CN115109983A - 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 and 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 percent, b is more than or equal to 5 and less than or equal to 30 at percent, c is more than or equal to 5 and less than or equal to 30 at percent, d is more than or equal to 5 and less than or equal to 30 at percent, a + b + c + d = x, x is more than or equal to 20 and less than or equal to 90 at percent, and M is any one of Ni, Cr, Cu and Mg; e is more than or equal to 0.5 and less than or equal to 15 at percent, f is more than or equal to 5 and less than or equal to 30 at percent, and g is more than or equal to 0.5 and less than or equal to 15at%, e + f + g = Y, RE is any one of the rare earths La, Ce, Y, x + Y = 100. The method of the invention is to uniformly mix the raw material powder, adopt the laser deposition coaxial powder feeding technology to carry out rapid hardening and forming, and then prepare the high-entropy hydrogen storage alloy powder through mechanical crushing. The hydrogen storage alloy has obviously refined crystal grains, effectively reduces the segregation of alloy elements, can absorb and release hydrogen without activation, and can keep the hydrogen storage capacity of more than 95 percent after hydrogen absorption and release cycles of 200 times, wherein the hydrogen absorption and release amount is more than 1.92 percent by weight. The material is used for manufacturing a hydrogen storage device, a driving part of a heat pump or an air conditioner and a hydrogen storage electrode, and is applied to a hydrogen fuel cell, a hydrogen energy storage functional carrier and an ultra-pure hydrogen source or applied to 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 and a preparation method and application thereof.
Background
With the excessive consumption of fossil energy, the contradiction between resource supply and demand will be increasingly prominent, and the fossil energy is difficult to meet the long-term industrial production and human living demand. On the other hand, the combustion utilization of fossil energy such as petroleum and coal at present stage discharges a large amount of CO 2 、SO 2 And the pollutants cause severe problems of global greenhouse effect, haze, acid rain and the like which affect the living environment of people. Both of these reasons have greatly stimulated and driven the development of clean renewable energy sources such as solar, wind, biomass, geothermal, tidal, etc. However, these renewable primary clean energy sources often have limitations such as instability, regional limitations, and time limitations, and usually need to adopt appropriate secondary energy carriers for storage, output, and other links. The hydrogen has high energy density, the reaction product only contains water, and CO is not discharged 2 And nitrogen oxides and other pollution products, the mass energy density and the volume energy density of the material are very high, the material is considered to be an ideal secondary energy carrier, the product water can release hydrogen through electrolysis, and the ideal environment-friendly circulating process has important significance for relieving and solving energy crisis and ecological crisis. Therefore, many countries attach great importance to the research of hydrogen energy and raise it to the national strategic level. The "sunshine" program was started as early as 1974 in japan, and research on hydrogen energy technology was vigorously conducted; the U.S. hydrogen energy roadmap project was introduced in 2002 in the united states and a similar project was developed in europe. The hydrogen energy is an important component of the future national energy system, and is an important carrier for realizing green low-carbon transformation by using an energy terminal, and the hydrogen energy industry is a strategic emerging industry and a key development direction of the future industry.
The key to the utilization of hydrogen energy is to realize the efficient and safe storage and transportation of hydrogen. Currently, compressed gas storage and liquid hydrogen storage are common storage methods. The high-capacity gas tank and the steel cylinder are used for storing and conveying the gaseous hydrogen, and the high pressure is used, so that certain danger is caused, the hydrogen storage amount is small, and the cost is increased; liquid hydrogen has higher density than gaseous hydrogen, but the liquefaction temperature of hydrogen is-239.7 ℃, the liquefaction consumes a large amount of energy and needs expensive equipment investment, and the liquefaction also needs excellent heat insulation protection, for example, a large carrier rocket uses liquid hydrogen as fuel, liquid oxygen as oxidant, and a storage device of the liquid hydrogen occupies more than half of the space of the whole rocket; even with super-insulated containers, losses due to evaporation per day are currently about 1%.
Mg was found by j.j.reilly and r.h.wisqall in bruke-haivin laboratories usa in 1964 2 Hydrogen storage characteristics of Ni (magnesium) alloys. The Philips laboratory discovered LaNi in 1969 5 The (rare earth) alloy has excellent hydrogen storage properties. In 1974, TiFe (titanium-based) hydrogen storage alloys were discovered again by j.j.reilly and r.h.wisqall. These significant findings have uncovered the pioneering screen for the study of metal hydride hydrogen storage materials. The solid hydrogen storing method has hydrogen storing density 1000 times that of hydrogen in standard state, the same as or higher than that of liquid hydrogen, and may be stored without complicated container and high purity hydrogen. The characteristics required to be met by the metal hydride hydrogen storage material as a hydrogen storage medium comprise high reversible hydrogen absorption and desorption amount, moderate hydrogen absorption and desorption P-C-T (pressure-composition-temperature) platform pressure, small hydrogen absorption and desorption platform slope and hysteresis, easy activation, high hydrogen absorption and desorption dynamic performance, good cycle stability, rich resources, low price and the like. Wherein, the hydrogen releasing temperature of the magnesium hydrogen storage material is too high (more than or equal to 250 ℃) and the hydrogen absorbing and releasing dynamic performance is poor; the rare earth hydrogen storage material has low hydrogen storage capacity and poor cycle stability; activation of the TiFe-based hydrogen storage material is difficult; the titanium zirconium hydrogen storage alloy has a Laves phase capable of absorbing hydrogen, has the advantages of high hydrogen storage capacity, long cycle life and the like, and has the defects of difficult activation, overhigh cost and the like which are difficult to overcome.
For the reasons, no metal hydrogen storage material capable of completely meeting the application requirements exists at present, and the development and application of hydrogen energy are severely restricted.
Chinese patent CN 107338385B discloses a hydrogen storage high-entropy alloy with body-centered cubic structure as main component and its preparation method
A method for preparing the same, the high-entropy alloyHas the composition 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 alloy is prepared by smelting in a non-consumable vacuum arc furnace, and the alloy is suction cast into a water-cooled copper mold by adopting a vacuum suction casting process to obtain the high-entropy alloy rod.
The above patents suffer from three significant drawbacks: firstly, alloying elements such as Nb, Hf, Co, W and the like are selected as rare precious metals, so that the cost is high; secondly, alloy bars are prepared by using vacuum melting and suction casting processes, and because of high viscosity and large melting point difference of alloy elements of a melt, segregation of the alloy elements is difficult to avoid in the melting and solidification processes; thirdly, although the high-entropy alloy has a hydrogen storage capacity of 3wt% or more, the amount of hydrogen released at 700 ℃ is less than 0.6wt%, and the effective hydrogen storage amount is low. The three significant drawbacks described above limit the practical application of this patent.
Disclosure of Invention
Aiming at the problems of low hydrogen storage capacity, difficult activation, and poor hydrogen absorption and desorption kinetics and cycle stability of the hydrogen storage alloy in the prior art, the invention aims to solve the technical problem of providing a laser rapid-hardening high-entropy hydrogen storage alloy and a preparation method and application thereof.
In order to solve the first technical problem, the hydrogen storage alloy of the present invention has a composition formula of (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 percent, b is more than or equal to 5 and less than or equal to 30 at percent, c is more than or equal to 5 and less than or equal to 30 at percent, d is more than or equal to 5 and less than or equal to 30 at percent, a + b + c + d = x, x is more than or equal to 20 and less than or equal to 90 at percent, and M is any one of Ni, Cr, Cu and Mg; e is more than or equal to 0.5 and less than or equal to 15 at percent, f is more than or equal to 5 and less than or equal to 30 at percent, g is more than or equal to 0.5 and less than or equal to 15 at percent, e + f + g = Y, RE is any one of the cheap rare earth La, Ce and Y, and x + Y = 100.
The letters in the above composition formula correspond to elements in the periodic table of elements except M, RE and the suffix letters.
The preparation method 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 Weighing Ti powder, Zr powder, Mn powder, M simple substance metal powder, RE simple substance powder, V powder and Fe powder in corresponding proportions by atom percentage metering, and putting the materials into a ball mill for mixing;
(3) putting the powder mixed in the step (2) into a vacuum drying oven, drying at constant temperature of 40-60 ℃ for more than 6h, and putting into a coaxial powder conveying bin of a laser deposition device;
(4) starting a laser beam of the laser deposition device, and depositing the powder material obtained in the step (3) on the substrate in a laminating manner by adopting a laser deposition coaxial powder feeding process;
(5) and (5) cooling the deposition layer and the substrate after the laser deposition in the step (4) to room temperature, cutting along the interface line of the substrate and the deposition layer to obtain a laser quick-setting hydrogen storage alloy strip, and mechanically crushing to obtain high-entropy hydrogen storage alloy powder.
And (3) the material mixing in the step (2), the laser deposition in the step (4) and the mechanical crushing in the step (5) are all completed in the atmosphere of argon or nitrogen.
Further, the Ti powder, the Zr powder, the Mn powder, the M simple substance metal powder, the RE simple substance powder, the V powder and the 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 1600W-6000W, the scanning speed is 700 mm/min-1600 mm/min, the spot diameter is 3 mm-20 mm, the powder feeding speed is 5 g/min-25 g/min, and the thickness of the deposition layer is 0.4 mm-1.2 mm.
Furthermore, the mechanical crushing mode in the step (5) is a hammer type or jaw type crusher, and the particle size of the powder obtained after crushing is 40-100 meshes.
The laser rapid-hardening high-entropy hydrogen storage alloy is used for manufacturing a hydrogen storage device. Such as: the hydrogen energy storage device provides a power source for a hydrogen fuel cell, provides a hydrogen energy storage function carrier for power grid peak shaving, and provides an ultra-pure hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or made into driving components of heat pump and air conditioner, used in refrigeration and heating industry; or made into hydrogen storage electrode, and is applied to the field of new energy automobiles.
The invention has the beneficial effects that: compared with the prior art, the (Ti) prepared by the technical scheme a Zr b Mn c M d ） x （RE e V f Fe g ） y The high-entropy hydrogen storage alloy has the advantages that crystal grains are obviously refined, the segregation of alloy elements is effectively reduced, the solid solubility of solute elements is improved, the alloy powder has high activity, the enthalpy of hydrogenation and dehydrogenation reaction is reduced, the hydrogen atom diffusion path is shortened, and the extremely high hydrogen diffusion rate and hydrogenation reaction interface of the alloy are ensured. The addition of the RE element has the effects of purifying a melt and reducing the interface bonding energy, the diffusion rate of hydrogen in the alloy is improved, the hydrogen absorption and desorption dynamic performance and the cycle stability are improved, the prepared high-entropy hydrogen storage alloy can complete hydrogen absorption and desorption circulation without activation, the hydrogen absorption and desorption capacity is kept by more than 95% for 200 times of hydrogen absorption and desorption circulation, and the alloy has the characteristics of high hydrogen storage capacity (more than 1.92wt% of hydrogen absorption and desorption capacity) and excellent hydrogen absorption and desorption dynamics.
Drawings
FIG. 1 shows 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 element surface of the alloy powder scanning electric mirror;
FIG. 2 shows 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 alloy powder scanning electron microscope Ti element surface scanning image;
FIG. 3 shows 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 of a Zr element surface of an alloy powder scanning electron microscope;
FIG. 4 shows an embodiment1 in Ti 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Scanning an image of an Mn element surface of an alloy powder scanning electron microscope;
FIG. 5 shows 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 of a Cr element surface of the alloy powder scanning electron microscope;
FIG. 6 shows 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 of a V element surface of an alloy powder scanning electron microscope;
FIG. 7 shows 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 absorption and desorption hydrogen cycle curve of the alloy at 313K;
FIG. 8 shows 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 kinetic curve of the alloy at 313K and 5MPa pressure.
Detailed Description
The invention will be further described with reference to the following examples for better understanding, but the scope of the invention is not limited to the examples.
Example 1
A laser rapid-hardening high-entropy hydrogen storage alloy has a composition formula as follows: 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 all 19.4 at%, Ce is 1.07at%, Fe is 1.93 at%, and at% is atomic% (the same below). The compositional formula may 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 a stainless steel substrate by using sand paper, cleaning by using absolute ethyl alcohol, and drying in a drying oven for later use;
(2) according to the composition formula Ti 19.4 Zr 19.4 Mn 19.4 Cr 19.4 Ce 1.07 V 19.4 Fe 1.93 Weighing Ti powder, Zr powder, Mn powder, Cr powder, Ce powder, V powder and Fe powder in corresponding proportions according to the atomic percentage (at%) metering, wherein the purity of the powder is more than 99.9%, the particle size of the powder is 100 meshes, placing the powder in a ball mill protected by argon atmosphere for mixing for 120min, and the rotating speed of the ball mill is 500 r/min;
(3) taking out the mixed powder from the ball mill, drying the powder in a vacuum drying oven at the constant temperature of 40 ℃ for 8 hours, and placing the powder into a coaxial powder conveying bin of a laser deposition device;
(4) starting a laser beam, and performing laser deposition coaxial powder feeding process under the protection of argon to deposit powder on the substrate in a laminated manner, 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) after laser deposition is finished and the temperature is cooled to room temperature, laser quick-setting hydrogen storage alloy plates are obtained by cutting along the boundary line of the substrate and the deposition layer, high-entropy hydrogen storage alloy powder is obtained by adopting an argon-protected jaw crusher crushing mode, and the particle size of the powder obtained after crushing is 60 meshes.
The substrate in the step (1) can adopt a titanium alloy substrate besides a stainless steel substrate, and the thickness and the size of the substrate are all in the range of the prior art.
In this embodiment, the laser deposition apparatus used is of LDM-800 type, including: the laser 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 feeding head through a powder pipe, the computer is connected with the coaxial powder feeding head, the powder feeder and the laser, and the used laser is a 3KW optical fiber laser of the Germany IPG company.
The technical effects obtained by the technical solution of the present 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 Scanning electrode for alloyThe mirror element surface distribution diagram shows that the elements of the main alloying elements Ti, Zr, Mn, Cr and V are uniformly distributed and dispersed, the segregation degree of the alloying elements forming the 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 fast melting and fast solidifying process improves the solid solubility of solute elements, and simultaneously the addition of rare earth Ce element can purify melt and reduce interface bonding energy, further improve the diffusion rate of hydrogen in alloy, and improve the dynamic performance and the cycling stability of hydrogen absorption and desorption.
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 The graph of the hydrogen absorption and desorption cycles of the alloy at 313K shows that the alloy retains 95.8 percent of hydrogen storage capacity after 200 hydrogen absorption and desorption cycles as shown in figure 7, and Ti is represented 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 FIG. 8 shows the hydrogen absorption kinetics of the alloy at 313K and 5MPa, where Ti is 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, reaches 91.5 percent of saturated hydrogen absorption amount within 60s, and the maximum hydrogen storage amount is 2.07wt percent.
The laser rapid-hardening high-entropy hydrogen storage alloy prepared by the embodiment is used for preparing a hydrogen storage device. Such as: the hydrogen energy storage device provides a power source for a hydrogen fuel cell, provides a hydrogen energy storage function carrier for power grid peak shaving, and provides an ultra-pure hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or made into driving components of heat pump and air conditioner, used in refrigeration and heating industry; or made into hydrogen storage electrode, and is applied to the field of new energy automobiles.
Example 2
A laser rapid-hardening high-entropy hydrogen storage alloy has a composition formula as follows: 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 compositional formula may 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 a stainless steel substrate by using abrasive paper, cleaning by using absolute ethyl alcohol and drying in a drying box for later use;
(2) according to the composition formula 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 corresponding proportions in atom percentage measurement, mixing for 240min in a ball mill protected by nitrogen atmosphere, wherein the purity of the powder is more than 99.9%, the particle size is 80 meshes, and the rotating speed of the ball mill is 1000 r/min;
(3) taking out the mixed powder from the ball mill, drying the powder in a vacuum drying oven at the constant temperature of 50 ℃ for 12 hours, and placing the powder into a coaxial powder conveying bin of a laser deposition device;
(4) starting a laser beam, and performing laser deposition coaxial powder feeding process under the protection of nitrogen to deposit powder on the substrate in a laminated manner, 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 a deposition layer is 0.6mm, and the flow rate of argon gas is 25L/min;
(5) after laser deposition is finished and the temperature is cooled to room temperature, laser quick-setting hydrogen storage alloy plates are obtained by cutting along the boundary line of the substrate and the deposition layer, high-entropy hydrogen storage alloy powder is obtained by adopting a nitrogen-protected hammer crusher crushing mode, and the particle size of the powder obtained after crushing is 100 meshes.
In this embodiment, the laser deposition apparatus used is of LDM-800 type, including: the laser 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 feeding head through a powder pipe, the computer is connected with the coaxial powder feeding head, the powder feeder and the laser, and the used laser is a 5KW optical fiber laser of a 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 percent of hydrogen storage capacity after 200 hydrogen absorption and desorption cycles at 313K, which shows that 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 percent of saturated hydrogen absorption amount within 60s, and the maximum hydrogen storage amount is 1.98 percent by weight.
The laser rapid-hardening high-entropy hydrogen storage alloy prepared by the embodiment is used for preparing a hydrogen storage device. Such as: the hydrogen energy storage device provides a power source for a hydrogen fuel cell, provides a hydrogen energy storage function carrier for power grid peak shaving, and provides an ultra-pure hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or made into driving components of heat pump and air conditioner, used in refrigeration and heating industry; or made into hydrogen storage electrode, and is applied to the field of new energy automobiles.
Example 3
A laser rapid-hardening high-entropy hydrogen storage alloy has a composition formula as follows: 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 compositional formula may 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 a stainless steel substrate by using sand paper, cleaning by using absolute ethyl alcohol, and drying in a drying oven for later use;
(2) according to the composition formula 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 corresponding proportions by atom percentage, mixing the materials in a ball mill protected by argon atmosphere for 300min, wherein the purity of the powder is more than 99.9 percent, and the particle size is 120 meshes;
(3) taking out the mixed powder from the ball mill, drying the powder in a vacuum drying oven at the temperature of 60 ℃ for 14 hours at constant temperature, and placing the powder into a coaxial powder conveying bin of a laser deposition device;
(4) starting a laser beam, and performing laser deposition coaxial powder feeding process under the protection of argon to deposit powder on the substrate in a laminated manner, 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 a deposition layer is 1.0mm, and the argon flow rate is 18L/min;
(5) after laser deposition is finished and the temperature is cooled to room temperature, a laser rapid-hardening hydrogen storage alloy plate is obtained by cutting along the boundary line of the substrate and the deposition layer, high-entropy hydrogen storage alloy powder is obtained by adopting an argon-protected jaw crusher crushing mode, and the particle size of the powder obtained after crushing is 40 meshes.
In this embodiment, the laser deposition apparatus used is of LDM-800 type, which includes: the laser 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 feeding head through a powder pipe, the computer is connected with the coaxial powder feeding head, the powder feeder and the laser, and the used laser is a 6KW optical fiber laser of the 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 percent of hydrogen storage capacity after 200 hydrogen absorption and desorption cycles at 313K, which shows that 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 of pressure95.2% of the saturated hydrogen absorption amount was achieved within 60 seconds, and the maximum hydrogen storage amount was 1.93 wt%.
The laser rapid-hardening high-entropy hydrogen storage alloy prepared by the embodiment is used for preparing a hydrogen storage device. Such as: the hydrogen energy storage device provides a power source for a hydrogen fuel cell, provides a hydrogen energy storage function carrier for power grid peak shaving, and provides an ultra-pure hydrogen source for integrated circuits, semiconductor devices, electronic materials and optical fiber industries; or made into driving components of heat pump and air conditioner, used in refrigeration and heating industry; or made into hydrogen storage electrode, and is applied to the field of new energy automobiles.
Claims (8)
1. The laser rapid-hardening high-entropy hydrogen storage alloy is characterized in that the composition formula of the hydrogen storage alloy is (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 percent, b is more than or equal to 5 and less than or equal to 30 at percent, c is more than or equal to 5 and less than or equal to 30 at percent, d is more than or equal to 5 and less than or equal to 30 at percent, a + b + c + d = x, x is more than or equal to 20 and less than or equal to 90 at percent, and M is any one of Ni, Cr, Cu and Mg; e is more than or equal to 0.5 and less than or equal to 15 at percent, f is more than or equal to 5 and less than or equal to 30 at percent, g is more than or equal to 0.5 and less than or equal to 15 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 as claimed in claim 1, characterized by comprising the steps of:
(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 Weighing Ti powder, Zr powder, Mn powder, M simple substance metal powder, RE simple substance powder, V powder and Fe powder in corresponding proportions by atom percentage metering, and putting the materials into a ball mill for mixing;
(3) putting the powder mixed in the step (2) into a vacuum drying box, drying for more than 6 hours at the constant temperature of 40-60 ℃, and putting into a coaxial powder conveying bin of a laser deposition device;
(4) starting a laser beam of the laser deposition device, and depositing the powder material obtained in the step (3) on the substrate in a laminating manner by adopting a laser deposition coaxial powder feeding process;
(5) and (4) cooling the deposition layer and the substrate after the laser deposition in the step (4) to room temperature, cutting along the substrate and the deposition layer interface line to obtain a laser rapid-hardening hydrogen storage alloy lath, and obtaining high-entropy hydrogen storage alloy powder in a mechanical crushing mode.
3. The method for preparing the laser rapid-hardening high-entropy hydrogen storage alloy as claimed in claim 2, wherein the Ti powder, the Zr powder, the Mn powder, the M elemental metal powder, the RE elemental powder, the V powder and the Fe powder in the step (2) are all powders with a purity of more than 99.9% and a particle size of 40-200 meshes.
4. The preparation method of the laser rapid-hardening high-entropy hydrogen storage alloy as claimed in claim 2, wherein the rotation speed of the ball mill in the step (2) is 200-1000 r/min, and the mixing time is 60-300 min.
5. The preparation method according to 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 performed under an argon or nitrogen protective atmosphere, and the flow rate of argon or nitrogen in the laser deposition process is 15L/min to 30L/min.
6. The method for preparing the laser rapid-hardening high-entropy hydrogen storage alloy as claimed in claim 2, wherein the laser deposition process parameters in the step (4) are as follows: the laser power is 1600W-6000W, the scanning speed is 700 mm/min-1600 mm/min, the spot diameter is 3 mm-20 mm, the powder feeding speed is 5 g/min-25 g/min, and the thickness of the deposition layer is 0.4 mm-1.2 mm.
7. The method for preparing the laser rapid-hardening high-entropy hydrogen storage alloy as claimed in claim 2, wherein the mechanical crushing in the step (5) is performed by a hammer crusher or a jaw crusher, and the particle size of the powder obtained after crushing is 40-100 meshes.
8. The application of the laser rapid-hardening high-entropy hydrogen storage alloy is characterized in that the laser rapid-hardening high-entropy hydrogen storage alloy is used for manufacturing a hydrogen storage device.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238756A (en) * | 1990-04-26 | 1993-08-24 | Ovonic Battery Company | Electrode alloy having decreased hydrogen overpressure and/or low self-discharge |
| 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 |
| CN1397658A (en) * | 2002-04-10 | 2003-02-19 | 浙江大学 | Non-crystal rare-earht-Mg based hydrogen bearing alloy and its preparing process |
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
| CN112501485A (en) * | 2020-11-16 | 2021-03-16 | 北京理工大学 | Reversible room-temperature hydrogen storage high-entropy alloy, and preparation and application thereof |
| CN113061763A (en) * | 2021-03-23 | 2021-07-02 | 广东省科学院智能制造研究所 | High-entropy alloy and preparation method thereof |
| CN114293086A (en) * | 2021-12-30 | 2022-04-08 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Hydrogen storage high-entropy alloy and preparation method thereof |
| CN114672714A (en) * | 2022-02-28 | 2022-06-28 | 华南理工大学 | High-entropy hydrogen storage alloy and preparation method thereof |
-
2022
- 2022-07-12 CN CN202210814042.3A patent/CN115109983B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238756A (en) * | 1990-04-26 | 1993-08-24 | Ovonic Battery Company | Electrode alloy having decreased hydrogen overpressure and/or low self-discharge |
| 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 |
| CN1397658A (en) * | 2002-04-10 | 2003-02-19 | 浙江大学 | Non-crystal rare-earht-Mg based hydrogen bearing alloy and its preparing process |
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
| CN112501485A (en) * | 2020-11-16 | 2021-03-16 | 北京理工大学 | Reversible room-temperature hydrogen storage high-entropy alloy, and preparation and application thereof |
| CN113061763A (en) * | 2021-03-23 | 2021-07-02 | 广东省科学院智能制造研究所 | High-entropy alloy and preparation method thereof |
| CN114293086A (en) * | 2021-12-30 | 2022-04-08 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Hydrogen storage high-entropy alloy and preparation method thereof |
| CN114672714A (en) * | 2022-02-28 | 2022-06-28 | 华南理工大学 | High-entropy hydrogen storage alloy and preparation method thereof |
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