CN112048651B - High-performance high-capacity hydrogen storage alloy for fuel cell and preparation method thereof - Google Patents
High-performance high-capacity hydrogen storage alloy for fuel cell and preparation method thereof Download PDFInfo
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C2202/04—Hydrogen absorbing
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- 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
- Y02E60/50—Fuel cells
Abstract
The invention relates to a high-performance high-capacity hydrogen storage alloy for fuel cells and a preparation method thereof, wherein the chemical composition of the hydrogen storage alloy is Mg expressed by atomic ratio80+x(Ce,Y)a(Ni,Co)bWherein x is more than or equal to 0 and less than or equal to 15, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 5 and less than or equal to 20; and a + b is more than or equal to 5 and less than or equal to 20; the alloy has a dual platform synergy mechanism. The preparation method adopts a 3+1 metallurgy method, a two-step smelting method and a one-step ball milling method, effectively inhibits the volatilization of magnesium, ensures the uniformity of alloy components, avoids the solid solution of Mg-Ni and Mg-Co compounds, and can generate single two magnesium compounds. After repeated hydrogenation, Mg with a high plateau pressure is formed2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5And (6) circulating. Dual platform induced Mg/MgH2Preferentially nucleate, thereby improving kinetic performance and reducing reaction temperature. The hydrogen storage alloy has hydrogen absorption capacity of more than 5 wt.%, has fast hydrogen absorption and desorption dynamics, and is expected to be a solid hydrogen source of a fuel cell.
Description
Technical Field
The invention belongs to the field of magnesium-based hydrogen storage alloy and a preparation process thereof, and particularly relates to a high-performance high-capacity hydrogen storage alloy with a double-platform cooperation mechanism for a fuel cell and a preparation method thereof.
Background
Hydrogen is a clean and efficient energy carrier, and can be prepared from fossil resources and various primary energy sources such as nuclear energy, renewable resources and the like. The method is not only beneficial to the realization of the multi-element optimization strategy of energy in China, but also beneficial to the realization of CO in the production of hydrogen fuel2Centralized processing. In addition, hydrogen energy can be efficiently converted into heat energy and electric energy through the fuel cell in the using process, and near zero emission is realized. Therefore, hydrogen energy is an important bridge for connecting fossil energy to renewable energy, and is an important green energy carrier in the 21 st century. Hydrogen energy is widely used in the fields of electronics, metallurgy, food, aerospace and the like, and with the development of fuel cells, the use of hydrogen as a source of automobile power is gaining more and more attention. However, hydrogen is the lightest of all elements, and the density is only 0.0899Kg/m under normal temperature and pressure3. Therefore, high density storage has been a world-wide challenge. At present, the safe, efficient and economic hydrogen storage technology becomes the bottleneck of the hydrogen fuel automobile towards practicability and scale. At present, a fuel-powered automobile can run 400-. It is estimated that a pem fuel cell powered car for 500km requires about 5-6kg of hydrogen, while the extra load is at least more than 300kg, calculated from the cylinder loading we usually use. Therefore, a high capacity hydrogen storage material has been desired based on practical application considerations, because it directly determines the energy density and power density at a certain weight and volume scale, especially for on-board hydrogen storage, which has become the most difficult factor in material design and development due to the need to operate within a narrow temperature range.
Magnesium-based hydride is the most promising high-capacity hydrogen storage material, the theoretical capacity of the magnesium-based hydride is as high as 7.6 wt.%, but due to the stable interaction of Mg-H bonds, the rapid hydrogen absorption and desorption of the magnesium-based hydride still needs more than 300 ℃ to be carried out, which is the most important factor for restricting the magnesium-based hydrogen storage alloy as the high-capacity hydrogen storage material for fuel automobiles. In view of this, many technologies at home and abroad, including preparation technology, component design, catalytic modification, surface modification, and compounding of various materials, have been studied with certain results, but still cannot meet the vehicle-mounted requirements established by the U.S. department of energy.
Disclosure of Invention
The invention aims to provide a high-performance high-capacity hydrogen storage alloy for a fuel cell, which is a Ce-RE-Mg-Ni-Co type magnesium-based hydrogen storage alloy, has a double-platform cooperation mechanism, has the characteristics of high performance, high capacity, low hydrogen absorption and desorption temperature (lower than 300 ℃), good dynamic performance and the like, and has good prospect in a hydrogen supply system of the fuel cell.
The invention also aims to provide a preparation method of the hydrogen storage alloy.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-performance high-capacity hydrogen storage alloy for fuel cells is a Ce-RE-Mg-Ni-Co type magnesium-based hydrogen storage alloy, and the chemical composition of the hydrogen storage alloy is expressed by atomic ratio as follows: mg (magnesium)80+x(Ce,Y)a(Ni,Co)bWherein x is more than or equal to 0 and less than or equal to 15, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 5 and less than or equal to 20; and a + b is more than or equal to 5 and less than or equal to 20; the hydrogen storage alloy has a dual platform synergy mechanism.
Preferably, x is 10, a is 3, and b is 7.
The hydrogen storage alloy has a multi-phase structure comprising CeMg12And Y5Mg24A metal compound phase, and Mg alone2Co phase and Mg2Ni phase other than Mg2(Co, Ni) phase.
The hydrogen storage alloy has three hydrogen absorption and desorption PCT platforms: relative to Mg/MgH2Cyclic plateaus, Mg with high plateaus2Ni/Mg2NiH4With circulation and low plateauMg6Co2H11/Mg2CoH5And (6) circulating.
The hydrogen storage alloy has the following double-platform synergistic mechanism: mg by high plateau2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5Cyclic, dual-platform induction of Mg/MgH2The nucleation is preferentially carried out in the process of absorbing and desorbing hydrogen.
The reversible hydrogen storage amount of the hydrogen storage alloy is more than 5 wt.% at the temperature of 280 ℃, 4 wt.% of hydrogen is absorbed for 30 minutes at the temperature of 100 ℃, the peak hydrogen release temperature is reduced to 270 ℃, and the initial hydrogen release temperature is reduced to below 200 ℃.
The saturated hydrogen absorption amount of the hydrogen storage alloy at the initial hydrogen pressure of 3.6MPa and the temperature of 300 ℃ is 5.04-5.72 wt.%; the hydrogen absorption amount in 5 minutes is 5.04-5.64 wt.% at an initial hydrogen pressure of 3MPa and at 300 ℃; 4.99-5.58 wt.% hydrogen evolution in 10 minutes at an initial pressure of 0.06MPa and 300 ℃; and the saturation percentage of hydrogen absorption after the 50 th cycle is 98.54-98.98%.
The preparation method of the hydrogen storage alloy comprises the following steps:
(1) chemical composition (Ce, Y) by atomic ratio at 1800 deg.C by vacuum induction melting methoda(Ni,Co)bPreparing a Ce-RE-Ni-Co intermediate alloy; wherein a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 5 and less than or equal to 20; and a + b is more than or equal to 5 and less than or equal to 20;
(2) preparing needed massive as-cast hydrogen storage alloy by pure Mg and the prepared Ce-RE-Ni-Co intermediate alloy according to a certain proportion through a vacuum induction melting method at 800 +/-10 ℃;
(3) ball-milling the obtained as-cast hydrogen storage alloy for 5 +/-0.5 hours at the speed of 300-350 revolutions per minute by adopting a mechanical ball milling method to prepare powdery ball-milled hydrogen storage alloy;
(4) and carrying out hydrogenation reaction on the obtained ball-milling alloy for multiple times under high-purity hydrogen.
In the step (1) and the step (2), vacuumizing is carried out to below 0.05Pa, and then helium with the pressure of 0.06 +/-0.01 MPa is introduced to serve as protective gas.
The smelting temperature in the step (1) is 1800 +/-20 ℃.
The additional amount of Mg added in step (2) was 5 wt.%.
The ball milling conditions in the step (3) are as follows: the ball material ratio is 20-30: 1; the ball milling speed is 300-350 r/m.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a 3+1 metallurgy method for preparation, effectively inhibits the volatilization of magnesium and the solid solution in nickel-magnesium and cobalt-magnesium compounds, and forms independent single Mg2Ni phase and Mg2The Co phase, rather than the Mg2(Co, Ni) phase, allows the hydrogen storage alloy to have three hydrogen absorption and desorption PCT (pressure-composition isotherm) platforms under hydrogenation, forming a phase corresponding to Mg/MgH2Platform of (2), Mg with high platform2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5And (6) circulating. Dual platform induced Mg/MgH2Preferentially nucleate, thereby improving kinetic performance and reducing reaction temperature. The reversible hydrogen storage amount of the hydrogen storage alloy is more than 5 wt.% at the temperature of 280 ℃, 4 wt.% of hydrogen can be absorbed in 30 minutes at the temperature of 100 ℃, the peak temperature of hydrogen release is reduced to 270 ℃, and the initial hydrogen release temperature is reduced to below 200 ℃.
Drawings
FIG. 1 is an SEM image of as-cast hydrogen storage alloys of examples 1, 2 and 3 of the present invention;
FIG. 2 is an XRD spectrum of a ball-milled hydrogen storage alloy and its hydrogen absorption and desorption in example 1 of the present invention;
FIG. 3 is a PCT curve of a hydrogen storage alloy of example 1 of the present invention;
FIG. 4 shows the microstructure and electron diffraction rings of the hydrogen storage alloy of examples 2 and 3 of the present invention under High Resolution Transmission Electron Microscopy (HRTEM).
Detailed Description
The design concept and the forming mechanism of the present invention will be described in further detail below with reference to the accompanying drawings and examples to make the technical solution of the present invention clearer.
The chemical components and the proportion of the specific embodiment of the invention are selected as follows:
example 1 Mg90(Ce,Y)3(Ni,Co)7(x＝10，a＝3，b＝7)
Example 2 Mg90(Ce,Y)5(Ni,Co)5(x＝10，a＝5，b＝5)
Example 3 Mg80(Ce,Y)10(Ni,Co)10(x＝0，a＝10，b＝10)
Example 1
Bulk cerium metal, yttrium metal, nickel metal and cobalt metal with the purity of more than or equal to 99.5 percent are selected. These metals are represented by the formula (Ce, Y)3(Ni,Co)7278.3 g of metal cerium, 176.6 g of metal yttrium, 272 g of metal nickel and 273.1 g of metal cobalt are weighed respectively. Putting the weighed metal into a magnesium oxide crucible of a medium-frequency induction furnace, vacuumizing to the vacuum degree of below 0.05Pa, and introducing helium gas of 0.06MPa as protective gas. And adjusting the heating power, controlling the temperature to be 1800 ℃, electromagnetically stirring for 5 minutes after all metals are completely melted, pouring the molten liquid into a casting mold, and cooling to room temperature to obtain the as-cast Ce-RE-Ni-Co intermediate alloy.
743.4 g of metal magnesium is taken, 256.6 g of prepared Ce-RE-Ni-Co intermediate alloy is placed in a magnesium oxide crucible of a medium frequency induction furnace, the vacuum degree is also pumped to be below 0.05Pa, and helium with 0.06MPa is introduced as protective gas. Regulating heating power, controlling the temperature at 800 ℃, electromagnetically stirring for 5 minutes after all metals are completely melted, pouring the molten liquid into a casting mold, and cooling to room temperature to obtain as-cast Mg90(Ce,Y)3(Ni,Co)7A hydrogen storage alloy.
Subjecting the obtained as-cast Mg90(Ce,Y)3(Ni,Co)7The hydrogen storage alloy is mechanically crushed and passes through a 200-mesh sieve, 5 g of alloy powder sample is taken and then put into a stainless steel ball milling tank, and ball milling is carried out under the protection of argon, wherein the ball milling conditions are as follows: the ball material ratio is 20: 1; rotating speed: 300 revolutions per minute. In order to prevent the temperature of the ball milling tank from being overhigh, the ball milling is stopped for 0.5 hour every 0.5 hour in the ball milling process, and the effective ball milling time is 5 hours in total. Cooling the ball-milled sample and sieving the cooled ball-milled sample with a 200-mesh sieve to obtain ball-milled Mg90(Ce,Y)3(Ni,Co)7A hydrogen storage alloy.
Taking 0.5 g of ball-milled hydrogen storage alloy powder, placing the ball-milled hydrogen storage alloy powder in a stainless steel cylindrical tank, placing the stainless steel cylindrical tank in a reactor, vacuumizing, raising the temperature to 360 ℃, continuing vacuumizing for 30 minutes to decompose stearic acid, completely pumping the stearic acid out, achieving a vacuum state again, then filling high-purity hydrogen, and performing multiple hydrogen absorption and desorption cycles on the alloy powder by using a full-automatic Sieverts equipment tester so as to achieve full hydrogenation. Wherein the hydrogenation conditions are as follows: the hydrogen absorption and desorption temperature is 360 ℃, the hydrogen absorption pressure is 3.6MPa, the hydrogen desorption pressure is 0.06MPa, the hydrogen absorption and desorption cycles are carried out for 6 times, and the hydrogen absorption and desorption time is more than 2 hours.
The as-cast state and the alloy morphology were observed by SEM, and the results are shown in FIG. 1; the microscopic components of the ball-milled alloys in various morphologies were analyzed by XRD and found to undergo a number of reversible phase transformations, the results of which are shown in fig. 2. PCT curves for the alloys were tested using a fully automated Sieverts and found to correspond to different hydrogen sorption and desorption platforms for a number of reversible reactions, with the results shown in fig. 3, and the gaseous hydrogen storage properties of the alloys also tested, with the results shown in table 1.
Referring to fig. 3, the alloy has three hydrogen absorption and desorption PCT platforms, and the middle long platform is the main hydrogen absorption and desorption platform, which determines the hydrogen absorption and desorption amount, the dynamics and the thermodynamics of the alloy. The low short platform at the front end mainly induces the platform in the middle to absorb hydrogen, and the high short platform at the rear end mainly induces the platform in the middle to release hydrogen, so that the hydrogen absorption and release dynamics can be improved simultaneously through the synergistic effect of the short platforms at the front end and the rear end.
Example 2
According to the formula Mg90(Ce,Y)5(Ni,Co)5404.2 g of cerium metal, 256.5 g of yttrium metal, 169.3 g of nickel metal, 170 g of cobalt metal and 716.3 g of magnesium metal are weighed, an as-cast master alloy is smelted according to the method of example 1, and then mechanical crushing, ball milling and activation treatment are carried out, wherein the weight of the master alloy is 283.7 g. The as-cast state and the alloy morphology were observed by SEM, and the results are shown in FIG. 1; the microstructure and the crystal state after activation are analyzed by HRTEM and electron diffraction (SAED), and the ball-milled alloy is found to have a nanocrystalline-amorphous structure, the alloy after activation is crystallized, but the grain size is very small, is 50 nanometers on average and is of a nanocrystalline structure, and the result is shown in the figure4. The gaseous hydrogen storage properties of the alloys were also tested and the results are shown in Table 1.
Example 3
According to the formula Mg80(Ce,Y)10(Ni,Co)10404.2 g of cerium metal, 256.5 g of yttrium metal, 169.3 g of nickel metal, 170 g of cobalt metal and 558 g of magnesium metal are weighed, an as-cast master alloy is smelted according to the method of example 1, and then mechanical crushing, ball milling and activation treatment are carried out, wherein the weight of the master alloy is 442 g. The as-cast state and the alloy morphology were observed by SEM, and the results are shown in FIG. 1; the microstructure and the crystal state after activation were analyzed by HRTEM and electron diffraction (SAED), and it was found that the ball-milled alloy had a nanocrystalline-amorphous structure, and the alloy crystallized after activation, but the grain size was very small, on average 50 nm, which was a nanocrystalline structure, and the results are shown in fig. 4. The gaseous hydrogen storage properties of the alloys were also tested and the results are shown in Table 1.
TABLE 1 Hydrogen storage Capacity and cycling stability of the Hydrogen storage alloys of examples 1-3 of the present invention
Cmax-saturated hydrogen uptake (wt.%) at an initial hydrogen pressure of 3.6MPa and 300 ℃;
S100＝C100/Cmaxx 100%, wherein CmaxIs the saturated hydrogen absorption of the alloy, C100Hydrogen uptake after 50 th cycle.
The results in table 1 show that compared with similar alloys studied at home and abroad, the hydrogen storage performance of the alloy of the invention in a low-temperature state is obviously improved, and the alloy has good hydrogen absorption and desorption circulation stability.
The above embodiments are preferred examples of the present invention, and the claims are not limited thereto, and any other modifications or equivalent substitutions which do not depart from the technical scope of the present invention are included in the scope of the present invention.
Claims (11)
1. A high-performance high-capacity hydrogen storage alloy for fuel cells is a Ce-RE-Mg-Ni-Co type magnesium-based hydrogen storage alloy, and is characterized in that the chemical composition of the hydrogen storage alloy is expressed by atomic ratio as follows: mg (magnesium)80+x(Ce,Y)a(Ni,Co)bWherein x is more than or equal to 0 and less than or equal to 15, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 5 and less than or equal to 20; and a + b is more than or equal to 5 and less than or equal to 20; the hydrogen storage alloy has the following dual-platform synergistic mechanism: mg by high plateau2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5Cyclic, dual-platform induction of Mg/MgH2The nucleation is preferentially carried out in the process of absorbing and desorbing hydrogen.
2. The hydrogen storage alloy according to claim 1, wherein x is 10, a is 3, and b is 7.
3. The hydrogen storage alloy according to claim 1, having a multi-phase structure comprising CeMg12And Y5Mg24A metal compound phase, and Mg alone2Co phase and Mg2Ni phase other than Mg2(Co, Ni) phase.
4. The hydrogen storage alloy according to claim 1, having three hydrogen absorption and desorption PCT platforms: relative to Mg/MgH2Cyclic plateaus, Mg with high plateaus2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5And (6) circulating.
5. The hydrogen storage alloy according to claim 1, wherein the reversible hydrogen storage amount of the hydrogen storage alloy is more than 5 wt.% at a temperature of 280 ℃, and 4 wt.% of hydrogen gas is absorbed for 30 minutes at a temperature of 100 ℃, and the hydrogen desorption peak temperature is reduced to 270 ℃ and the initial hydrogen desorption temperature is reduced to 200 ℃ or less.
6. The hydrogen storage alloy according to claim 1, wherein the saturated hydrogen absorption amount of the hydrogen storage alloy at an initial hydrogen pressure of 3.6MPa and 300 ℃ is 5.04 to 5.72 wt.%; the hydrogen absorption amount in 5 minutes is 5.04-5.64 wt.% at an initial hydrogen pressure of 3MPa and at 300 ℃; 4.99-5.58 wt.% hydrogen evolution in 10 minutes at an initial pressure of 0.06MPa and 300 ℃; and the saturation percentage of hydrogen absorption after the 50 th cycle is 98.54-98.98%.
7. A method for producing the hydrogen storage alloy according to claim 1, comprising the steps of:
(1) chemical composition (Ce, Y) by atomic ratio at 1800 deg.C by vacuum induction melting methoda(Ni,Co)bPreparing a Ce-RE-Ni-Co intermediate alloy; wherein a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 5 and less than or equal to 20; and a + b is more than or equal to 5 and less than or equal to 20; the hydrogen storage alloy has the following dual-platform synergistic mechanism: mg by high plateau2Ni/Mg2NiH4Cyclic and low plateau Mg6Co2H11/Mg2CoH5Cyclic, dual-platform induction of Mg/MgH2Preferentially forming nuclei in the process of hydrogen absorption and desorption;
(2) preparing needed massive as-cast hydrogen storage alloy by pure Mg and the prepared Ce-RE-Ni-Co intermediate alloy according to a certain proportion through a vacuum induction melting method at 800 +/-10 ℃;
(3) ball-milling the obtained as-cast hydrogen storage alloy for 5 +/-0.5 hours at the speed of 300-350 revolutions per minute by adopting a mechanical ball milling method to prepare powdery ball-milled hydrogen storage alloy;
(4) and carrying out hydrogenation reaction on the obtained ball-milling alloy for multiple times under high-purity hydrogen.
8. The preparation method according to claim 7, wherein in the step (1) and the step (2), vacuum is pumped to below 0.05Pa, and then helium gas with the pressure of 0.06 +/-0.01 MPa is introduced as protective gas.
9. The method according to claim 7, wherein the melting temperature in the step (1) is 1800 ± 20 ℃.
10. The method of claim 7, wherein the additional amount of Mg added in step (2) is 5 wt.%.
11. The preparation method according to claim 7, wherein the ball milling conditions in the step (3) are as follows: the ball material ratio is 20-30: 1; the ball milling speed is 300-350 r/m.
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