Preparation method of high-temperature and high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material

Abstract

This invention discloses a high-temperature, high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material and its preparation method. The Ti-Zr-Hf-Ni-Cu alloy involved in this invention is a solid-solid phase change energy storage material based on a high-entropy shape memory alloy, belonging to the fields of high-entropy shape memory alloys, energy storage, and thermal management technology. The main content of the high-entropy shape memory alloy in this invention is: Ti: 25 ≤ x ≤30at.%; Zr:5≤ y ≤15at.%; Ni:28≤ a ≤35at.%; Cu:10≤ b ≤15at.%; n+m=100; This invention discloses a high-temperature, high-performance Ti-Zi-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material, which has a high phase change temperature, and its phase change temperature can be precisely adjusted in a wide temperature range by composition control. According to calculations, the FOM of this type of alloy is 20 times higher than that of currently commercially available high-temperature solid-liquid phase change materials. In addition, this type of alloy exhibits high thermal conductivity and can be used for transient thermal management of high-power electronic components.

Description

Technical Field

[0001] This invention belongs to the fields of high-entropy shape memory alloys, energy storage and thermal management technology. Specifically, it relates to a high-temperature high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material and its preparation method. Background Technology

[0002] With the development of the times, people's demand for energy is constantly increasing. The continuous development and utilization of non-renewable energy sources has not only exacerbated the energy crisis but also triggered a series of environmental problems. To achieve sustainable socio-economic development, the search for new renewable energy sources has become a research hotspot in today's society. However, most renewable energy sources are unstable and cannot meet the demand for a continuous and stable energy supply. Energy storage technology is a thermal energy storage technology that has developed rapidly alongside the development and utilization of renewable energy. It is worth noting that thermal energy storage can not only solve the mismatch between supply and demand of renewable energy but also improve energy utilization efficiency, showing great application prospects in solar energy utilization, industrial waste heat and residual heat recovery, and thermal management of high-power electronic components.

[0003] Energy storage technologies can be broadly categorized into three types: sensible heat energy storage, latent heat energy storage, and chemical reaction energy storage. Sensible heat energy storage utilizes the ability of materials to absorb energy at high temperatures. However, this type of energy storage has low energy density, requires large-scale devices, and experiences significant temperature fluctuations during storage. Chemical reaction energy storage utilizes the heat of reaction generated during reversible chemical reactions. This method is technically complex, has poor operability, and faces significant challenges in practical applications. Latent heat energy storage utilizes the energy absorption or release characteristics of phase change materials during phase transitions. Compared to other energy storage forms, latent heat energy storage devices are simpler, have higher energy density, and exhibit smaller temperature fluctuations. Therefore, latent heat energy storage technology has become the most researched area of ​​focus in current thermal energy storage technologies.

[0004] Phase change materials (PCMs) are crucial for latent heat energy storage systems. PCMs are media that possess both thermal energy storage and bidirectional temperature regulation capabilities, absorbing energy from solar energy, industrial waste heat, and other sources, and releasing this energy when needed. Based on the type of phase change, they can be classified as: solid-solid PCMs, solid-liquid PCMs, and solid-gas PCMs. Solid-liquid PCMs absorb heat and change from a solid to a liquid state when the temperature is above the phase change temperature; when the temperature is below the phase change temperature, the material releases energy and reverts to a solid state. Solid-liquid PCMs suffer from drawbacks such as easy leakage and corrosion of encapsulation materials when in the liquid phase. In contrast, solid-solid PCMs offer advantages such as non-corrosiveness, low supercooling, no need for encapsulation, and no phase separation.

[0005] With the continuous development of the energy and information industries, advanced sustainable energy storage and high-power electronic thermal management urgently require phase change materials with phase change temperatures above 200℃. For example, industrial waste heat recovery requires phase change temperatures above 200℃, while integrated solar power generation and AlGaN / GaN integrated circuits operate at temperatures of 250-750℃. Although some high-temperature molten salts have been used in high-temperature thermal energy storage systems, molten salts can corrode pipes and containers under high-temperature conditions, posing a risk of liquid phase leakage. Therefore, exploring solid-solid phase change materials with efficient thermal energy storage performance at high temperatures has become an imperative trend. Summary of the Invention

[0006] To address the above deficiencies, this invention provides a high-temperature, high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material and its preparation method.

[0007] A high-temperature, high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material has the following composition: Ti:25≤ x ≤30at.%; Zr:5≤ y ≤15at.%; Ni:28≤ a ≤35at.%; Cu:10≤ b ≤15at.%; n+m=100.

[0008] Furthermore, the preparation method of the Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material is as follows:

[0009] Step 1, according to Weigh out the high-purity raw materials according to the specified proportions;

[0010] Step 2: The weighed raw materials are melted in a non-consumable high-vacuum electric arc melting furnace. The raw materials are melted at least six times, each time for three minutes to ensure uniform composition. High-purity argon is used as a protective atmosphere throughout the melting process.

[0011] Step 3: Seal the ingot obtained from the melting process in Step 2 into a quartz tube filled with argon gas;

[0012] Step 4: Place the sealed quartz tube from Step 3 into a box-type heat treatment furnace and hold it at 1000℃ for 48 hours. Then, perform ice water quenching treatment. The quenched button ingot is the target alloy.

[0013] Furthermore, the preparation method of the Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material is as follows:

[0014] Step 1, according to Weigh out the high-purity raw materials according to the specified proportions;

[0015] Step 2: The weighed raw materials are melted in a non-consumable high-vacuum electric arc melting furnace. The raw materials are melted four times, each time for three minutes and magnetically stirred for two minutes to ensure uniform composition. High-purity argon is used as a protective atmosphere throughout the melting process.

[0016] Step 3: Seal the ingot obtained from the melting process in Step 2 into a quartz tube filled with argon gas;

[0017] Step 4: Place the sealed quartz tube from Step 3 into a box-type heat treatment furnace and hold it at 1000℃ for 48 hours. Then, perform ice water quenching treatment. The quenched button ingot is the target alloy.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] This invention discloses a high-temperature, high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material. This material exhibits a high phase transition temperature, which can be precisely adjusted over a wide temperature range through composition control. Calculations show that the Form of Measuring (FOM) of this alloy is 20 times higher than that of currently commercially available high-temperature solid-liquid phase change materials (e.g.,...). Figure 11 (As shown). In addition, this type of alloy exhibits high thermal conductivity, which can be used for transient thermal management of high-power electronic components. Attached Figure Description

[0020] Figure 1 In this invention Photograph of high-entropy shape memory alloy solid-solid phase change thermal storage material.

[0021] Figure 2 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0022] Figure 3 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0023] Figure 4 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0024] Figure 5 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0025] Figure 6 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0026] Figure 7 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0027] Figure 8 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0028] Figure 9 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0029] Figure 10 In this invention DSC curves of high-entropy shape memory alloy solid-solid phase change thermal storage materials.

[0030] Figure 11 This is a comparison of the FOM and phase transition temperature of typical SS-PCMs and high-temperature SL-PCMs in this invention. Detailed Implementation

[0031] To facilitate understanding of the present invention, the apparatus of the present invention will now be described more fully with reference to the accompanying drawings. Embodiments of the apparatus are shown in the drawings. However, the apparatus can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to make the disclosure of the present invention more thorough and complete.

[0032] Example 1

[0033] This embodiment provides a high-temperature, high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material with the following composition: Ti:25≤ x ≤30at.%; Zr:5≤ y ≤15at.%; Ni:28≤ a ≤35at.%; Cu:10≤ b ≤15at.%; n+m=100, where n=x+y+20, m=a+b, that is, n represents the sum of the atomic percentages of Ti, Zr and Hf, and m represents the sum of the atomic percentages of Ni and Cu.

[0034] Its preparation method is as follows:

[0035] Step 1, according to Weigh out the high-purity raw materials according to the specified proportions;

[0036] Step 2: The weighed raw materials are melted in a non-consumable high-vacuum electric arc melting furnace. The raw materials are melted at least six times, each time for three minutes to ensure uniform composition. High-purity argon is used as a protective atmosphere throughout the melting process.

[0037] Step 3: Seal the ingot obtained from the melting process in Step 2 into a quartz tube filled with argon gas.

[0038] Step 4: Place the sealed quartz tube from Step 3 into a box-type heat treatment furnace and hold it at 1000℃ for 48 hours, followed by ice-water quenching. The quenched button ingot is the target alloy.

[0039] The DSC measurement curve of the alloy obtained by the above process is as follows: Figure 2 As shown: Phase transition temperature Af = 307℃, latent heat of phase transition ,density Thermal conductivity is .

[0040] Example 2

[0041] The preparation methods of Example 2 and Example 1 differ as follows:

[0042] Step 1, according to Weigh out the high-purity raw materials according to the specified proportions;

[0043] Step 2: The weighed raw materials are melted in a non-consumable high-vacuum electric arc melting furnace. The raw materials are melted four times, each time for three minutes and magnetically stirred for two minutes to ensure uniform composition. High-purity argon is used as a protective atmosphere throughout the melting process.

[0044] Step 3: Seal the ingot obtained from the melting process in Step 2 into a quartz tube filled with argon gas.

[0045] Step 4: Place the sealed quartz tube from Step 3 into a box-type heat treatment furnace and hold it at 1000℃ for 48 hours, followed by ice-water quenching. The quenched button ingot is the target alloy.

[0046] The DSC measurement curve of the alloy obtained by the above process is as follows: Figure 9 As shown: Phase transition temperature Af = 339℃, latent heat of phase transition ,density Thermal conductivity is .

[0047] Example 3

[0048] The Ti29Zr6Hf20Ni35Cu10 alloy was prepared using the same preparation method as in Example 1. Its performance parameters are: phase transformation temperature Af = 326℃, latent heat of phase transformation... ,density Thermal conductivity is Its DSC curve is as follows Figure 3 As shown.

[0049] Example 4

[0050] Prepared using the same preparation method as in Example 1 Alloy, with the following properties: phase transformation temperature Af = 349℃, latent heat of phase transformation ,density Thermal conductivity is Its DSC curve is as follows Figure 4 As shown.

[0051] Example 5

[0052] Prepared using the same preparation method as in Example 1 Alloy. Its performance parameters: phase transformation temperature Af = 366℃, latent heat of phase transformation ,density Thermal conductivity is Its DSC curve is as follows Figure 5 As shown.

[0053] Example 6

[0054] Prepared using the same preparation method as in Example 1 Alloy. Its performance parameters: phase transformation temperature Af = 413℃, latent heat of phase transformation ,density Thermal conductivity is Its DSC curve is as follows Figure 6 As shown.

[0055] Example 7

[0056] Prepared using the same preparation method as in Example 1 Alloy. Its performance parameters: phase transformation temperature Af = 449℃, latent heat of phase transformation... ,density Thermal conductivity is Its DSC curve is as follows Figure 7 As shown.

[0057] Example 8

[0058] Prepared using the same preparation method as in Example 1 Alloy. Its performance parameters: phase transformation temperature Af = 469℃, latent heat of phase transformation ,density Thermal conductivity is Its DSC curve is as follows Figure 8 As shown.

[0059] Example 9

[0060] Prepared using the same preparation method as in Example 2 Alloy. Its performance parameters: phase transformation temperature Af = 476℃, latent heat of phase transformation ,density Thermal conductivity is Its DSC curve is as follows Figure 10 As shown.

[0061] It should be noted that the phase transformation temperature in the above embodiments is related to the elements and composition of the alloy, and the phase transformation temperature is controlled by composition adjustment.

[0062] It should be noted that the structure described in this invention can be implemented in many different forms and is not limited to the embodiments described. Any equivalent transformations made by those skilled in the art based on the description and drawings of this invention, or direct or indirect applications in other related technical fields, such as the loading and unloading of other items, are included within the protection scope of this invention.

Claims

1. A high temperature high performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase transition energy storage material, characterized in that: The composition of the Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase transition energy storage material is as follows: ; Ti: 25≤x≤30 at.%; Zr: 5≤y≤15 at.%; Ni: 28≤a≤35 at.%; Cu: 10≤b≤15 at.%; n+m=100, n=x+y+20, m=a+b, that is, n represents the sum of the atomic percentages of Ti, Zr and Hf, and m represents the sum of the atomic percentages of Ni and Cu.

2. The preparation method of high-temperature and high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material according to claim 1, characterized in that: The preparation method of the Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material is: Step one, according to High purity raw materials are weighed in proportion; Step two, the weighed raw materials are melted by using a non-consumable high vacuum arc melting furnace, the raw materials are melted for at least six times, each time for three minutes to ensure uniformity of the components, and high-purity argon is used as a protective atmosphere during the whole melting process; Step three, the ingot obtained by melting in step two is sealed in a quartz tube filled with argon; Step four, the sealed quartz tube in step three is placed in a box-type heat treatment furnace and heat treated at 1000 DEG C for 48 hours, and then subjected to ice water quenching treatment, and the button ingot after quenching is the target alloy.

3. The preparation method of high-temperature and high-performance Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material according to claim 1, characterized in that: The preparation method of the Ti-Zr-Hf-Ni-Cu high-entropy shape memory alloy solid-solid phase change energy storage material is: Step one, according to High purity raw materials are weighed in proportion; Step two, the weighed raw materials are melted by using a non-consumable high vacuum arc melting furnace, the raw materials are melted for at least six times, each time for three minutes to ensure uniformity of the components, and high-purity argon is used as a protective atmosphere during the whole melting process; Step three, the ingot obtained by melting in step two is sealed in a quartz tube filled with argon; Step four, the sealed quartz tube in step three is placed in a box-type heat treatment furnace and heat treated at 1000 DEG C for 48 hours, and then subjected to ice water quenching treatment, and the button ingot after quenching is the target alloy.

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