High-stability vanadium-based solid solution hydrogen storage alloy
By optimizing the composition ratio and process, a highly stable vanadium-based solid solution hydrogen storage alloy was prepared, which solved the problems of low hydrogen absorption and poor cycle performance of traditional alloys, and achieved efficient hydrogen storage performance and long-term stability.
Patent Information
- Application Number
- CN202511112006.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-08
- Publication Date
- 2025-11-14
AI Technical Summary
Traditional vanadium-based solid solution hydrogen storage alloys have low hydrogen absorption capacity and long hydrogen absorption/desorption time at room temperature. Their performance deteriorates significantly after multiple cycles, limiting their practical application efficiency.
A high-stability vanadium-based solid solution hydrogen storage alloy was prepared by optimizing the composition ratio, adding transition elements and trace additives, and combining low-pressure vacuum sintering and mechanical ball milling techniques.
It significantly improves the hydrogen absorption capacity and cycle stability of the alloy, shortens the saturation time, and enhances hydrogen storage and desorption efficiency, demonstrating excellent hydrogen storage performance and long-term stability.
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Figure CN120945265A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hydrogen storage alloy preparation, and particularly to highly stable vanadium-based solid solution hydrogen storage alloys. Background Technology
[0002] Traditional vanadium-based solid solution hydrogen storage alloys have low hydrogen absorption capacity at room temperature, typically between 1.8 and 2.5 wt.%, and poor hydrogen absorption and desorption performance at 300°C. The time for traditional alloys to reach hydrogen saturation is relatively long, usually more than 150 minutes, which limits their efficiency in practical applications. After multiple hydrogen absorption and desorption cycles, the hydrogen storage performance of traditional alloys deteriorates significantly, typically by more than 10% after 50-100 cycles.
[0003] Therefore, it is necessary to propose a highly stable vanadium-based solid solution hydrogen storage alloy to solve the above problems. Summary of the Invention
[0004] The purpose of this invention is to provide a highly stable vanadium-based solid solution hydrogen storage alloy to solve the problems mentioned in the background art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: a high-stability vanadium-based solid solution hydrogen storage alloy, comprising main components, minor components, transition elements and trace additives;
[0006] The main component includes metallic vanadium with a purity of ≥99.5%;
[0007] The secondary components include metallic magnesium powder with a purity of ≥99.8%;
[0008] Transition elements include nickel, zirconium, manganese, and titanium;
[0009] The trace additives are selected from rare earth elements such as yttrium, silicon carbide powder, or aluminum nitride powder.
[0010] Preferably, the vanadium metal accounts for 36% by weight, the magnesium metal powder accounts for 59.5% by weight, the mixture of transition elements accounts for 4% by weight, and the rare earth element yttrium accounts for 0.5% by weight.
[0011] Preferably, the vanadium metal accounts for 38% by weight, the magnesium metal powder accounts for 55% by weight, the mixture of transition elements accounts for 5% by weight, and the silicon carbide powder accounts for 2% by weight.
[0012] Preferably, the vanadium metal accounts for 34% by weight, the magnesium metal powder accounts for 58% by weight, the mixture of transition elements accounts for 6% by weight, and the silicon carbide powder accounts for 2% by weight.
[0013] Preferably, the particle size of the magnesium powder is 147 μm to 75 μm.
[0014] Preferably, the trace additive is silicon carbide powder with a particle size of 10 μm.
[0015] Preferably, the trace additive is aluminum nitride powder with a particle size of 5 μm.
[0016] This invention also discloses a method for preparing a highly stable vanadium-based solid solution hydrogen storage alloy, comprising the following steps:
[0017] S101: Alloy preparation, a mixture of transition elements and metallic vanadium are mixed in a weight ratio, and repeatedly melted in a vacuum arc furnace four to six times to obtain an ingot. After that, the ingot is mechanically crushed and mechanically ball-milled, and then screened to obtain vanadium alloy fine powder with a size of less than 75μm.
[0018] S102: Mixing, the vanadium alloy fine powder is mixed with magnesium powder and trace additives in a uniform ratio to ensure that the components are in full contact.
[0019] S103: Cold pre-pressing, the mixed powder is cold pre-pressed at a pressure of 50-100MPa and a holding time of 5-10 minutes to form a pre-pressed blank;
[0020] S104: Low-pressure vacuum sintering. The pre-pressed billet is placed in a low-pressure vacuum sintering furnace, and the furnace is evacuated to 10⁻⁵-10⁻³ Pa. Argon gas is introduced for protection, and the argon gas pressure is controlled at 0.01-0.1 MPa. The sintering temperature is set to 500-600℃, and the sintering time is 10-15 minutes. The billet is then cooled to room temperature in the furnace.
[0021] S105: Post-treatment, the sintered alloy is mechanically ball-milled for 2-4 hours at a speed of 300-400 rpm to obtain high-stability vanadium-based solid solution hydrogen storage alloy fine powder with a particle size of less than 75 μm.
[0022] Preferably, when the trace additive selected in S102 is silicon carbide powder, a high-energy ball mill is used for ball milling, the ball milling time is 4 hours, and the rotation speed is 400 rpm.
[0023] Preferably, when the trace additive selected in S102 is aluminum nitride powder, the ball milling is performed by ultrasonic-assisted ball milling for 5 hours, with an ultrasonic power of 300W and a frequency of 40kHz.
[0024] The technical effects and advantages of this invention are as follows:
[0025] 1. By optimizing the alloy's formulation and process, especially by adding transition elements and trace additives to the vanadium-based solid solution, the hydrogen absorption capacity of the alloy was significantly improved; Example 3 showed a hydrogen absorption capacity of 3.0 wt.% at room temperature and 6.2 wt.% at 300°C, demonstrating excellent hydrogen storage performance.
[0026] 2. The use of low-pressure vacuum sintering and mechanical ball milling technology significantly shortens the saturation time of the alloy; in Example 3, the saturation time at both room temperature and 300°C is shortened to less than 90 minutes, improving the efficiency of hydrogen storage and desorption.
[0027] 3. By adding trace additives (such as yttrium, silicon carbide, aluminum nitride, etc.), the cycle stability of the alloy is significantly improved; after 200 hydrogen absorption and desorption cycles, the performance of Example 3 decreased by only 3%, demonstrating excellent cycle stability and making it suitable for long-term use. Attached Figure Description
[0028] Figure 1 This diagram illustrates the preparation method of the high-stability vanadium-based solid solution hydrogen storage alloy of the present invention.
[0029] Figure 2 For the present invention Figure 1 A schematic diagram of S102 in Example 2.
[0030] Figure 3 For the present invention Figure 1 A schematic diagram of S102 in Example 23. Detailed Implementation
[0031] Example 1, the present invention provides as follows Figures 1-3 The high-stability vanadium-based solid solution hydrogen storage alloy shown comprises three main parts. The first part consists of vanadium (V) with a purity ≥99.5% as the main component, with an equal weight mixture of transition elements nickel (Ni), zirconium (Zr), manganese (Mn), and titanium (Ti), accounting for 40% of the total weight, of which vanadium accounts for 36% and the transition element mixture accounts for 4%. The second part consists of magnesium powder with a purity ≥99.8% and a particle size of 147μm~75μm (100~200 mesh), accounting for 59.5% by weight. The third part consists of 0.5% rare earth element yttrium (Y) added to improve the alloy's corrosion resistance and hydrogen storage stability.
[0032] The preparation process of this highly stable vanadium-based solid solution hydrogen storage alloy includes:
[0033] 1. Alloy preparation: The mixture of transition elements and metallic vanadium were mixed at a weight ratio of 4% and 36%, and repeatedly melted in a vacuum arc furnace four times to obtain an ingot. The ingot was then mechanically crushed and ball-milled, and screened to obtain vanadium alloy fine powder with a particle size of less than 75 μm.
[0034] 2. Mixing: Mix the vanadium alloy fine powder with magnesium powder and yttrium powder in a uniform ratio to ensure that all components are in full contact.
[0035] 3. Cold pre-pressing: The mixed powder is cold pre-pressed at a pressure of 50 MPa for 5 minutes to form a pre-pressed blank.
[0036] 4. Low-pressure vacuum sintering: Place the pre-pressed billet into a low-pressure vacuum sintering furnace and evacuate to 10°C. -3 Pa, argon gas was introduced for protection, and the argon gas pressure was controlled at 0.1 MPa. The sintering temperature was set to 500℃, the sintering time was 10 minutes, and the furnace was cooled to room temperature.
[0037] 5. Post-processing: The sintered alloy was subjected to mechanical ball milling for 2 hours at a speed of 300 rpm to obtain high-stability vanadium-based solid solution hydrogen storage alloy fine powder with a particle size of less than 75 μm.
[0038] Example 2, the present invention provides as follows Figures 1-3 The high-stability vanadium-based solid solution hydrogen storage alloy shown comprises three main parts. The first part consists of vanadium (V) with a purity ≥99.5% as the main component, with an equal weight mixture of transition elements nickel (Ni), zirconium (Zr), manganese (Mn), and titanium (Ti), accounting for 43% of the total weight, of which vanadium accounts for 38% and the transition element mixture accounts for 5%. The second part consists of magnesium powder with a purity ≥99.8% and a particle size of 147μm to 75μm (100 to 200 mesh), accounting for 55% of the weight. The third part consists of 2% silicon carbide (SiC) powder with a particle size of 10μm, used to improve the alloy's thermal stability and thermal shock resistance.
[0039] The preparation process of this highly stable vanadium-based solid solution hydrogen storage alloy includes:
[0040] 1. Alloy preparation: The mixture of transition elements and metallic vanadium were mixed at a weight ratio of 5% and 38%, and repeatedly melted in a vacuum electric arc furnace five times to obtain an ingot. The ingot was then mechanically crushed and mechanically ball-milled, and screened to obtain vanadium alloy fine powder with a particle size of less than 75 μm.
[0041] 2. Mixing: Mix vanadium alloy fine powder with magnesium powder and silicon carbide powder in a uniform ratio, and then ball mill using a high-energy ball mill for 4 hours at a speed of 400 rpm to ensure that all components are fully mixed and the particles are fined.
[0042] 3. Cold pre-pressing: The mixed powder is cold pre-pressed at a pressure of 80 MPa for 8 minutes to form a pre-pressed blank.
[0043] 4. Low-pressure vacuum sintering: Place the pre-pressed billet into a low-pressure vacuum sintering furnace and evacuate to 10°C. -4 Pa, argon gas was introduced for protection, and the argon gas pressure was controlled at 0.05 MPa. The sintering temperature was set to 550℃, the sintering time was 12 minutes, and the furnace was cooled to room temperature.
[0044] 5. Post-processing: The sintered alloy was subjected to mechanical ball milling for 3 hours at a speed of 300 rpm to obtain high-stability vanadium-based solid solution hydrogen storage alloy fine powder with a particle size of less than 75 μm.
[0045] Example 3, the present invention provides as follows Figures 1-3 The high-stability vanadium-based solid solution hydrogen storage alloy shown comprises three main parts. The first part consists of vanadium (V) with a purity ≥99.5% as the main component, with an equal weight mixture of transition elements nickel (Ni), zirconium (Zr), manganese (Mn), and titanium (Ti), accounting for 40% of the total weight, of which vanadium accounts for 34% and the transition element mixture accounts for 6%. The second part consists of magnesium powder with a purity ≥99.8% and a particle size of 147μm to 75μm (100 to 200 mesh), accounting for 58% of the weight. The third part consists of 2% aluminum nitride (AlN) powder with a particle size of 5μm, used to improve the thermal conductivity of the alloy and the thermal stability during hydrogen storage.
[0046] The preparation process of this highly stable vanadium-based solid solution hydrogen storage alloy includes:
[0047] 1. Alloy preparation: A mixture of transition elements and metallic vanadium were mixed at a weight ratio of 6% and 34%, and repeatedly melted in a vacuum arc furnace six times to obtain an ingot. The ingot was then mechanically crushed and ball-milled, and screened to obtain vanadium alloy fine powder with a particle size of less than 75 μm.
[0048] 2. Mixing: Vanadium alloy fine powder is mixed evenly with magnesium powder and aluminum nitride powder in a certain proportion. The mixture is then ball-milled using ultrasonic-assisted ball milling for 5 hours. The ultrasonic power is 300W and the frequency is 40kHz to ensure that the components are mixed evenly and that the particle surface is activated.
[0049] 3. Cold pre-pressing: The mixed powder is cold pre-pressed at a pressure of 100 MPa for 10 minutes to form a pre-pressed blank.
[0050] 4. Low-pressure vacuum sintering: Place the pre-pressed billet into a low-pressure vacuum sintering furnace and evacuate to 10°C. -5 Pa, argon gas was introduced for protection, and the argon gas pressure was controlled at 0.01 MPa. The sintering temperature was set to 600℃, the sintering time was 15 minutes, and the furnace was cooled to room temperature.
[0051] 5. Post-processing: The sintered alloy was subjected to mechanical ball milling for 4 hours at a speed of 400 rpm to obtain high-stability vanadium-based solid solution hydrogen storage alloy fine powder with a particle size of less than 75 μm.
[0052] Table 1 Performance Test Table
[0053]
[0054] In Table 1, the following parameters are given: Hydrogen absorption (room temperature) (wt.%): represents the maximum hydrogen absorption of the alloy at room temperature, expressed as a weight percentage; Hydrogen absorption (300℃) (wt.%): represents the maximum hydrogen absorption of the alloy at 300℃, expressed as a weight percentage; Saturation time (room temperature) (min): represents the time required for the alloy to reach its maximum hydrogen absorption at room temperature, expressed in minutes; Saturation time (300℃) (min): represents the time required for the alloy to reach its maximum hydrogen absorption at 300℃, expressed in minutes; Performance degradation (number of cycles): represents the number of cycles after which the alloy's performance begins to degrade; Performance degradation (%): represents the percentage of performance degradation of the alloy after multiple hydrogen absorption and desorption cycles; Thermal stability test (300℃, 24h): represents the structural and performance changes of the alloy after continuous heating at 300℃ for 24 hours.
[0055] Example 3 exhibited the highest hydrogen absorption capacity at room temperature and 300°C, at 3.0 wt.% and 6.2 wt.%, respectively. It also had the shortest saturation time, at 90 minutes (room temperature) and 90 minutes (300°C). After 200 hydrogen absorption / desorption cycles, Example 3 showed only a 3% performance decrease, demonstrating the best cycle stability. All examples showed no significant changes in structure and performance after continuous heating at 300°C for 24 hours, indicating good thermal stability. These data demonstrate that Example 3 performed best in terms of hydrogen absorption capacity, saturation time, cycle stability, and thermal stability, making it the superior performer among the three examples.
[0056] Therefore, the low-pressure vacuum sintering technology employed in this invention significantly improves the thermal stability of the alloy. All embodiments showed no significant changes in structure and properties after continuous heating at 300°C for 24 hours, making them suitable for use in high-temperature environments. The low-pressure vacuum sintering technology simplifies the production process, shortens sintering time, and reduces production costs. Simultaneously, optimized ingredient proportions and processes improve material utilization, further reducing production costs. The use of low-pressure vacuum sintering and mechanical ball milling shortens the production cycle and improves production efficiency. For example, the sintering time in Example 3 was only 15 minutes, significantly improving production efficiency. The addition of trace additives and the use of low-pressure vacuum sintering technology significantly improve the overall performance of the alloy. The alloy of this invention not only exhibits excellent hydrogen storage performance but also demonstrates superior performance in corrosion resistance, thermal stability, and cycle stability, making it suitable for use under various complex operating conditions.
Claims
1. A high-stability vanadium-based solid solution hydrogen storage alloy, characterized in that: Includes main components, minor components, transition elements, and trace additives; The main component includes metallic vanadium with a purity of ≥99.5%; The secondary components include metallic magnesium powder with a purity of ≥99.8%; Transition elements include nickel, zirconium, manganese, and titanium; The trace additives are selected from rare earth elements such as yttrium, silicon carbide powder, or aluminum nitride powder.
2. The high-stability vanadium-based solid solution hydrogen storage alloy according to claim 1, characterized in that: The composition of the metal vanadium is 36% by weight, the composition of the metal magnesium powder is 59.5% by weight, the composition of the mixture of transition elements is 4% by weight, and the composition of the rare earth element yttrium is 0.5% by weight.
3. The high-stability vanadium-based solid solution hydrogen storage alloy according to claim 1, characterized in that: The composition of the metal vanadium is 38% by weight, the composition of the metal magnesium powder is 55% by weight, the composition of the transition element mixture is 5% by weight, and the composition of the silicon carbide powder is 2% by weight.
4. The high-stability vanadium-based solid solution hydrogen storage alloy according to claim 1, characterized in that: The vanadium metal accounts for 34% by weight, the magnesium metal powder accounts for 58% by weight, the mixture of transition elements accounts for 6% by weight, and the silicon carbide powder accounts for 2% by weight.
5. The high-stability vanadium-based solid solution hydrogen storage alloy according to any one of claims 1-4, characterized in that: The particle size of the magnesium powder is 147 μm to 75 μm.
6. The high-stability vanadium-based solid solution hydrogen storage alloy according to any one of claims 1-4, characterized in that: The trace additive is made of silicon carbide powder with a particle size of 10 μm.
7. The high-stability vanadium-based solid solution hydrogen storage alloy according to any one of claims 1-4, characterized in that: When the trace additive is selected from aluminum nitride powder, the particle size is 5 μm.
8. A method for preparing a high-stability vanadium-based solid solution hydrogen storage alloy, characterized in that: The high-stability vanadium-based solid solution hydrogen storage alloy according to any one of claims 1-4 includes the following steps: S101: Alloy preparation, a mixture of transition elements and metallic vanadium are mixed in a weight ratio, and repeatedly melted in a vacuum arc furnace four to six times to obtain an ingot. After that, the ingot is mechanically crushed and mechanically ball-milled, and then screened to obtain vanadium alloy fine powder with a size of less than 75μm. S102: Mixing, the vanadium alloy fine powder is mixed with magnesium powder and trace additives in a uniform ratio to ensure that the components are in full contact. S103: Cold pre-pressing, the mixed powder is cold pre-pressed at a pressure of 50-100MPa and a holding time of 5-10 minutes to form a pre-pressed blank; S104: Low-pressure vacuum sintering. The pre-pressed billet is placed in a low-pressure vacuum sintering furnace and evacuated to 100°C. -5 -10 -3 Pa, argon gas is introduced for protection, and the argon gas pressure is controlled at 0.01-0.1 MPa. The sintering temperature is set to 500-600℃, the sintering time is 10-15 minutes, and the furnace is cooled to room temperature. S105: Post-treatment, the sintered alloy is mechanically ball-milled for 2-4 hours at a speed of 300-400 rpm to obtain high-stability vanadium-based solid solution hydrogen storage alloy fine powder with a particle size of less than 75 μm.
9. The method for preparing a high-stability vanadium-based solid solution hydrogen storage alloy according to claim 8, characterized in that: When the trace additive selected in S102 is silicon carbide powder, a high-energy ball mill is used for ball milling for 4 hours at a speed of 400 rpm.
10. The method for preparing the high-stability vanadium-based solid solution hydrogen storage alloy according to claim 8, characterized in that: When the trace additive selected in S102 is aluminum nitride powder, it is ball-milled using ultrasonic-assisted ball milling for 5 hours, with an ultrasonic power of 300W and a frequency of 40kHz.