CN114592136B - Device and method for preparing magnesium-based hydrogen storage alloy with assistance of ultrasonic waves - Google Patents
Device and method for preparing magnesium-based hydrogen storage alloy with assistance of ultrasonic waves Download PDFInfo
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- CN114592136B CN114592136B CN202210106605.3A CN202210106605A CN114592136B CN 114592136 B CN114592136 B CN 114592136B CN 202210106605 A CN202210106605 A CN 202210106605A CN 114592136 B CN114592136 B CN 114592136B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0042—Intermetallic compounds; Metal alloys; Treatment thereof only containing magnesium and nickel; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
- C22B9/026—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves by acoustic waves, e.g. supersonic waves
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention belongs to the technical field of hydrogen storage material preparation and processing, and relates to a device and a method for preparing magnesium-based hydrogen storage alloy by ultrasonic wave assistance. The invention has the advantages that: the bottom of the corundum crucible is connected with the ultrasonic melt processing system, so that impurity elements are reduced, the shape of the crucible is reasonably designed, ultrasonic waves fully act on the alloy melt, the volatilization and oxidation of the alloy melt are avoided through the efficient gas protection system, elements in the prepared magnesium-based hydrogen storage alloy are uniformly distributed, the microstructure is obviously refined, and the hydrogen absorption and desorption performance is obviously improved.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage material preparation and processing, and relates to a device and a method for preparing magnesium-based hydrogen storage alloy by ultrasonic assistance.
Background
As a clean energy source, hydrogen has the highest energy density per unit mass in addition to nuclear energy, and thus hydrogen energy is considered as one of the most potential energy carriers. Efficient preparation, safe storage and transportation and reasonable application of hydrogen are three key links of hydrogen energy development and utilization. With the gradual maturity of hydrogen production technology and the rapid development of fuel cell technology, safe, efficient and economic hydrogen storage and transportation technology becomes a bottleneck restricting the application of hydrogen energy. At normal temperature and pressure, hydrogen has the lowest gas density of all energy sources, and is flammable and explosive. At present, the storage modes of hydrogen mainly comprise high-pressure gas state, cooling liquid state and solid material hydrogen storage. The high-pressure gaseous hydrogen storage density is low, and the leakage and even explosion are easy; the energy loss of cooling liquid hydrogen storage accounts for 30% -45% of the total energy of hydrogen storage, and the cost of the ultralow temperature container for storing liquid hydrogen is extremely high.
The solid material stores hydrogen by means of physical adsorption or chemical bonding of the material to hydrogen, and has high hydrogen storing density, high safety and reliability, and mass and volume hydrogen storing density even higher than that of liquid low temperature hydrogen storing. Among various solid hydrogen storage materials, the Mg-based hydrogen storage material has the advantages of high theoretical hydrogen storage density (7.6 wt.%), good hydrogen absorption and desorption reversibility, rich resources and no toxicity, and has good application prospect. However, the thermodynamic stability of the Mg-H bond is too high, resulting in MgH 2 The hydrogen discharge temperature of (2) is higher than 300 ℃, and the enthalpy of dehydrogenation reaction is increased to 75kJ/mol. At the same time H 2 Dissociation of molecules on the surface of metal Mg and H atom on MgH 2 Surface layer recombination is relatively difficult and H atoms are in Mg, especially MgH 2 Internal diffusion is difficult, resulting in unsatisfactory hydrogen absorption and desorption kinetics of the Mg-based hydrogen storage material.
The inventor finds that: for high-capacity Mg-based hydrogen storage alloy, the hydrogen storage capacity of a system is greatly reduced due to excessive alloying elements, and a small amount of alloying elements are generally easy to segregate and distribute, so that primary alpha-Mg dendrites in the alloy are coarse, a 'blocking effect' is generated, the diffusion of H atoms and the nucleation and decomposition of a hydrogenated phase are hindered, and the further optimization of hydrogen absorption and desorption performances is influenced. For example, the transition metal Ni is considered to be the most effective alloying element for Mg-based hydrogen storage alloys, where Mg is 2 Ni can be hydrogenated at 200 ℃ to generate Mg 2 NiH 0.3 And Mg 2 NiH 4 . In high capacity Mg-Ni alloys, the Mg content is high and Mg-Mg is contained 2 A Ni eutectic structure. Therefore, compared with metal Mg, the Mg-Ni alloy has obviously improved hydrogen storage performance. However, the primary alpha-Mg dendrite size in the alloy is large,the solidification structure is unevenly distributed, and further improvement of the hydrogen storage performance is limited. Therefore, it is urgently needed to develop a preparation and processing method of high-capacity Mg-Ni hydrogen storage alloy, which is simple in operation, low in cost and suitable for industrial application.
Disclosure of Invention
Object of the Invention
The core technical problem of the invention is to solve the problems of large dendritic crystal size of primary alpha-Mg, uneven distribution of alloying elements and solidification structures and easy pollution of alloy melt in the high-capacity Mg-based hydrogen storage alloy caused by the traditional smelting method, and the invention develops a device and a method for preparing the magnesium-based hydrogen storage alloy by utilizing ultrasonic wave assistance. The device and the method provide a simple, efficient and low-cost way for obtaining the high-purity Mg-based hydrogen storage alloy, so that the prepared alloy has the advantages of uniform refinement of solidification structure, uniform distribution of elements and extremely low impurity content.
In order to achieve the purpose, the invention provides the following technical scheme:
an ultrasonic-assisted magnesium-based hydrogen storage alloy preparation device comprises an alloy smelting system, a gas protection system, an ultrasonic melt processing system and a control system,
the alloy smelting system comprises a smelting furnace, a corundum crucible and a crucible support, wherein the crucible support is arranged on a bottom plate in the smelting furnace, the vertical section of the corundum crucible is in an inverted trapezoid shape, the corundum crucible is arranged on the crucible support, and the crucible support is provided with an ultrasonic vibration connecting port; the gas protection system is communicated with the smelting furnace; the ultrasonic melt processing system passes through the ultrasonic vibration connecting port and is abutted with the bottom of the corundum crucible;
the smelting furnace comprises a furnace body, a furnace cover and an induction heating coil, wherein the induction heating coil is arranged along the circumferential direction of the inner side wall of the furnace body to form an induction heating zone, the setting height of the bottom of the induction heating zone is the same as the height of the bottom of the corundum crucible, and the setting height of the top of the induction heating zone is the same as the height of the top of the corundum crucible; the furnace cover is provided with an observation port, and the top of the furnace cover is also provided with a barometer for detecting the air pressure in the furnace body;
the gas is protectedThe protection system comprises a protection gas cylinder and SF 6 +CO 2 A mixed gas bottle, a vacuum pump and a communicating pipeline system,
the communication pipeline system comprises a first pressurizing pipeline, a second pressurizing pipeline, a vacuum pipeline and an exhaust pipeline; the protective gas cylinder is communicated with the furnace body through a first pressurizing pipeline, and a first pressurizing valve is arranged on the first pressurizing pipeline; the SF 6 +CO 2 The mixed gas bottle is communicated with the furnace body through a second pressurizing pipeline, and a second pressurizing valve is arranged on the second pressurizing pipeline; the vacuum pump is communicated with the furnace body through a vacuum pipeline, and a vacuum extraction valve is arranged on the vacuum pipeline; one end of the exhaust pipeline is communicated with the furnace body, and the other end of the exhaust pipeline is communicated with the gas sealing device through an exhaust valve.
As a further description of the above scheme, the ultrasonic melt processing system includes an ultrasonic transducer, an ultrasonic horn and a tool head, the ultrasonic transducer is disposed on a bottom plate in the furnace body through a connecting member, the ultrasonic horn is connected with the ultrasonic transducer, and the ultrasonic horn is located above the ultrasonic transducer; the tool head is connected with the ultrasonic amplitude transformer, the tool head is positioned above the ultrasonic amplitude transformer, and the tool head penetrates through the ultrasonic vibration connecting port of the crucible support and is attached to the bottom of the corundum crucible.
As a further description of the above aspect, the control system includes a display device, an induced current controller, an ultrasonic vibration output current controller, an ultrasonic vibration frequency controller, a temperature sensor, and a temperature detection module;
the temperature sensor is arranged in the corundum crucible and is electrically connected with the temperature detection module; the ultrasonic vibration output current controller is electrically connected with the ultrasonic transducer; the ultrasonic vibration frequency controller is electrically connected with the ultrasonic amplitude transformer; the induction current controller is electrically connected with the induction heating coil;
the display equipment is connected with the induction current controller, the ultrasonic vibration output current controller, the ultrasonic vibration frequency controller, the temperature sensor and the temperature detection module, and displays the working states of the ultrasonic amplitude transformer, the ultrasonic transducer and the induction heating coil and the temperature information of the melt in the corundum crucible in real time.
As a further description of the above solution, the gas sealing device includes an exhaust duct, an oil-sealed tank, an elastic sealing assembly and a diffusing pipe, the exhaust duct has an exhaust pipe connecting section, a sealed connecting section and a sealed tank connecting section, one end of the exhaust pipe connecting section is connected with the exhaust pipeline through a flange, and the other end of the exhaust pipe connecting section penetrates through the top of the oil-sealed tank and is connected with the top end of the sealed connecting section; the pipe diameter of the sealing connection pipe section is larger than that of the exhaust pipe connection pipe section; the sealing box body connecting section comprises a grid and an end plate; the plurality of grate bars are arranged at the bottom end of the seal connecting pipe section at intervals along the circumferential direction, and extend downwards to be connected with the end plate; the end plate is fixedly connected with a bottom plate of the oil seal box body; the elastic sealing assembly comprises a sealing element, a first spiral spring and a second spiral spring, the sealing element comprises a pipeline plugging section and a spring connecting section, the vertical section of the pipeline plugging section is trapezoidal, the diameter of the upper end face of the pipeline plugging section is smaller than the inner diameter of the exhaust pipe connecting pipe section, a preset distance is reserved between the lower end face of the pipeline plugging section and the inner wall of the sealed connecting pipe section, the spring connecting section is fixedly connected with the lower end face of the pipeline plugging section, the first spiral spring is sleeved on the spring connecting section, and the other end of the first spiral spring extends downwards and is connected with the end plate; one end of the second spiral spring is connected with the bottom of the spring connecting section, and the other end of the second spiral spring extends downwards to be connected with the end plate; the diffusing pipe is arranged at the upper part of the oil seal box body.
As a further description of the above scheme, the gas sealing device further includes a liquid level meter, the liquid level meter is disposed outside the oil seal box, the first and second coil springs are in a pre-compressed state, and a cross-sectional dimension of the spring connection section is smaller than a dimension of a lower end face of the pipe plugging section.
An application method of a device for preparing magnesium-based hydrogen storage alloy by ultrasonic assistance comprises the following steps:
the method comprises the following steps: placing magnesium-based hydrogen storage alloy raw materials in a corundum crucible, closing a furnace cover and locking;
step two: sequentially opening the vacuum pump and the vacuum pumping valve, and sequentially closing the vacuum pumping valve and the vacuum pump when the barometer displays that the air pressure value is zero;
step three: opening a first pressurizing valve, introducing protective gas, and closing the first pressurizing valve and the protective gas bottle when the barometer displays that the air pressure value is standard air pressure;
step four: repeating the second step to the third step;
step five: starting the induction current controller, and sequentially starting SF 6 +CO 2 Smelting the mixed gas cylinder and a second pressurizing valve;
step six: adjusting the output power and the vibration frequency of ultrasonic waves through an ultrasonic vibration output current controller and an ultrasonic vibration frequency controller, and carrying out ultrasonic melt treatment;
step seven: and cooling and sampling the magnesium-based hydrogen storage alloy.
As a further description of the scheme, in the sixth step, after the ultrasonic melt is processed for 15 minutes, the induction current controller is closed, and the melt is naturally cooled; and when the temperature shows that the melt temperature is lower than 500 ℃, closing the ultrasonic vibration output current controller to finish the ultrasonic melt treatment.
As a further description of the above scheme, in the fifth step, the furnace body 1 is set with a rated temperature of 750 ℃, a heating rate of 30 ℃ per minute, the state of the alloy melt is observed through an observation port every 10 minutes, and when the display device reaches the rated temperature, the heat is continuously preserved for 30 minutes;
the seventh step of cooling and sampling the magnesium-based hydrogen storage alloy further comprises the following steps:
closing the second pressurized valve and SF 6 +CO 2 Mixing the gas cylinder, opening the protective gas cylinder and the first pressurizing valve, and introducing protective gas; when the temperature is lower than 50 ℃, closing the first pressure valve and the protective gas cylinder; opening the furnace cover to take out the magnesium-based materialHydrogen alloying and storing.
Advantages and effects
1. The invention utilizes the ultrasonic vibration device to connect the bottom of the corundum crucible, thereby avoiding introducing impurity elements into Mg alloy melt through an alloy head; the crucible is designed into an inverted trapezoid shape reasonably, so that the efficiency of ultrasonic vibration is improved, and primary alpha-Mg dendrites in the Mg-based hydrogen storage alloy are obviously refined and alloying elements and microstructures are uniformly distributed by virtue of a cavitation effect, a sound flow effect and a mechanical effect.
2. In the invention, high-purity Ar gas and SF are introduced in the ultrasonic melt treatment process 6 +CO 2 The protective gas reduces the volatilization and oxidation of Mg alloy melt, and the high-purity Mg-based hydrogen storage alloy is prepared. Wherein the high-purity Ar gas is used for exhausting air in the furnace body and keeping the balance of the air pressure inside and outside the furnace body, and SF 6 +CO 2 The protective gas serves to further reduce volatilization and oxidation of the alloy melt by forming a protective film. Different from other Mg alloy smelting devices, the invention introduces SF into the closed furnace body 6 +CO 2 The protective gas prevents oxygen and water vapor from contacting with the alloy melt, and the preparation of the high-purity Mg-based hydrogen storage alloy is realized.
3. The invention utilizes the mode of combining induction melting and ultrasonic vibration to make the Mg alloy melt flow sufficiently, thereby avoiding impurity introduction and melt volatilization caused by mechanical stirring and long-time heat preservation, and being beneficial to the cleaning of the alloy melt and the accurate control of components. Meanwhile, the inverted trapezoidal crucible can effectively improve the action efficiency of the ultrasonic vibration on the melt at the bottom of the crucible, the defect that the traditional ultrasonic melt treatment is difficult to act on the melt at the bottom of the crucible is overcome, and the effect of uniformly refining the Mg-based hydrogen storage alloy is obviously improved.
Drawings
FIG. 1 is a schematic structural view of an ultrasonic melt processing apparatus for magnesium-based hydrogen storage alloys according to an embodiment of the present invention;
FIG. 2 is a schematic view of the gas sealing apparatus of FIG. 1;
FIG. 3 is ultrasonic melt treatment vs. Mg 98 Ni 2 A refinement of the microstructure of the alloy in a microstructure diagram in which:
FIG. 3- (a) without sonication; FIG. 3- (b) the ultrasonically treated alloy;
FIG. 4 shows Mg before and after ultrasonic melt treatment 98 Ni 2 The hydrogen absorption and desorption performance of the alloy is compared with a curve chart, wherein:
FIG. 4- (a) comparative graph of hydrogen absorption performance; FIG. 4- (b) graph comparing hydrogen release performance.
Description of reference numerals:
1-furnace body; 2, furnace cover; 3-an induction heating coil; 4-corundum crucible; 5-a viewing port; 6-crucible support; 7-protection gas cylinder; 8-SF 6 +CO 2 A mixed gas cylinder; 9-a vacuum pump; 10-gas sealing means; 101-a flange; 102-an exhaust pipe connection pipe section; 103-oil sealed box body; 104-oil; 105-sealing the connecting pipe section; 106-grate bar; 107-end plate; 108-a resilient seal assembly; 1081-a pipeline plugging section; 1082-a spring connection section; 1083-a first coil spring; 1084-a second coil spring; 109-a liquid level meter; 1010-a diffusing pipe; 11-a first pressurized valve; 12-a second pressurized valve; 13-vacuum extraction valve; 14-an exhaust valve; 15-an ultrasonic transducer; 16-an ultrasonic horn; 17-a tool head; 18-a display device; 19-an inductive current control module; 20-ultrasonic vibration output current control module; 21-ultrasonic vibration frequency control module; 23-a first pressurization line; 24-a second pressurization line; 25-an exhaust line; 26-vacuum line.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following descriptions are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
As shown in fig. 1 to 4, the present invention provides the following technical solutions:
a device for preparing magnesium-based hydrogen storage alloy by ultrasonic assistance comprises an alloy smelting system, a gas protection system, an ultrasonic melt processing system and a control system, wherein the alloy smelting system comprises a smelting furnace, a corundum crucible 4 and a crucible support 6, the crucible support 6 is arranged on a bottom plate in the smelting furnace, the vertical section of the corundum crucible 4 is in an inverted trapezoid shape, the corundum crucible 4 is arranged on the crucible support 6, and the crucible support 6 is provided with an ultrasonic vibration connecting port; the gas protection system is communicated with the smelting furnace; the ultrasonic melt processing system passes through the ultrasonic vibration connecting port and is abutted with the bottom of the corundum crucible 4. The design of the invention utilizes the ultrasonic vibration device to connect the bottom of the corundum crucible 4, and avoids introducing impurity elements into Mg alloy melt through an alloy head; the crucible is designed into an inverted trapezoid shape reasonably, so that the efficiency of ultrasonic vibration is improved, and primary alpha-Mg dendrites in the Mg-based hydrogen storage alloy are obviously refined by virtue of cavitation effect, acoustic flow effect and mechanical effect, and alloying elements and microstructures are uniformly distributed.
The gas protection system comprises a protection gas bottle 7 and SF 6 +CO 2 The system comprises a mixed gas cylinder 8, a vacuum pump 9 and a communication pipeline system, wherein the communication pipeline system comprises a first pressurizing pipeline 23, a second pressurizing pipeline 24, a vacuum pipeline 26 and an exhaust pipeline 25; the protective gas bottle 7 is communicated with the furnace body 1 through a first pressurizing pipeline 23, and a first pressurizing valve 11 is arranged on the first pressurizing pipeline 23; SF 6 +CO 2 The mixed gas bottle 8 is communicated with the furnace body 1 through a second pressurizing pipeline 24, and a second pressurizing valve 12 is arranged on the second pressurizing pipeline 24; the vacuum pump 9 is communicated with the furnace body 1 through a vacuum pipeline 26, and a vacuum extraction valve 13 is arranged on the vacuum pipeline 26; one end of the exhaust pipeline 25 is communicated with the furnace body 1, and the exhaust pipelineThe other end of 25 communicates with the gas sealing device 10 through the exhaust valve 14. The design of the invention is that high-purity Ar gas and SF are introduced in the ultrasonic melt treatment process 6 +CO 2 The protective gas reduces the volatilization and oxidation of Mg alloy melt, and the high-purity Mg-based hydrogen storage alloy is prepared. Wherein the high purity Ar gas is used for exhausting air in the furnace body 1 and maintaining the balance of the air pressure inside and outside the furnace body, SF 6 +CO 2 The protective gas serves to further reduce volatilization and oxidation of the alloy melt by forming a protective film. Different from other Mg alloy smelting devices, the invention introduces SF into the closed furnace body 6 +CO 2 The protective gas prevents oxygen and water vapor from contacting with the alloy melt, and the preparation of the high-purity Mg-based hydrogen storage alloy is realized.
The protective gas cylinder 7 of the embodiment of the present invention is preferably a high-purity argon gas cylinder, but the protective gas is not limited to using only high-purity argon gas.
The ultrasonic melt processing system of the device of the embodiment of the invention comprises an ultrasonic transducer 15, an ultrasonic amplitude transformer 16 and a tool head 17, wherein the ultrasonic transducer 15 is arranged on a bottom plate in the furnace body 1 through a connecting piece, the ultrasonic amplitude transformer 16 is connected with the ultrasonic transducer 15, and the ultrasonic amplitude transformer 16 is positioned above the ultrasonic transducer 15; the tool head 17 is connected with the ultrasonic amplitude transformer 16, the tool head 17 is positioned above the ultrasonic amplitude transformer, and the tool head 17 passes through the ultrasonic vibration connecting port of the crucible support 6 and is attached to the bottom of the corundum crucible 4. The design of the invention ensures that the Mg alloy melt flows fully, thereby avoiding impurity introduction and melt volatilization caused by mechanical stirring and long-time heat preservation, and being beneficial to the cleaning of the alloy melt and the accurate control of components. Meanwhile, the inverted trapezoidal crucible can effectively improve the efficiency of the action of ultrasonic vibration on the melt at the bottom of the crucible, the defect that the traditional ultrasonic melt treatment is difficult to act on the melt at the bottom of the crucible is improved, and the effect of uniformly refining the Mg-based hydrogen storage alloy is obviously improved.
Specifically, the smelting furnace provided by the embodiment of the invention comprises a furnace body 1, a furnace cover 2 and an induction heating coil 3, wherein the induction heating coil 3 is arranged along the circumferential direction of the inner side wall of the furnace body 1 to form an induction heating area, the setting height of the bottom of the induction heating area is the same as that of the bottom of a corundum crucible 4, and the setting height of the top of the induction heating area is the same as that of the top of the corundum crucible 4; the furnace cover 2 is provided with an observation port 5, and the top of the furnace cover 2 is also provided with an air pressure meter for detecting the air pressure in the furnace body 1. The induction heating coil 3 designed by the invention can further promote the flow of alloy melt, and simultaneously, the magnesium-based hydrogen storage alloy can flow more fully in an induction heating mode and a mode of introducing ultrasonic vibration by virtue of the outer bottom of the crucible, so that the structure height of the magnesium-based hydrogen storage alloy is uniformly refined.
The inside furnace lining that still is equipped with heat preservation usefulness of furnace body 1 of this embodiment, be located 4 peripheries of corundum crucible, the internal diameter of furnace lining from top to bottom reduces gradually, still be provided with the mounting groove that is used for fixed induction heating coil on the inner wall of furnace lining, the inner wall circumference spiral setting of furnace lining is followed to the mounting groove, this kind of design can be according to the heating scope of the crucible adjustment induction heating coil 3 of reducing, it is more simple and convenient to make induction heating coil 3's adjustment, the installation is more stable, also do benefit to induction heating coil 3 later maintenance and change simultaneously.
The control system of the embodiment of the invention comprises a display device 18, an induction current controller 19, an ultrasonic vibration output current controller 20, an ultrasonic vibration frequency controller 21, a temperature sensor and a temperature detection module, wherein the temperature sensor is arranged in a corundum crucible 4 and is electrically connected with the temperature detection module; the ultrasonic vibration output current controller 20 is electrically connected with the ultrasonic transducer 15; the ultrasonic vibration frequency controller 21 is electrically connected with the ultrasonic amplitude transformer 16; the induction current controller 19 is electrically connected with the induction heating coil 3; the display device 18 is connected with the induction current controller 19, the ultrasonic vibration output current controller 20, the ultrasonic vibration frequency controller 21, the temperature sensor and the temperature detection module, and displays the working states of the ultrasonic amplitude transformer 16, the ultrasonic transducer 15 and the induction heating coil 3 and the temperature information of the melt in the corundum crucible 4 in real time.
The gas sealing device 10 of the embodiment of the invention comprises an exhaust guide pipe, an oil sealing box body 103, an elastic sealing assembly 108 and a diffusing pipe 1010, wherein the exhaust guide pipe is provided with an exhaust pipe connecting pipe section 102, a sealing connecting pipe section 105 and a sealing box body connecting section; the pipe diameter of the sealing connection pipe section 105 is larger than that of the exhaust pipe connection pipe section 102; the sealing box body connecting section comprises a grid 106 and an end plate 107; the number of the grate bars 106 is multiple, the grate bars 106 are arranged at the bottom end of the seal connecting pipe section 105 at intervals along the circumferential direction, and the grate bars 106 extend downwards to be connected with an end plate 107; the end plate 107 is fixedly connected with the bottom plate of the oil seal box body 103; the elastic sealing assembly 108 comprises a sealing element, a first spiral spring 1083 and a second spiral spring 1084, the sealing element comprises a pipeline plugging section 1081 and a spring connecting section 1082, the vertical cross section of the pipeline plugging section 1081 is trapezoidal, the diameter of the upper end face of the pipeline plugging section 1082 is smaller than the inner diameter of the exhaust pipe connecting pipe section 102, a preset distance is reserved between the lower end face of the pipeline plugging section 1082 and the inner wall of the sealing connecting pipe section 105, the spring connecting section 1082 is fixedly connected with the lower end face of the pipeline plugging section 1081, the first spiral spring 1083 is sleeved on the spring connecting section 1082, and the other end of the first spiral spring 1083 extends downwards to be connected with the end plate 107; one end of the second coil spring 1084 is connected to the bottom of the spring connecting section 1082, and the other end of the second coil spring 1084 extends downward and is connected to the end plate 107; the blow-off pipe 1010 is provided at the upper portion of the oil-tight casing 103.
The gas sealing device 10 of the above embodiment further includes a liquid level meter 109, the liquid level meter 109 is disposed outside the oil seal box 103, the first coil spring 1083 and the second coil spring 1084 are in a pre-compressed state, the cross-sectional dimension of the spring connecting section 1082 is smaller than the dimension of the lower end face of the pipe plugging section 1081, specifically, the elastic sealing assembly 108 has a sealing state and a gas discharging state, in the gas discharging state, the first coil spring 1083 and the second coil spring 1084 are compressed, the sealing member moves downward, and the gas in the furnace body is discharged through the gap of the grid 106 of the sealing box connecting section; in a sealing state, under the action of the first coil spring 1083 and the second coil spring 1084, the pipe plugging section 1081 of the sealing element is tightly attached to the inner wall of the exhaust pipe connecting pipe section 102 to form a seal.
The ultrasonic transducer 15 of the embodiment of the invention is of a piezoelectric ceramic type, and the output amplitude of the ultrasonic transducer 15 is 5 to 7 μm; the ultrasonic amplitude transformer 16 is made of aluminum alloy; the tool bit 17 is made of T8 tool steel.
An embodiment of the invention comprises the following steps:
the method comprises the following steps: placing magnesium-based hydrogen storage alloy raw materials in a corundum crucible 4, closing a furnace cover 2 and locking;
step two: sequentially opening the vacuum pump 9 and the vacuum pumping valve 13, and sequentially closing the vacuum pumping valve 13 and the vacuum pump 9 when the barometer 22 displays that the air pressure value is zero;
step three: opening the first pressurizing valve 11, introducing argon, and closing the first pressurizing valve 11 and the argon bottle when the barometer 22 displays that the air pressure value is the standard air pressure;
step four: repeating the second step to the third step, and washing gas; the magnesium-based hydrogen storage alloy is extremely sensitive to oxygen and water vapor in the air, and even trace oxygen and water vapor pollution can greatly reduce the hydrogen storage performance of the alloy, so that oxygen and water vapor are prevented from being mixed in the high-temperature smelting process of the magnesium-based hydrogen storage alloy. The impurity gas content in the furnace in the alloy smelting process can be obviously reduced by repeatedly carrying out the gas washing processes of introducing high-purity argon and vacuumizing, and the impurity gas content can be lower than that in the pure vacuumizing process by several orders of magnitude.
Step five: starting the inductive current controller 19 and starting SF 6 +CO 2 Smelting by using a mixed gas bottle 8 and a second pressure valve 12, wherein the rated temperature in the furnace body 1 is 750 ℃, the heating rate is 30 ℃/min, the state of the alloy melt is observed through an observation port 5 every 10 min, and when the temperature is up to the rated temperature, the heat is continuously preserved for 30 min;
step six: regulating the output power and the vibration frequency of ultrasonic waves through an ultrasonic vibration output current controller 20 and an ultrasonic vibration frequency controller 21, then carrying out ultrasonic melt treatment, and closing an induction current controller 19 after the ultrasonic melt treatment is carried out for 15 minutes to naturally cool the melt; when the temperature shows that the melt temperature is lower than 500 ℃, closing the ultrasonic vibration output current controller 20 to finish ultrasonic melt treatment;
step seven: cooling and sampling of the Mg-based hydrogen storage alloy is performed by first closing the second pressurizing valve 12 and SF 6 +CO 2 Mixing a gas cylinder 8, then opening an argon gas cylinder and a first pressure valve 11 in sequence, and introducing high-purity argon gas; when the temperature display 18 is lower than 50 ℃, the first pressure valve 11 and the protective gas cylinder 7 are closed; and opening the furnace cover 2, and taking out and storing the magnesium-based hydrogen storage alloy.
FIG. 3- (a) shows Mg without ultrasonic melt treatment in the examples of the present invention 98 Ni 2 Alloy microstructure, FIG. 3- (b) is Mg treated with ultrasonic melt in the examples of the present invention 98 Ni 2 Alloy microstructure, it can be seen that Mg prepared using the ultrasonic melt processing apparatus and method of the present invention 98 Ni 2 The microstructure in the alloy is obviously uniformly refined, and the dendrite size of primary alpha-Mg is obviously reduced, wherein the dendrite size of the maximum alpha-Mg in the graph is reduced from 300 mu m in figure 3- (a) to 200 mu m in figure 3- (b). Therefore, the device and the method for preparing the magnesium-based hydrogen storage alloy by ultrasonic assistance can realize uniform refinement of the structure of the magnesium-based hydrogen storage alloy.
FIGS. 4- (a) and 4- (b) are views of ultrasonic melt treatment on Mg in examples of the present invention 98 Ni 2 Influence of hydrogen absorption and desorption performance of the alloy, wherein the hydrogen absorption condition is 300 ℃ and 2.5MPa hydrogen pressure, and the hydrogen desorption condition is 300 ℃ and 0.1MPa hydrogen pressure. It can be seen that the apparatus and method for ultrasonic melt treatment of the present invention can be used to treat Mg in the examples 98 Ni 2 The hydrogen absorption and desorption performance of the alloy is obviously improved, and for the hydrogen absorption process, the hydrogen absorption amount in 6 minutes is increased from 4.83wt.% to 5.01wt.%, and the hydrogen absorption amount in 150 minutes is increased from 5.75wt.% to 5.99wt.%; for the hydrogen discharge process, the hydrogen discharge amount in 3 minutes is increased from 4.34wt.% to 4.71wt.%, and the hydrogen discharge completion time is shortened from 9 minutes to 5.75 minutes. Therefore, the device and the method for preparing the magnesium-based hydrogen storage alloy by ultrasonic assistance can realize the cooperative optimization of hydrogen absorption and desorption performance by regulating and controlling the structure of the magnesium-based hydrogen storage alloy.
Compared with the prior art, the invention reduces the introduction of impurity elements by connecting the bottom of the corundum crucible with the ultrasonic melt processing system, ensures that the ultrasonic waves fully act on the alloy melt by reasonably designing the shape of the crucible, avoids the volatilization and oxidation of the alloy melt by the efficient gas protection system, uniformly distributes elements in the prepared magnesium-based hydrogen storage alloy, obviously refines the microstructure and obviously improves the hydrogen absorption and desorption performance.
Claims (8)
1. The utility model provides an ultrasonic wave assists device of preparation magnesium base hydrogen storage alloy which characterized in that: comprises an alloy smelting system, a gas protection system, an ultrasonic melt processing system and a control system,
the alloy smelting system comprises a smelting furnace, a corundum crucible (4) and a crucible support (6), wherein the crucible support (6) is arranged on a bottom plate in the smelting furnace, the vertical section of the corundum crucible (4) is in an inverted trapezoid shape, the corundum crucible (4) is arranged on the crucible support (6), and the crucible support (6) is provided with an ultrasonic vibration connecting port; the gas protection system is communicated with the smelting furnace; the ultrasonic melt processing system passes through the ultrasonic vibration connecting port and is connected with the bottom of the corundum crucible (4) in an abutting mode;
the smelting furnace comprises a furnace body (1), a furnace cover (2) and an induction heating coil (3), wherein the induction heating coil (3) is arranged along the circumferential direction of the inner side wall of the furnace body (1) to form an induction heating zone, the setting height of the bottom of the induction heating zone is the same as the bottom height of a corundum crucible (4), and the setting height of the top of the induction heating zone is the same as the top height of the corundum crucible (4); an observation port (5) is formed in the furnace cover (2), and a barometer for detecting the air pressure in the furnace body (1) is further arranged at the top of the furnace cover (2);
the gas protection system comprises a protection gas cylinder (7) and SF 6 +CO 2 A mixed gas bottle (8), a vacuum pump (9) and a communicating pipeline system,
the communication pipeline system comprises a first pressurizing pipeline (23), a second pressurizing pipeline (24), a vacuum pipeline (26) and an exhaust pipeline (25); the protective gas cylinder (7) is connected with a first pressurizing pipeline (23)The first pressurizing pipeline (23) is communicated with the furnace body (1) and is provided with a first pressurizing valve (11); the SF 6 +CO 2 The mixed gas bottle (8) is communicated with the furnace body (1) through a second pressurizing pipeline (24), and a second pressurizing valve (12) is arranged on the second pressurizing pipeline (24); the vacuum pump (9) is communicated with the furnace body (1) through a vacuum pipeline (26), and a vacuum extraction valve (13) is arranged on the vacuum pipeline (26); one end of the exhaust pipeline (25) is communicated with the furnace body (1), and the other end of the exhaust pipeline (25) is communicated with the gas sealing device (10) through an exhaust valve (14).
2. The apparatus of claim 1, wherein the ultrasonic-assisted preparation of the magnesium-based hydrogen storage alloy comprises: the ultrasonic melt processing system comprises an ultrasonic transducer (15), an ultrasonic amplitude transformer (16) and a tool head (17), wherein the ultrasonic transducer (15) is arranged on a bottom plate in the furnace body (1) through a connecting piece, the ultrasonic amplitude transformer (16) is connected with the ultrasonic transducer (15), and the ultrasonic amplitude transformer (16) is positioned above the ultrasonic transducer (15); the tool head (17) is connected with the ultrasonic amplitude transformer (16), the tool head (17) is positioned above the ultrasonic amplitude transformer, and the tool head (17) passes through the ultrasonic vibration connecting port of the crucible support (6) to be attached to the bottom of the corundum crucible (4).
3. The apparatus for ultrasonic-assisted preparation of magnesium-based hydrogen storage alloy according to any of claims 1 to 2, wherein: the control system comprises a display device (18), an induction current controller (19), an ultrasonic vibration output current controller (20), an ultrasonic vibration frequency controller (21), a temperature sensor and a temperature detection module;
the temperature sensor is arranged in the corundum crucible (4), and is electrically connected with the temperature detection module; the ultrasonic vibration output current controller (20) is electrically connected with the ultrasonic transducer (15); the ultrasonic vibration frequency controller (21) is electrically connected with the ultrasonic amplitude transformer (16); the induction current controller (19) is electrically connected with the induction heating coil (3);
the display device (18) is connected with the induction current controller (19), the ultrasonic vibration output current controller (20), the ultrasonic vibration frequency controller (21), the temperature sensor and the temperature detection module, and displays the working states of the ultrasonic amplitude transformer (16), the ultrasonic transducer (15) and the induction heating coil (3) and the temperature information of the melt in the corundum crucible (4) in real time.
4. The apparatus of claim 2, wherein the ultrasonic-assisted preparation of the magnesium-based hydrogen storage alloy comprises: the gas sealing device (10) comprises an exhaust guide pipe, an oil sealing box body (103), an elastic sealing assembly (108) and a diffusing pipe (1010);
the exhaust guide pipe is provided with an exhaust pipe connecting pipe section (102), a sealing connecting pipe section (105) and a sealing box body connecting section, one end of the exhaust pipe connecting pipe section (102) is connected with an exhaust pipeline (25) through a flange (101), and the other end of the exhaust pipe connecting pipe section (102) penetrates through the top of the oil sealing box body (103) and is connected with the top end of the sealing connecting pipe section (105); the pipe diameter of the sealing connection pipe section (105) is larger than that of the exhaust pipe connection pipe section (102);
the sealing box body connecting section comprises a grate bar (106) and an end plate (107); the number of the grate bars (106) is multiple, the grate bars (106) are arranged at the bottom end of the seal connecting pipe section (105) at intervals along the circumferential direction, and the grate bars (106) extend downwards to be connected with an end plate (107);
the end plate (107) is fixedly connected with a bottom plate of the oil seal box body (103);
the elastic sealing assembly (108) comprises a sealing element, a first spiral spring (1083) and a second spiral spring (1084), the sealing element comprises a pipeline plugging section (1081) and a spring connecting section (1082), the vertical cross section of the pipeline plugging section (1081) is trapezoidal, the diameter of the upper end face of the pipeline plugging section (1082) is smaller than the inner diameter of the exhaust pipe connecting pipe section (102), a preset distance is reserved between the lower end face of the pipeline plugging section (1082) and the inner wall of the sealing connecting pipe section (105), the spring connecting section (1082) is fixedly connected with the lower end face of the pipeline plugging section (1081), the first spiral spring (1083) is sleeved on the spring connecting section (1082), and the other end of the first spiral spring (1083) extends downwards to be connected with the end plate (107); one end of the second spiral spring (1084) is connected with the bottom of the spring connecting section (1082), and the other end of the second spiral spring (1084) extends downwards to be connected with the end plate (107);
the diffusing pipe (1010) is arranged at the upper part of the oil seal box body (103).
5. The apparatus of claim 4, wherein the ultrasonic-assisted preparation of the magnesium-based hydrogen storage alloy comprises: the gas sealing device (10) further comprises a liquid level meter (109), the liquid level meter (109) is arranged on the outer side of the oil sealing box body (103), the first spiral spring (1083) and the second spiral spring (1084) are in a pre-compression state, and the cross section size of the spring connecting section (1082) is smaller than the size of the lower end face of the pipeline plugging section (1081).
6. A method for preparing a magnesium-based hydrogen storage alloy by using the ultrasonic-assisted magnesium-based hydrogen storage alloy preparation device of claim 2, comprising the steps of:
the method comprises the following steps: putting a magnesium-based hydrogen storage alloy raw material into a corundum crucible (4), closing a furnace cover (2) and locking;
step two: sequentially opening the vacuum pump (9) and the vacuum pumping valve (13), and sequentially closing the vacuum pumping valve (13) and the vacuum pump (9) when the air pressure value displayed by the air pressure gauge (22) is zero;
step three: opening a first pressurizing valve (11), introducing protective gas, and closing the first pressurizing valve (11) and the protective gas bottle (7) when the barometer (22) displays that the air pressure value is standard air pressure;
step four: repeating the second step to the third step;
step five: starting the induction current controller (19), in turn starting the SF 6 +CO 2 Smelting the mixed gas cylinder (8) and a second pressure valve (12);
step six: the ultrasonic melt treatment is carried out by adjusting the output power and the vibration frequency of ultrasonic waves through an ultrasonic vibration output current controller (20) and an ultrasonic vibration frequency controller (21);
step seven: and cooling and sampling the magnesium-based hydrogen storage alloy.
7. The method of claim 6 using an ultrasonic-assisted magnesium-based hydrogen storage alloy preparation apparatus for ultrasonic-assisted preparation of magnesium-based hydrogen storage alloy, wherein: step six, after the ultrasonic melt is processed for 15 minutes, the induction current controller (19) is closed, and the melt is naturally cooled; when the temperature indicates (18) that the melt temperature is below 500 ℃, the ultrasonic vibration output current controller (20) is closed, and the ultrasonic melt treatment is completed.
8. The method of claim 6 using an ultrasonic-assisted magnesium-based hydrogen storage alloy preparation apparatus for ultrasonic-assisted preparation of magnesium-based hydrogen storage alloy, wherein: setting a rated temperature of 750 ℃ in the furnace body (1), setting a heating rate of 30 ℃/min, observing the state of the alloy melt through the observation port (5) every 10 min, and keeping the temperature for 30 min when the display equipment (18) reaches the rated temperature;
the step seven of cooling and sampling the magnesium-based hydrogen storage alloy comprises the following steps:
closing the second pressurized valve (12) and SF 6 +CO 2 Mixing a gas cylinder (8), then opening a protective gas cylinder (7) and a first pressure valve (11) in sequence, and introducing protective gas; when the temperature display (18) is lower than 50 ℃, the first pressure valve (11) and the protective gas cylinder (7) are closed; and opening the furnace cover (2), and taking out and storing the magnesium-based hydrogen storage alloy.
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