Ni, cr, cu, mg; e is more than or equal to 0.5 and less than or equal to 15 and at percent, f is more than or equal to 5 and less than or equal to 30 and at percent, g is more than or equal to 0.5 and less than or equal to 15 and at percent, e+f+g=y, RE is any one of rare earth La, ce and Y, and x+y=100. The method of the invention is to uniformly mix raw material powder, adopt a laser deposition coaxial powder feeding process to carry out rapid hardening molding, and then prepare the high-entropy hydrogen storage alloy powder through mechanical crushing. The grain of the hydrogen storage alloy is obviously refined, the segregation of alloy elements is effectively reduced, hydrogen can be absorbed and released without activation, the hydrogen absorption and release cycle is 200 times, more than 95 percent of hydrogen storage capacity is maintained, and the hydrogen absorption and release amount is more than 1.92 weight percent. The method is used for manufacturing a driving component and a hydrogen storage electrode of a hydrogen storage device, a heat pump or an air conditioner, and is applied to a hydrogen fuel cell, a hydrogen energy storage function carrier, an ultra-high purity hydrogen source or a new energy automobile.
Description
Technical Field
The invention relates to the field of high-efficiency hydrogen storage materials, in particular to a laser rapid-hardening high-entropy hydrogen storage alloy, a preparation method and application thereof.
Background
With excessive consumption of fossil energy, the contradiction between resource supply and demand will be increasingly prominent, and fossil energy is difficult to meet long-term industrial production and human living demands. On the other hand, the combustion utilization of fossil energy such as petroleum, coal and the like in the current stage discharges a large amount of CO 2 、SO 2 And pollutants such as global warming effect, haze, acid rain and the like are caused to influence the serious problem of the living environment of people. The two reasons greatly stimulate and drive the development of clean renewable energy sources such as solar energy, wind energy, biomass, geothermal energy, tides and the like. However, these renewable primary clean energy sources often have unstable, regional and time limitation factors, and usually require storage, output, and other links by adopting a suitable secondary energy carrier. The hydrogen has high energy density, the reaction product is only water, and CO is not discharged 2 And any pollution products such as nitrogen oxides, etc., the mass energy density and the volume energy density of the catalyst are very high, and the catalyst is considered to be very ideal secondary energy carrierThe body and the product water can release hydrogen through electrolysis, and the ideal environment-friendly circulation process has important significance for relieving and solving the energy crisis and ecological crisis. Therefore, many countries pay great attention to the study of hydrogen energy and raise it to the national strategic level. The project of sunlight is started in 1974 in japan, and the research of hydrogen energy technology is greatly developed; the united states developed a "united states hydrogen energy roadmap" program in 2002, and europe also developed a similar program. The hydrogen energy is an important component of an energy system of the future country, and the hydrogen energy is an important carrier for realizing green low-carbon transformation by using energy terminals, and the hydrogen energy industry is a strategic emerging industry and the important development direction of the future industry.
The realization of efficient and safe storage and transportation of hydrogen is a key point of hydrogen energy utilization. The storage methods commonly used at present are a compressed gas storage method and a liquid hydrogen storage method. The high-capacity gas tank and the steel cylinder are used for storing and conveying the gaseous hydrogen, and the high-pressure gas tank and the steel cylinder have certain dangers, and the hydrogen storage amount is small, so that the cost is increased; liquid hydrogen has a higher density than gaseous hydrogen, but the liquefaction temperature of hydrogen is-239.7 ℃, the liquefaction consumes a great amount of energy and requires expensive equipment investment, and excellent adiabatic protection is also required, for example, a large carrier rocket uses liquid hydrogen as fuel and liquid oxygen as an oxidant, and a storage device occupies more than half of the space of the whole rocket; even with super insulated containers, the loss due to evaporation is about 1% per day.
Mg was found in J.J.Reilly and R.H.Wisqall from Bruce-sea laboratories in 1964 2 Hydrogen storage characteristics of Ni (magnesium-based) alloys. The Philips laboratory found LaNi in 1969 5 The (rare earth system) alloy has good hydrogen storage performance. In 1974, J.J.Reilly and R.H.Wisqall have found TiFe (titanium-based) hydrogen storage alloys. These significant findings have revealed a prelude to the study of metal hydride hydrogen storage materials. The solid hydrogen storage method is used for storing hydrogen, and the volume hydrogen storage density is about 1000 times of that of hydrogen in a standard state due to the difference of metals and alloys, is the same as or exceeds that of liquid hydrogen, can store hydrogen without a complex container, and can obtain high-purity hydrogen, so that the solid hydrogen storage method is an economic and effective hydrogen storage method. Metal hydride hydrogen storage as hydrogen storage mediumThe characteristics to be met by the material include high reversible hydrogen absorption and desorption amount, moderate hydrogen absorption and desorption P-C-T (pressure-composition-temperature) platform pressure, small slope and hysteresis of the hydrogen absorption and desorption platform, easy activation, high hydrogen absorption and desorption dynamics performance, good circulation stability, rich resources, low price and the like. Wherein, the hydrogen desorption temperature of the magnesium hydrogen storage material is over high (more than or equal to 250 ℃) and the hydrogen absorption and desorption kinetic performance is poor; the rare earth hydrogen storage material has low hydrogen storage capacity and poor cycle stability; the TiFe hydrogen storage material is difficult to activate; the titanium-zirconium hydrogen storage alloy has Laves phase capable of absorbing hydrogen, has the advantages of high hydrogen storage capacity, long cycle life and the like, but has the defects of difficult activation, overhigh cost and the like which are difficult to overcome.
For the above reasons, no metal hydrogen storage material capable of completely meeting application requirements exists at present, and the development and application of hydrogen energy are severely restricted.
Chinese patent CN 107338385B discloses a hydrogen-storing high entropy alloy with body-centered cubic structure as main material
The preparation method comprises the following steps of (Ti a Zr b Nb c ) x M y M is any one or more of Hf, fe, co, cr, mn, ni, mo and W. The invention adopts a non-consumable vacuum arc furnace to smelt and prepare alloy, adopts a vacuum suction casting process to suction cast the alloy into a water-cooled copper mold, and obtains the high-entropy alloy rod.
The above patent has three main significant drawbacks: firstly, the alloying elements Nb, hf, co, W and other elements are rare and precious metals, so that the cost is high; secondly, preparing alloy bars by using a vacuum smelting and suction casting process, wherein segregation of alloy elements is difficult to avoid in smelting and solidification processes due to high viscosity of a melt and larger melting point difference of the alloy elements; third, the high-entropy alloy has a hydrogen storage capacity of 3-wt%, but the hydrogen release amount at 700 ℃ is less than 0.6wt%, and the effective hydrogen storage amount is low. The three significant disadvantages described above limit the practical application scope of this patent.
Disclosure of Invention
Aiming at the problems of low hydrogen storage capacity, difficult activation and poor hydrogen absorption and desorption dynamics and cycle stability of the hydrogen storage alloy in the prior art, the invention aims to provide the laser rapid-hardening high-entropy hydrogen storage alloy and the preparation method and the application thereof.
To solve the first technical problem, the hydrogen storage alloy of the invention has a composition formula (Ti a Zr b Mn c M d ） x （RE e V f Fe g ） y A is more than or equal to 5 and less than or equal to 30 at%, b is more than or equal to 5 and less than or equal to 30 at%, c is more than or equal to 5 and less than or equal to 30 at%, d is more than or equal to 5 and less than or equal to 30 at%, a+b+c+d=x, x is more than or equal to 20 and less than or equal to 90 at%, and M is any one of Ni, cr, cu, mg; 0.5 E is more than or equal to 1 at%, f is more than or equal to 5 and less than or equal to 30 and at percent, g is more than or equal to 0.5 and less than or equal to 15 and at percent, e+f+g=y, RE is any one of inexpensive rare earth La, ce and Y, and x+y=100.
The letters in the above formulas, except M, RE and the letter of the suffix, correspond to the elements in the periodic table of elements.
The preparation method of the invention comprises the following steps:
(1) Polishing, cleaning and drying the surface of the substrate for later use;
(2) According to the composition formula (Ti a Zr b Mn c M d ） x （RE e V f Fe g ） y Metering atomic percentages, weighing Ti powder, zr powder, mn powder, M simple substance metal powder, RE simple substance powder, V powder and Fe powder in corresponding proportions, and putting the materials into a ball mill for mixing;
(3) Placing the powder mixed in the step (2) into a vacuum drying oven, drying at a constant temperature of 40-60 ℃ for more than 6 hours, and placing into a coaxial powder feeding bin of a laser deposition device;
(4) Starting a laser beam of a laser deposition device, and adopting a laser deposition coaxial powder feeding process to laminate and deposit the powder material in the step (3) on a substrate;
(5) And (3) cooling the deposition layer and the substrate subjected to laser deposition in the step (4) to room temperature, cutting along the interface line between the substrate and the deposition layer to obtain a laser rapid-hardening hydrogen storage alloy strip, and obtaining the high-entropy hydrogen storage alloy powder through a mechanical crushing mode.
The mixing in the step (2), the laser deposition in the step (4) and the mechanical crushing in the step (5) are all completed under the protection of argon or nitrogen.
Further, the Ti powder, zr powder, mn powder, M simple substance metal powder, RE simple substance powder, V powder and Fe powder in the step (2) are all powder with the purity of more than 99.9 percent and the particle size of 40-200 meshes.
Further, the rotating speed of the ball mill in the step (2) is 200-1000 r/min, and the mixing time is 60-300 min.
Further, the flow rate of argon or nitrogen in the laser deposition process in the step (4) is 15L/min-30L/min.
Further, the laser deposition process parameters in the step (4) are as follows: the laser power is 1600-6000W, the scanning speed is 700-1600 mm/min, the diameter of the light spot is 3-20 mm, the powder feeding speed is 5-25 g/min, and the thickness of the deposition layer is 0.4-1.2 mm.
Further, the mechanical crushing mode in the step (5) is hammer type or jaw type crusher crushing, and the particle size of the obtained powder is 40-100 meshes after crushing.
The laser rapid hardening high-entropy hydrogen storage alloy is used for manufacturing a hydrogen storage device. Such as: providing a power source for the hydrogen fuel cell, providing a hydrogen energy storage function carrier for peak shaving of a power grid, and providing an ultra-high purity hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or is made into a driving part of a heat pump and an air conditioner and is used in the refrigeration and heating industry; or is made into a hydrogen storage electrode and applied to the field of new energy automobiles.
The beneficial effects of the invention are as follows: compared with the prior art, the method for preparing the (Ti a Zr b Mn c M d ） x （RE e V f Fe g ） y The high-entropy hydrogen storage alloy has obviously refined crystal grains, effectively reduces the segregation of alloy elements, improves the solid solubility of solute elements, has high activity, reduces the enthalpy of hydrogenation and dehydrogenation reactions, shortens the diffusion path of hydrogen atoms, and ensures the extremely high hydrogen diffusion rate and hydrogenation reaction interface of the alloy. The RE element has the functions of purifying melt, reducing interface binding energy, raising the diffusion rate of hydrogen in alloy and improving the absorption and release of hydrogenThe prepared high-entropy hydrogen storage alloy can complete hydrogen absorption and desorption cycles without activation, the hydrogen absorption and desorption cycles keep more than 95 percent of hydrogen storage capacity for 200 times, and simultaneously, the high-entropy hydrogen storage alloy has the characteristics of high hydrogen storage capacity (more than 1.92 weight percent of hydrogen absorption and desorption) and excellent hydrogen absorption and desorption dynamics.
Drawings
FIG. 1 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an element surface of the alloy powder scanning electron microscope;
FIG. 2 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an image on the Ti element surface of the alloy powder scanning electron microscope;
FIG. 3 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an image on the Zr element surface of the alloy powder scanning electron microscope;
FIG. 4 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 An Mn element surface scanning image of the alloy powder scanning electron microscope;
FIG. 5 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an image on the Cr element surface of the alloy powder scanning electron microscope;
FIG. 6 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an image on the V element surface of the alloy powder scanning electron microscope;
FIG. 7 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 The hydrogen absorption and desorption cycle curve of the alloy at 313K;
FIG. 8 is a diagram of Ti in example 1 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Alloy at 313K, pressThe force is a hydrogen absorption kinetic curve under 5 MPa.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to examples, but the scope of the present invention is not limited to the description of the embodiments.
Example 1
A laser rapid hardening high entropy hydrogen storage alloy has the composition formula: ti (Ti) 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Wherein Ti, zr, mn, cr and V are 19.4 at%, ce is 1.07at%, fe is 1.93 at%, at% is atomic percent (the same applies below). The composition can also be expressed as: (Ti) 19.4 Zr 19.4 Mn 19.4 Cr 19.4 ） 77.6 （Ce 1.07 V 19.4 Fe 1.93 ） 22.4 。
The preparation method comprises the following steps:
(1) Polishing the surface of the stainless steel substrate by sand paper, cleaning by absolute ethyl alcohol, and drying in a drying oven for later use;
(2) According to the composition of Ti 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Metering Ti powder, zr powder, mn powder, cr powder, ce powder, V powder and Fe powder in corresponding proportion, wherein the purity of the powder is more than 99.9%, the particle size of the powder is 100 meshes, mixing materials in a ball mill protected by argon atmosphere for 120min, and the rotating speed of the ball mill is 500r/min;
(3) Taking out the mixed powder from the ball mill, drying the powder at constant temperature for 8 hours in a vacuum drying oven at 40 ℃, and placing the powder into a coaxial powder feeding bin of a laser deposition device;
(4) Starting a laser beam, and adopting a laser deposition coaxial powder feeding process under the protection of argon to laminate and deposit powder on a substrate, wherein the laser deposition process parameters are as follows: laser power 3000W, scanning speed 1000mm/min, spot diameter 8mm, powder feeding rate 14g/min, deposition layer thickness 0.8mm, argon flow rate 20L/min;
(5) And (3) after the laser deposition is completed and cooled to room temperature, cutting along the interface line of the substrate and the deposition layer to obtain a laser rapid hardening hydrogen storage alloy plate, crushing by adopting a jaw crusher protected by argon to obtain high-entropy hydrogen storage alloy powder, and obtaining the powder with the particle size of 60 meshes after crushing.
The substrate in the step (1) can be a titanium alloy substrate besides a stainless steel substrate, and the thickness dimension of the substrate is in the category of the prior art.
In this embodiment, the laser deposition apparatus is of the LDM-800 type, and includes: the laser device comprises a laser, a powder feeder, an argon protection box and a computer, wherein laser emitted by the laser is transmitted to a laser head through an optical fiber, the powder feeder blows powder for laser deposition manufacturing to a coaxial powder feeder through a powder tube, the computer is connected with the coaxial powder feeder, the powder feeder and the laser, and the laser is a 3KW optical fiber laser of Germany IPG company.
The technical effects obtained by the technical scheme of the embodiment are shown in fig. 1 to 8.
FIGS. 1 to 6 show Ti prepared in this example 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 The scanning electron microscope element surface distribution diagram of the alloy shows that the elements of the main alloying element Ti, zr, mn, cr, V are uniformly distributed and dispersed, the segregation degree of the alloying elements forming a multi-element high-entropy system is obviously weakened, the diffusion resistance of hydrogen atoms in the hydrogenation and dehydrogenation process is reduced, and the high hydrogen diffusion rate is ensured. The laser rapid melting and rapid hardening process improves the solid solubility of solute elements, and simultaneously, the addition of rare earth Ce elements can purify melt, reduce interface binding energy, further improve the diffusion rate of hydrogen in the alloy and improve the hydrogen absorption and desorption kinetic performance and the circulation stability.
FIG. 7 shows Ti prepared in this example 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 As can be seen from FIG. 7, the hydrogen storage capacity of the alloy at 313K is maintained at 95.8% by 200 cycles, indicating Ti 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 The alloy has excellent hydrogen absorption and desorption cycle stability.
FIG. 8 shows Ti prepared in this example 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 As can be seen from FIG. 8, the hydrogen absorption kinetics graph of the alloy at 313K and 5MPa is that of Ti 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 The alloy has good hydrogen absorption dynamic performance, and reaches 91.5% of saturated hydrogen absorption in 60s, and the maximum hydrogen storage amount is 2.07wt%.
The laser rapid hardening high-entropy hydrogen storage alloy prepared in the embodiment is used for manufacturing a hydrogen storage device. Such as: providing a power source for the hydrogen fuel cell, providing a hydrogen energy storage function carrier for peak shaving of a power grid, and providing an ultra-high purity hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or is made into a driving part of a heat pump and an air conditioner and is used in the refrigeration and heating industry; or is made into a hydrogen storage electrode and applied to the field of new energy automobiles.
Example 2
A laser rapid hardening high entropy hydrogen storage alloy has the composition formula: ti (Ti) 16.8 Zr 16.8 Mn 16.8 Cu 16.8 Y 5.68 V 16.8 Fe 10.32 Wherein, ti, zr, mn, cu and V are 16.8 at%, Y is 5.68at%, and Fe is 10.32 at%. The composition can also be expressed as: (Ti) 16.8 Zr 16.8 Mn 16.8 Cu 16.8 ） 67.2 （Y 5.68 V 16.8 Fe 10.32 ） 32.8 。
The preparation method comprises the following steps:
(1) Polishing the surface of the stainless steel substrate by sand paper, cleaning by absolute ethyl alcohol, and drying in a drying oven for later use;
(2) According to the composition of Ti 16.8 Zr 16.8 Mn 16.8 Cu 16.8 Y 5.68 V 16.8 Fe 10.32 Weighing Ti powder, zr powder, mn powder, cu powder, Y powder, V powder and Fe powder in a corresponding proportion by atomic percent, placing the Ti powder, zr powder, mn powder, cu powder, Y powder, V powder and Fe powder in a ball mill protected by nitrogen atmosphere, mixing for 240min, wherein the powder purity is more than 99.9%, the particle size is 80 meshes, and the rotating speed of the ball mill is 1000r/min;
(3) Taking out the mixed powder from the ball mill, drying the powder at constant temperature in a vacuum drying oven at 50 ℃ for 12 hours, and placing the powder into a coaxial powder feeding bin of a laser deposition device;
(4) Starting a laser beam, and adopting a laser deposition coaxial powder feeding process under the protection of nitrogen to laminate and deposit powder on a substrate, wherein the laser deposition process parameters are as follows: the laser power is 5000W, the scanning speed is 1200mm/min, the spot diameter is 5mm, the powder feeding speed is 20g/min, the thickness of the deposition layer is 0.6mm, and the argon flow rate is 25L/min;
(5) And (3) after the laser deposition is completed and cooled to room temperature, cutting along the interface line of the substrate and the deposition layer to obtain a laser rapid-hardening hydrogen storage alloy plate, crushing by adopting a nitrogen-protected hammer crusher to obtain high-entropy hydrogen storage alloy powder, and obtaining the powder with the particle size of 100 meshes after crushing.
In this embodiment, the laser deposition apparatus is of the LDM-800 type, and includes: the laser device comprises a laser, a powder feeder, an argon protection box and a computer, wherein laser emitted by the laser is transmitted to a laser head through an optical fiber, the powder feeder blows powder for laser deposition manufacturing to a coaxial powder feeder through a powder tube, the computer is connected with the coaxial powder feeder, the powder feeder and the laser, and the laser is a 5KW optical fiber laser of Germany IPG company.
Ti prepared in this example 16.8 Zr 16.8 Mn 16.8 Cu 16.8 Y 5.68 V 16.8 Fe 10.32 The alloy retains 95.6% of hydrogen storage capacity after 200 hydrogen absorption and desorption cycles at 313K, which shows Ti 16.8 Zr 16.8 Mn 16.8 Cu 16.8 Y 5.68 V 16.8 Fe 10.32 The alloy has excellent hydrogen absorption and desorption cycle stability.
Ti prepared in this example 16.8 Zr 16.8 Mn 16.8 Cu 16.8 Y 5.68 V 16.8 Fe 10.32 The alloy absorbs hydrogen under 313K and 5MPa, and reaches 93.4% of saturated hydrogen absorption in 60s, and the maximum hydrogen storage amount is 1.98wt%.
The laser rapid hardening high-entropy hydrogen storage alloy prepared in the embodiment is used for manufacturing a hydrogen storage device. Such as: providing a power source for the hydrogen fuel cell, providing a hydrogen energy storage function carrier for peak shaving of a power grid, and providing an ultra-high purity hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or is made into a driving part of a heat pump and an air conditioner and is used in the refrigeration and heating industry; or is made into a hydrogen storage electrode and applied to the field of new energy automobiles.
Example 3
A laser rapid hardening high entropy hydrogen storage alloy has the composition formula: ti (Ti) 15.6 Zr 15.6 Mn 15.6 Ni 15.6 La 13.43 V 15.6 Fe 8.57 Wherein, ti, zr, mn, ni and V are 15.6 at%, la is 13.43at%, and Fe is 8.57 at%. The composition can also be expressed as: (Ti) 15.6 Zr 15.6 Mn 15.6 Cu 15.6 ） 62.4 （Y 13.43 V 15.6 Fe 8.57 ） 37.6 。
The preparation method comprises the following steps:
(1) Polishing the surface of the stainless steel substrate by sand paper, cleaning by absolute ethyl alcohol, and drying in a drying oven for later use;
(2) According to the composition of Ti 15.6 Zr 15.6 Mn 15.6 Ni 15.6 La 13.43 V 15.6 Fe 8.57 Weighing Ti powder, zr powder, mn powder, ni powder, la powder, V powder and Fe powder in a corresponding proportion by atomic percent, mixing the materials in a ball mill protected by argon atmosphere for 300min, wherein the powder purity is more than 99.9%, the particle size is 120 meshes, and the rotating speed of the ball mill is 200r/min;
(3) Taking out the mixed powder from the ball mill, drying the powder at constant temperature in a vacuum drying oven at 60 ℃ for 14 hours, and placing the powder into a coaxial powder feeding bin of a laser deposition device;
(4) Starting a laser beam, and adopting a laser deposition coaxial powder feeding process under the protection of argon to laminate and deposit powder on a substrate, wherein the laser deposition process parameters are as follows: the laser power is 6000W, the scanning speed is 800mm/min, the spot diameter is 12mm, the powder feeding speed is 10g/min, the thickness of the deposition layer is 1.0mm, and the argon flow rate is 18L/min;
(5) And (3) after the laser deposition is completed and cooled to room temperature, cutting along the interface line of the substrate and the deposition layer to obtain a laser rapid hardening hydrogen storage alloy plate, crushing by adopting a jaw crusher protected by argon to obtain high-entropy hydrogen storage alloy powder, and obtaining the powder with the particle size of 40 meshes after crushing.
In this embodiment, the laser deposition apparatus is of the LDM-800 type, and includes: the laser device comprises a laser, a powder feeder, an argon protection box and a computer, wherein laser emitted by the laser is transmitted to a laser head through an optical fiber, the powder feeder blows powder for laser deposition manufacturing to a coaxial powder feeder through a powder tube, the computer is connected with the coaxial powder feeder, the powder feeder and the laser, and the laser is a 6KW optical fiber laser of Germany IPG company.
Ti prepared in this example 15.6 Zr 15.6 Mn 15.6 Ni 15.6 La 13.43 V 15.6 Fe 8.57 The alloy retains 96.3% of hydrogen storage capacity after 200 hydrogen absorption and desorption cycles at 313K, which shows Ti 15.6 Zr 15.6 Mn 15.6 Ni 15.6 La 13.43 V 15.6 Fe 8.57 The alloy has excellent hydrogen absorption and desorption cycle stability.
Ti prepared in this example 15.6 Zr 15.6 Mn 15.6 Ni 15.6 La 13.43 V 15.6 Fe 8.57 The alloy absorbs hydrogen under 313K and 5MPa, reaches 95.2% of saturated hydrogen absorption in 60s, and has the maximum hydrogen storage amount of 1.93wt%.
The laser rapid hardening high-entropy hydrogen storage alloy prepared in the embodiment is used for manufacturing a hydrogen storage device. Such as: providing a power source for the hydrogen fuel cell, providing a hydrogen energy storage function carrier for peak shaving of a power grid, and providing an ultra-high purity hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or is made into a driving part of a heat pump and an air conditioner and is used in the refrigeration and heating industry; or is made into a hydrogen storage electrode and applied to the field of new energy automobiles.
Claims (4)
1. A laser rapid hardening high-entropy hydrogen storage alloy is characterized in that the hydrogen storage alloy has the composition of Ti a Zr b Mn c M d RE e V f Fe g A is more than or equal to 5 and less than or equal to 30 at%, b is more than or equal to 5 and less than or equal to 30 at%, c is more than or equal to 5 and less than or equal to 30 at%, d is more than or equal to 5 and less than or equal to 30 at%, a+b+c+d=x, x is more than or equal to 20 and less than or equal to 90 at%, and M is any one of Ni, cr, cu, mg;0.5 E is more than or equal to 15 and at percent, f is more than or equal to 5 and less than or equal to 30 and at percent, g is more than or equal to 0.5 and less than or equal to 15 and at percent, e+f+g=y, RE is any one of rare earth La, ce and Y, and x+y=100.
2. A method for preparing the laser rapid hardening high entropy hydrogen storage alloy according to claim 1, comprising the steps of:
(1) Polishing, cleaning and drying the surface of the substrate for later use;
(2) According to the composition of Ti a Zr b Mn c M d RE e V f Fe g Metering atomic percentages, namely weighing Ti powder, zr powder, mn powder, M simple substance metal powder, RE simple substance powder, V powder and Fe powder in corresponding proportions, wherein the purity of the metal powder is more than 99.9%, the particle size is 40-200 meshes, mixing materials in a ball mill, the rotating speed of the ball mill is 200-1000 r/min, and the mixing time is 60-300 min;
(3) Placing the powder mixed in the step (2) into a vacuum drying oven, drying at a constant temperature of 40-60 ℃ for more than 6 hours, and placing into a coaxial powder feeding bin of a laser deposition device;
(4) Starting a laser beam of a laser deposition device, and adopting a laser deposition coaxial powder feeding process to laminate and deposit the powder material in the step (3) on a substrate; the laser deposition process parameters are as follows: laser power is 1600-6000W, scanning speed is 700-1600 mm/min, spot diameter is 3-20 mm, powder feeding speed is 5-25 g/min, and deposition layer thickness is 0.4-1.2 mm;
(5) Cooling the deposition layer and the substrate subjected to laser deposition in the step (4) to room temperature, and then cutting along the interface line between the substrate and the deposition layer to obtain a laser rapid-hardening hydrogen storage alloy strip, and obtaining high-entropy hydrogen storage alloy powder through a mechanical crushing mode; the mechanical crushing mode is crushing by a hammer or jaw crusher, and the particle size of the obtained powder is 40-100 meshes.
3. The preparation method of claim 2, wherein the ball milling in the step (2), the laser deposition in the step (4) and the mechanical crushing in the step (5) are all completed under the protection of argon or nitrogen, and the flow rate of the argon or nitrogen in the laser deposition is 15-30L/min.
4. Use of a laser rapid hardening high entropy hydrogen storage alloy according to claim 1 for the manufacture of a hydrogen storage device.
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| US5407761A (en) * | 1991-08-14 | 1995-04-18 | Ovinic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries fabricated from these alloys having significantly improved capacity |
| US5238756A (en) * | 1990-04-26 | 1993-08-24 | Ovonic Battery Company | Electrode alloy having decreased hydrogen overpressure and/or low self-discharge |
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| CN112501485B (en) * | 2020-11-16 | 2022-04-12 | 北京理工大学 | Reversible room-temperature hydrogen storage high-entropy alloy, and preparation and application thereof |
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