Vanadium-based solid solution hydrogen storage alloy with long cycle life and preparation method thereof

Abstract

The invention discloses a long-cycle-life vanadium-based solid solution hydrogen storage alloy and a preparation method thereof, and relates to the technical field of vanadium-based solid solution hydrogen storage alloys, the long-cycle-life vanadium-based solid solution hydrogen storage alloy comprises V, Cr, Ni and Co, the weight percentage of V: Cr: Ni: Co is a: b: c: d, the value range of a is 31-51, the value range of b is 9-29, the value range of c is 12-28, and the value range of d is 11-31. According to the vanadium-based solid solution hydrogen storage alloy with the long cycle life, under optimized composition and preparation process conditions, the cycle life of the vanadium-based solid solution hydrogen storage alloy is remarkably prolonged compared with that of a traditional hydrogen storage alloy, so that in the repeated charging and discharging cycle process, the alloy can keep good structural stability, pulverization and performance degradation are not prone to occurring, and the service life of the alloy is prolonged. And the performance requirements of energy storage devices such as nickel-metal hydride batteries in the long-term use process can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of vanadium-based solid solution hydrogen storage alloys, in particular to a vanadium-based solid solution hydrogen storage alloy with a long cycle life and a preparation method thereof. Background Art

[0002] As energy issues become increasingly prominent, hydrogen storage materials, as key media for energy storage and conversion, have crucial applications in numerous fields, including new energy vehicles and renewable energy storage. Nickel-metal hydride batteries, with their high energy density, long cycle life, and pollution-free properties, are widely used in various portable electronic devices, hybrid vehicles, and renewable energy storage systems.

[0003] Hydrogen storage alloys are a key core material in nickel-metal hydride batteries, and their properties directly impact the overall performance of the battery. Currently, a variety of common hydrogen storage alloy systems exist, including AB, AB2, and AB5. However, some existing hydrogen storage alloys still lack key performance indicators such as cycle life and hydrogen storage capacity, making it difficult to meet the growing demand for high-performance energy storage.

[0004] Therefore, it is necessary to propose a long cycle life vanadium-based solid solution hydrogen storage alloy and a preparation method thereof to solve the above problems. Summary of the Invention

[0005] The present invention aims to provide a vanadium-based solid solution hydrogen storage alloy with a long cycle life and a method for preparing the same. This addresses the problem that hydrogen storage alloys are a key core material in nickel-hydrogen batteries, whose performance directly impacts the overall performance of the battery. Currently, common hydrogen storage alloys include various systems, such as AB, AB2, and AB5. However, some existing hydrogen storage alloys still lack key performance indicators such as cycle life and hydrogen storage capacity, making it difficult to meet the growing demand for high-performance energy storage.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: a long cycle life vanadium-based solid solution hydrogen storage alloy, comprising vanadium (V), chromium (Cr), nickel (Ni), and cobalt (Co), with a weight percentage of V:Cr:Ni:Co=a:b:c:d, wherein a ranges from 31 to 51, b ranges from 9 to 29, c ranges from 12 to 28, d ranges from 11 to 31, and a+b+c+d=100.

[0007] Preferably, the hydrogen storage alloy also includes trace additive elements, and the trace additive elements include one or more of zirconium (Zr), titanium (Ti), niobium (Nb), tantalum (Ta), molybdenum (Mo), and tungsten (W), and their total content does not exceed 5% of the total weight of the hydrogen storage alloy.

[0008] Preferably, the particle size of the hydrogen storage alloy is in the range of 10 to 100 μm.

[0009] Preferably, the grain size of the hydrogen storage alloy is in the range of 0.1 to 1 μm.

[0010] The present invention also discloses a method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life, which is applied to prepare the above-mentioned vanadium-based solid solution hydrogen storage alloy with a long cycle life, and further comprises the following steps:

[0011] S1. Pretreatment: Dry, degrease and remove impurities of vanadium, chromium, nickel and cobalt raw materials respectively;

[0012] S2. Melting: placing the pretreated raw materials in a non-consumable vacuum induction melting furnace and melting them under an argon protective atmosphere to obtain a vanadium-based solid solution hydrogen storage alloy melt;

[0013] S3, ingot casting: casting the vanadium-based solid solution hydrogen storage alloy melt into a casting mold, and obtaining a vanadium-based solid solution hydrogen storage alloy ingot after cooling;

[0014] S4, crushing: crushing the vanadium-based solid solution hydrogen storage alloy ingot using a crushing device, and then performing a ball milling process to obtain a vanadium-based solid solution hydrogen storage alloy powder;

[0015] S5. Heat treatment: placing the vanadium-based solid solution hydrogen storage alloy powder in an argon protective atmosphere for heat treatment to obtain a vanadium-based solid solution hydrogen storage alloy with a long cycle life.

[0016] Preferably, the crushing equipment includes a processing box installed on the frame, two crushing rollers that cooperate with each other are rotatably provided on the processing box, the top of the processing box is connected to a feed box, a stacking barrel is provided above the feed box, the bottom end of the stacking barrel is connected to a dispersion hopper, and the bottom end of the dispersion hopper faces the junction of the two crushing rollers, and the stacking barrel drives the dispersion hopper to move back and forth along the axis of the crushing roller, and at the same time swing back and forth up and down.

[0017] Preferably, a slide groove is provided on the outer walls of both sides of the stacking barrel, and a slide seat is slidingly provided inside the slide groove, one of the slide seats is slidably connected to a guide rod, and the guide rod is fixedly provided on the feed box, and the other slide seat is matched with a reciprocating screw, and the reciprocating screw is rotatably provided on the feed box, and cross bars are fixedly connected to the outer walls of both sides of the stacking barrel, and corrugated plates are fixedly connected to the tops of both sides of the feed box, and the cross bars cooperate with the corresponding corrugated plates.

[0018] Preferably, elastic components are provided at both upper and lower ends of the slide, and the elastic components include a support block and an elastic telescopic rod. The support block is fixedly connected to the outer wall of the stacking barrel, one end of the elastic telescopic rod is fixedly connected to the support block, and the other end of the elastic telescopic rod is fixedly connected to the slide.

[0019] Preferably, a gear is fixedly connected to the crushing roller, and the two gears are meshed and connected. A transmission assembly is provided between one of the crushing rollers and the reciprocating screw. The transmission assembly includes a first pulley, a second pulley and a belt. The first pulley is fixedly connected to the crushing roller, and the second pulley is fixedly connected to the reciprocating screw. The first pulley and the second pulley are connected by belt transmission.

[0020] Preferably, elastic plates are fixedly connected to both sides of the dispersion hopper, the bottom ends of the two elastic plates are close to each other, and the two elastic plates are distributed in a one-to-one correspondence with the two crushing rollers.

[0021] Technical effects and advantages of the present invention:

[0022] 1. Under optimized composition and preparation process conditions, the vanadium-based solid solution hydrogen storage alloy of the present invention has a significantly improved cycle life compared to traditional hydrogen storage alloys. This allows the alloy to maintain good structural stability during repeated charge and discharge cycles, is less susceptible to pulverization and performance degradation, and can meet the performance requirements of energy storage devices such as nickel-hydrogen batteries during long-term use.

[0023] 2. The present invention realizes uniform feeding by providing a stacking barrel, a dispersion hopper and other structures, ensuring that the vanadium-based solid solution hydrogen storage alloy ingot is fully crushed, and the crushing roller can participate in the crushing as a whole; at the same time, the reciprocating feeding can avoid excessive accumulation of the vanadium-based solid solution hydrogen storage alloy ingot on the crushing roller, reduce the load pressure of the crushing roller, and improve the preparation efficiency of the vanadium-based solid solution hydrogen storage alloy;

[0024] 3. By setting up structures such as cross bars and wave plates, the stacking barrel and dispersion bucket can be made to swing back and forth up and down, thus avoiding blockage and ensuring feeding efficiency.

[0025] 4. When the vanadium-based solid solution hydrogen storage alloy ingot slides from the bottom of the dispersion hopper to the junction of the two crushing rollers, the elastic plate can slow down and buffer, reducing the impact force with the crushing rollers. At the same time, the bottom ends of the two elastic plates move closer to each other, ensuring that the vanadium-based solid solution hydrogen storage alloy ingot fully falls at the junction of the two crushing rollers, thereby improving the crushing efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Flow chart of the preparation method of the long cycle life vanadium-based solid solution hydrogen storage alloy of the present invention

[0027] Figure 2 This is a structural schematic diagram of the crushing equipment from one perspective of the present invention.

[0028] Figure 3 For the present invention Figure 2 A magnified schematic diagram of the structure in the middle.

[0029] Figure 4 This is a schematic structural diagram of the crushing equipment from another perspective of the present invention.

[0030] Figure 5 For the present invention Figure 4 A magnified schematic diagram of the structure at point B in the middle.

[0031] Figure 6 It is a schematic diagram of the structure of the feed box and dispersion hopper of the present invention.

[0032] Figure 7 For the present invention Figure 6 Enlarged schematic diagram of the structure at point C in the middle.

[0033] In the figure: 1. frame; 2. processing box; 3. feed box; 4. stacking barrel; 5. dispersion hopper; 6. crushing roller; 7. gear; 8. first pulley; 9. second pulley; 10. belt; 11. reciprocating screw; 12. guide rod; 13. slide; 14. slide; 15. support block; 16. elastic telescopic rod; 17. cross bar; 18. corrugated plate; 19. discharge hopper; 20. motor; 21. elastic plate. DETAILED DESCRIPTION

[0034] The present invention provides Figures 1 to 7 The long cycle life vanadium-based solid solution hydrogen storage alloy shown includes vanadium (V), chromium (Cr), nickel (Ni), and cobalt (Co), and the weight percentage is V:Cr:Ni:Co=a:b:c:d, where the value range of a is 31 to 51, the value range of b is 9 to 29, the value range of c is 12 to 28, the value range of d is 11 to 31, and a+b+c+d=100.

[0035] Example 1, V:Cr:Ni:Co=40:20:20:20.

[0036] Example 2, V:Cr:Ni:Co=35:15:25:25.

[0037] The hydrogen storage alloy (i.e., long cycle life vanadium-based solid solution hydrogen storage alloy) also includes trace additive elements, which include one or more of zirconium (Zr), titanium (Ti), niobium (Nb), tantalum (Ta), molybdenum (Mo), and tungsten (W), and their total content does not exceed 5% of the total weight of the hydrogen storage alloy.

[0038] The particle size of the hydrogen storage alloy ranges from 10 to 100 μm.

[0039] The grain size of the hydrogen storage alloy ranges from 0.1 to 1 μm.

[0040] The present invention also discloses a method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life, which is applied to prepare the above-mentioned vanadium-based solid solution hydrogen storage alloy with a long cycle life, and further comprises the following steps:

[0041] S1. Pretreatment: Select vanadium, chromium, nickel and cobalt raw materials with a purity of not less than 99.6%, and carry out drying, degreasing and impurity removal treatment respectively to remove impurities and oil stains on the surface of the raw materials, ensure the smooth progress of the subsequent smelting process, and improve the purity and performance stability of the alloy;

[0042] S2. Melting: The pre-treated vanadium, chromium, nickel, and cobalt raw materials are mixed according to the preset weight percentages and placed in a non-consumable vacuum induction melting furnace for melting under an argon atmosphere. The melting temperature is controlled at 1450-1750°C for 11-29 minutes to obtain a vanadium-based solid solution hydrogen storage alloy melt, preventing the alloy from oxidation and nitridation, and ensuring the chemical composition and properties of the alloy.

[0043] S3. Ingot casting: The vanadium-based solid solution hydrogen storage alloy melt obtained by smelting is cast into a mold preheated to 180-360°C, and after cooling, a vanadium-based solid solution hydrogen storage alloy ingot is obtained. Preheating the mold helps control the solidification process of the alloy, reduce the generation of internal stress and defects, and improve the density and uniformity of the alloy;

[0044] S4. Crushing: The vanadium-based solid solution hydrogen storage alloy ingot is crushed by crushing equipment, and then subjected to ball milling to obtain vanadium-based solid solution hydrogen storage alloy powder. By combining the crushing process with the ball milling process, the alloy block material can be gradually crushed and ground to a desired particle size range, providing alloy powder of suitable particle size for subsequent heat treatment and battery production, while also facilitating sufficient contact between the alloy and the electrolyte, thereby improving the efficiency of the hydrogen storage reaction;

[0045] S5. Heat treatment: The vanadium-based solid solution hydrogen storage alloy powder is placed in an argon protective atmosphere for heat treatment at a temperature of 450-750°C for 0.8-4.5 hours. After heat preservation, the powder is cooled to room temperature with the furnace to obtain a vanadium-based solid solution hydrogen storage alloy with a long cycle life. The heat treatment process can eliminate the internal stress generated by the alloy during the crushing process, improve the crystal structure of the alloy, promote the formation and improvement of the solid solution, and improve the hydrogen storage activity and cycle stability of the alloy.

[0046] Under optimized composition and preparation process conditions, the vanadium-based solid solution hydrogen storage alloy in the present invention has a significantly improved cycle life compared to traditional hydrogen storage alloys, so that during repeated charge and discharge cycles, the alloy can maintain good structural stability and is not prone to pulverization and performance degradation, thus meeting the performance requirements of energy storage devices such as nickel-hydrogen batteries during long-term use.

[0047] The crushing equipment includes a processing box 2 mounted on a frame 1. Two mutually cooperating crushing rollers 6 are rotatably mounted on the processing box 2, one on the left and one on the right. Gears 7 are fixedly connected to the crushing rollers 6, and the two gears 7 are meshed. A motor 20 is mounted on the processing box 2, with one crushing roller 6 fixedly connected to the drive shaft of the motor 20. When the motor 20 operates, it rotates the crushing roller 6, which is fixedly connected to its drive shaft. Due to the meshing connection of the two gears 7, the other crushing roller 6 also rotates, thereby crushing the material (vanadium-based solid solution hydrogen storage alloy ingot).

[0048] The top of the processing box 2 is connected to the feed box 3, and the bottom of the processing box 2 is connected to the discharge hopper 19. The feed box 3 is used for loading, and the discharge hopper 19 is used for discharging.

[0049] Taking into account the existing technology, the vanadium-based solid solution hydrogen storage alloy ingot is usually poured directly into the interior of the feed box 3 as a whole, which will bring a large load to the crushing roller 6 and increase wear; at the same time, some positions on the crushing roller 6 are always in use, while some positions are difficult to participate in crushing, the wear is uneven, and the crushing roller 6 needs to be replaced according to the position with faster wear, thereby shortening the service life of the crushing roller 6. In order to ensure the uniformity of crushing, a stacking barrel 4 is provided above the feed box 3, and the bottom end of the stacking barrel 4 is connected to a dispersion hopper 5, and the bottom end of the dispersion hopper 5 faces the junction of the two crushing rollers 6, and the material is directly loaded to the junction of the two crushing rollers 6, which can ensure the efficiency of crushing.

[0050] A slide groove 13 is provided on the outer walls of both sides of the stacking barrel 4, and a slide seat 14 is provided inside the slide groove 13 for sliding. In actual use, balls or the like can be provided between the slide seat 14 and the inner wall of the slide groove 13 to improve the smoothness of the slide seat 14 sliding inside the slide groove 13.

[0051] A guide rod 12 is slidably connected to one of the slides 14, and the guide rod 12 is fixedly set on the feed box 3. The other slide 14 is equipped with a reciprocating screw 11, and the reciprocating screw 11 is rotatably set on the feed box 3. Elastic components are provided at the upper and lower ends of the slide 14, and the elastic components include a support block 15 and an elastic telescopic rod 16. The support block 15 is fixedly connected to the outer wall of the stacking barrel 4. One end of the elastic telescopic rod 16 is fixedly connected to the support block 15, and the other end of the elastic telescopic rod 16 is fixedly connected to the slide 14. The elastic telescopic rod 16 has appropriate strength.

[0052] A transmission assembly is provided between one of the crushing rollers 6 and the reciprocating screw 11. The transmission assembly includes a first pulley 8, a second pulley 9 and a belt 10. The first pulley 8 is fixedly connected to the crushing roller 6, and the second pulley 9 is fixedly connected to the reciprocating screw 11. The first pulley 8 and the second pulley 9 are connected by a belt 10.

[0053] The present invention is provided with a stacking barrel 4, a dispersion bucket 5 and other structures. When actually used, the motor 20 is started, and the motor 20 drives the crushing roller 6 fixedly connected to its drive shaft to rotate. Since the two gears 7 are engaged and connected, the other crushing roller 6 also rotates, and the vanadium-based solid solution hydrogen storage alloy ingot can be crushed.

[0054] The corresponding crushing roller 6 drives the first pulley 8 to rotate. Since the first pulley 8 is connected to the second pulley 9 by a belt 10, the second pulley 9 drives the reciprocating screw 11 to rotate, and with the cooperation of the guide rod 12, the stacking barrel 4 drives the dispersion bucket 5 to move back and forth along the axial direction of the crushing roller 6, and directly loads the material to the junction of the two crushing rollers 6 to achieve uniform loading, ensure that the vanadium-based solid solution hydrogen storage alloy ingot is fully crushed, and the crushing roller 6 can participate in the crushing as a whole; at the same time, the reciprocating loading can avoid excessive accumulation of the vanadium-based solid solution hydrogen storage alloy ingot on the crushing roller 6, reduce the load pressure of the crushing roller 6, and thus improve the preparation efficiency of the vanadium-based solid solution hydrogen storage alloy.

[0055] At the same time, cross bars 17 are fixedly connected to the outer walls of both sides of the stacking barrel 4, and corrugated plates 18 are fixedly connected to the tops of both sides of the feed box 3, and the cross bars 17 cooperate with the corresponding corrugated plates 18.

[0056] When the stacking barrel 4 drives the dispersion bucket 5 to reciprocate along the axial direction of the crushing roller 6, and with the cooperation of the elastic components at the upper and lower ends of the slide 14, when the cross bar 17 contacts the high point of the wave plate 18, the stacking barrel 4 swings upward, the elastic telescopic rod 16 at the upper end contracts, and the elastic telescopic rod 16 at the lower end extends; and when the cross bar 17 contacts the low point of the wave plate 18, the stacking barrel 4 swings downward, the elastic telescopic rod 16 at the upper end extends, and the elastic telescopic rod 16 at the lower end contracts, thereby achieving the effect of reciprocating up and down swinging of the stacking barrel 4 and the dispersion bucket 5, avoiding blockage and ensuring feeding efficiency.

[0057] Elastic plates 21 are fixedly connected to both sides of the dispersion hopper 5. The bottom ends of the two elastic plates 21 are close together, and the two elastic plates 21 are arranged in a one-to-one correspondence with the two crushing rollers 6. When the vanadium-based solid solution hydrogen storage alloy ingot slides from the bottom of the dispersion hopper 5 to the intersection of the two crushing rollers 6, the elastic plates 21 can slow down and buffer it, reducing the impact force on the crushing rollers 6. At the same time, the bottom ends of the two elastic plates 21 are close together, ensuring that the vanadium-based solid solution hydrogen storage alloy ingot lands fully at the intersection of the two crushing rollers 6, improving crushing efficiency.

Claims

1. Long cycle life vanadium-based solid solution hydrogen storage alloy, characterized by: The invention comprises V, Cr, Ni and Co, and the weight percentage is V:Cr:Ni:Co=a:b:c:d, wherein the value range of a is 31 to 51, the value range of b is 9 to 29, the value range of c is 12 to 28, the value range of d is 11 to 31, and a+b+c+d=100.

2. The vanadium-based solid solution hydrogen storage alloy with long cycle life according to claim 1, characterized in that: The hydrogen storage alloy further comprises trace additive elements, which include one or more of Zr, Ti, Nb, Ta, Mo, and W, and the total content of the trace additive elements does not exceed 5% of the total weight of the hydrogen storage alloy.

3. The vanadium-based solid solution hydrogen storage alloy with long cycle life according to claim 1, characterized in that: The particle size of the hydrogen storage alloy ranges from 10 to 100 μm.

4. The vanadium-based solid solution hydrogen storage alloy with long cycle life according to claim 1, characterized in that: The grain size of the hydrogen storage alloy is in the range of 0.1 to 1 μm.

5. A method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life, characterized in that: The method is applied to prepare the vanadium-based solid solution hydrogen storage alloy with a long cycle life as claimed in any one of claims 1 to 4, further comprising the following steps: S1. Pretreatment: Dry, degrease and remove impurities of vanadium, chromium, nickel and cobalt raw materials respectively; S2. Melting: placing the pretreated raw materials in a non-consumable vacuum induction melting furnace and melting them under an argon protective atmosphere to obtain a vanadium-based solid solution hydrogen storage alloy melt; S3, ingot casting: casting the vanadium-based solid solution hydrogen storage alloy melt into a casting mold, and obtaining a vanadium-based solid solution hydrogen storage alloy ingot after cooling; S4, crushing: crushing the vanadium-based solid solution hydrogen storage alloy ingot using a crushing device, and then performing a ball milling process to obtain a vanadium-based solid solution hydrogen storage alloy powder; S5. Heat treatment: placing the vanadium-based solid solution hydrogen storage alloy powder in an argon protective atmosphere for heat treatment to obtain a vanadium-based solid solution hydrogen storage alloy with a long cycle life.

6. The method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life according to claim 5, characterized in that: The crushing equipment includes a processing box (2) installed on a frame (1), two mutually cooperating crushing rollers (6) are rotatably provided on the processing box (2), the top of the processing box (2) is connected to a feed box (3), a stacking barrel (4) is provided above the feed box (3), the bottom end of the stacking barrel (4) is connected to a dispersion hopper (5), and the bottom end of the dispersion hopper (5) faces the junction of the two crushing rollers (6), and the stacking barrel (4) drives the dispersion hopper (5) to move back and forth along the axial direction of the crushing roller (6) and to swing back and forth up and down at the same time.

7. The method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life according to claim 6, characterized in that: The outer walls of both sides of the stacking barrel (4) are provided with a slide groove (13), and a slide seat (14) is slidably provided inside the slide groove (13), one of the slide seats (14) is slidably connected to a guide rod (12), and the guide rod (12) is fixedly provided on the feed box (3), and the other slide seat (14) is matched with a reciprocating screw (11), and the reciprocating screw (11) is rotatably provided on the feed box (3), and the outer walls of both sides of the stacking barrel (4) are fixedly connected with a cross bar (17), and the tops of both sides of the feed box (3) are fixedly connected with a wave plate (18), and the cross bar (17) is matched with the corresponding wave plate (18).

8. The method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life according to claim 7, wherein: The upper and lower ends of the slide (14) are both provided with elastic components, and the elastic components include a support block (15) and an elastic telescopic rod (16). The support block (15) is fixedly connected to the outer wall of the stacking barrel (4), one end of the elastic telescopic rod (16) is fixedly connected to the support block (15), and the other end of the elastic telescopic rod (16) is fixedly connected to the slide (14).

9. The method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life according to claim 7, wherein: A gear (7) is fixedly connected to the crushing roller (6), and the two gears (7) are meshed and connected. A transmission assembly is provided between one of the crushing rollers (6) and the reciprocating screw (11). The transmission assembly comprises a first pulley (8), a second pulley (9) and a belt (10). The first pulley (8) is fixedly connected to the crushing roller (6), and the second pulley (9) is fixedly connected to the reciprocating screw (11). The first pulley (8) and the second pulley (9) are connected by a belt (10).

10. The method for preparing a vanadium-based solid solution hydrogen storage alloy with a long cycle life according to claim 6, characterized in that: Both sides of the dispersion hopper (5) are fixedly connected with elastic plates (21), the bottom ends of the two elastic plates (21) are close to each other, and the two elastic plates (21) are distributed in a one-to-one correspondence with the two crushing rollers (6).

Images