A gallium-based low-freezing-point liquid alloy material and a preparation method thereof

Abstract

The application belongs to the technical field of liquid alloy materials, and discloses a gallium-based liquid alloy material with a low freezing point and a preparation method thereof.The liquid alloy material is composed of raw materials with the following mass fractions: 79-86 parts of gallium, 6-14 parts of indium, 3.5-6.0 parts of tin, 1-4.5 parts of zinc, 0-0.2 parts of copper, and 0-0.1 parts of silver.The application precisely focuses on the core demand of liquid cooling heat dissipation, and clearly distinguishes the melting point and the freezing point of the gallium-based alloy;for the application scene of the high-cold region as low as-40 DEG C, the alloy component distribution ratio is optimized, the product with a freezing temperature as low as-47 DEG C can be obtained, the lowest freezing point (-45.6 DEG C) of the prior art is further reduced, the application limitation of the liquid cooling coolant under the high-cold environment is effectively broken, the technical advantage is prominent, and the application is suitable for the heat dissipation demand of high-power equipment.

Description

Technical Field

[0001] This invention belongs to the field of liquid alloy technology, and specifically relates to a gallium-based liquid alloy material with a low freezing point and its preparation method. Background Technology

[0002] With the rapid development of new energy and artificial intelligence technologies, the demands on computing power and power density for high-power equipment such as data centers, outdoor energy storage cabinets, and outdoor supercharging piles are continuously increasing. The heat generated by their internal core chips increases dramatically during operation, making heat dissipation a key bottleneck restricting equipment performance and reliability. Especially in frigid regions such as Northwest and Northeast China, these devices face ambient temperatures approaching -40°C and must maintain uninterrupted, stable operation year-round, placing extremely stringent requirements on the thermal management system of the core chips.

[0003] Currently, liquid cooling solutions for core chips mainly include air cooling, liquid cooling, and phase change cooling. Among these, microchannel liquid cooling systems based on liquid coolants have become the mainstream technology due to their compact structure and high heat transfer efficiency. Existing commercial cooling media, such as deionized water / ethylene glycol aqueous solutions, fluorinated liquids, and mineral oils, generally have thermal conductivity in the low range of 0.06–0.6 W / m·K, resulting in inherent limitations in heat transfer efficiency. These materials are no longer sufficient to meet the long-term, efficient, and stable heat dissipation requirements of high-power chips in cold regions.

[0004] Compared to traditional coolants, liquid metal alloys, especially gallium-based liquid metals, have gradually become a new generation of coolants for thermal management of core chips in data centers, energy storage, and supercharging due to their high thermal conductivity, non-volatility, non-flammability, and non-toxicity. The thermal conductivity of gallium-based liquid metal alloys can reach 20-30 W / m·K, nearly two orders of magnitude higher than that of water and ethylene glycol. To broaden the flow temperature range, researchers have developed a series of low-melting-point gallium-based alloys. Currently, the developed gallium-based liquid metal alloy Galinstan has a melting point as low as -10°C. Literature reports that representative liquid metal alloys already on the market are composed of gallium, indium, and tin, with melting points as low as -19°C. However, in reality, due to supercooling, the measured melting point and freezing point of gallium-based alloys do not coincide during heating and cooling processes. For liquid alloys used as coolants, the loss of fluidity due to solidification caused by excessively low ambient temperatures is a major concern. Therefore, liquid metals with low freezing points have a greater advantage in this scenario. In most reports, the studies have not strictly distinguished between melting point and freezing point; for Galinstan, the reported phase transition temperature as low as -19°C is actually its freezing point temperature.

[0005] In recent years, researchers have reported some gallium-based alloys with freezing points below -20°C. However, for applications with higher heat dissipation requirements and more demanding environments, it is still necessary to explore alloy systems with even lower freezing points and develop preparation processes suitable for large-scale production. Patent "202110662282.1 A method for preparing a low-melting-point pentagonal gallium-based liquid alloy" uses gallium, indium, tin, zinc, and aluminum to react in an argon-protected graphite crucible at 700-750℃ to obtain a liquid alloy, with an initial solidification temperature of approximately -32℃. Patent "201510079410.4 A room-temperature liquid alloy with a low melting temperature, preparation process, and thermometer" discloses a liquid alloy composed of gallium, indium, tin, and silver, with a solidification point of approximately -40℃, requiring melting in a vacuum furnace at 900-1500℃ under 510-3 Pa. Patent "201910524309.3 Gallium-based liquid alloy, its preparation method and application, and temperature measuring device" discloses a pentagonal liquid alloy composed of gallium, indium, tin, zinc, iron, and sulfur, with an initial solidification temperature of -42.4-45.6℃. This alloy requires melting at a temperature not exceeding 5×10⁻⁶ Pa. -3 It is obtained by melting at 450℃-850℃ for 4-10 hours under vacuum conditions.

[0006] As the proportion of liquid metal components increases, the processes of lattice restructuring and alloying become more complex, and the requirements for preparation conditions become more stringent. Obtaining liquid alloys with extremely low freezing points, especially those below -40°C, that could potentially replace mercury, and achieving large-scale, low-energy production of such alloys under relatively mild conditions, remains a formidable challenge.

[0007] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0008] The purpose of this invention is to provide a gallium-based liquid alloy material with a low freezing point and its preparation method, thereby overcoming the defects in the prior art.

[0009] To achieve the above objectives, the present invention provides a gallium-based liquid alloy material with a low freezing point, which is composed of the following raw materials in parts by weight: 79-86 parts gallium, 6-14 parts indium, 3.5-6.0 parts tin, 1-4.5 parts zinc, 0-0.2 parts copper, and 0-0.1 parts silver.

[0010] Preferably, the purity of the gallium, indium, tin, zinc, copper, and silver elements is 99.9% or higher.

[0011] The present invention also provides a method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point, comprising the following steps: S1: Weigh out the elements gallium, indium, tin, zinc, copper, and silver according to their weight fractions, place them in a vacuum container, and add 0.1-0.5% of the total mass of the raw materials to the container as an ionic compound; S2: Evacuate the container to 0.03-0.1MPa, introduce argon gas and evacuate again. Repeat this process three times. Then fill the container with argon gas to 80-90% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55-65℃, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 20-40 minutes; then heat the material in the container to 115-125℃ and continue stirring for 2-3 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2-5 minutes, then place it in a cold trap to cool for 5-10 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0012] Preferably, the ionic compound in step S1 is one or a mixture of more than one of calcium chloride, sodium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, and 1-butyl-3-methylimidazolium tetrafluoroborate.

[0013] Preferably, the amount of ionic compound used in step S1 is 0.2-0.4%.

[0014] Preferably, in step S2, the container is evacuated to 0.05-0.08 MPa.

[0015] Preferably, the argon gas introduced in step S3 accounts for 85-88% of the container volume.

[0016] Preferably, the cold trap in step S4 is liquid nitrogen, a dry ice-acetone mixture, or a dry ice-ethanol mixture.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention precisely focuses on the core needs of liquid cooling heat dissipation, clearly distinguishing the melting point and solidification point of gallium-based alloys; for application scenarios in extremely cold regions with temperatures as low as -40°C, the alloy composition ratio is optimized to obtain products with a solidification temperature as low as -47.7°C, which is further reduced compared to the lowest solidification point of existing technologies (-45.6°C), effectively breaking through the application limitations of liquid coolants in extremely cold environments, with outstanding technical advantages, and adapting to the heat dissipation needs of high-power equipment; The present invention introduces low-melting-point ionic compounds during preparation, which solves the problems of complex lattice recombination and easy oxidation of active metals in existing multi-component gallium-based alloys. The added specific ionic compounds can destroy the lattice of the raw material metals and accelerate alloying, while inhibiting the oxidation of metals such as zinc, ensuring uniform alloy composition and stable performance. No additional antioxidants are required, which greatly simplifies the preparation process and improves preparation efficiency. This invention employs mild conditions of up to 115-125℃, combined with conventional equipment, and simplifies the process, reduces energy consumption and costs through the synergistic effect of segmented temperature-controlled stirring and cold trap cooling. It breaks through the limitations of existing processes and is easier to promote industrially. Attached Figure Description

[0018] Figures 1-10 The following are DSC curves of the liquid metals obtained in Examples 1-10. Detailed Implementation

[0019] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0020] The following provides a brief overview of one or more aspects to offer a basic understanding of them. This overview is not an exhaustive summary of all conceived aspects, nor is it intended to identify key or decisive elements of all aspects, nor to define the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form to prepare for the more detailed descriptions that follow.

[0021] Example 1: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 85 parts gallium, 6.4 parts indium, 4.8 parts tin, 3.8 parts zinc and 0.01 parts silver by weight, put them into a vacuum container, and add 0.4% sodium chloride and 0.1% calcium chloride by weight of the total raw material mass to the container. S2: Evacuate the container to 0.08 MPa, introduce argon gas, and then evacuate it again. Repeat this process three times. Then fill the container with argon gas that fills 80-85% of the container volume, and place the container in a silicone oil bath. S3: Heat the material in the container to 60°C while stirring until the solidified material in the container disappears, and continue stirring at this temperature for 30 minutes; then heat the material in the container to 120°C and continue stirring for 2.5 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 3 minutes, then place it in a cold trap to cool for 7 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0022] The solidification point of the obtained liquid alloy is -44.7℃.

[0023] Example 2: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 83.8 parts of gallium, 7.3 parts of indium, 4.8 parts of tin, 4 parts of zinc, 0.09 parts of copper and 0.01 parts of silver by weight fraction, put them into a vacuum container, and add 0.2% sodium chloride and 0.05% 1-butyl-3-methylimidazole chloride by weight fraction of the total raw material mass to the container. S2: Evacuate the container to 0.05 MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 20 minutes; then heat the material in the container to 120°C and continue stirring for 2.5 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2 minutes, then place it in a cold trap to cool for 5 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0024] The solidification point of the obtained liquid alloy is -47.7℃.

[0025] Example 3: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 83 parts of gallium, 6.4 parts of indium, 4.8 parts of tin, 3.95 parts of zinc and 0.05 parts of silver by weight fraction, put them into a vacuum container, and add 0.3% sodium chloride and 0.02% 1-butyl-3-methylimidazolium hexafluorophosphate by weight fraction of the total raw materials into the container. S2: Evacuate the container to 0.09 MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 65°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 20 minutes; then heat the material in the container to 120°C and continue stirring for 3 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 5 minutes, then place it in a cold trap to cool for 8 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0026] The solidification point of the obtained liquid alloy is -45.2℃.

[0027] Example 4: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 81.5 parts of gallium, 10.5 parts of indium, 3.4 parts of tin, 4.5 parts of zinc, 0.03 parts of copper, and 0.07 parts of silver by weight fraction, place them in a vacuum container, and add 0.2% calcium chloride and 0.05% 1-butyl-3-methylimidazolium tetrafluoroborate by weight fraction of the total raw materials to the container; S2: Evacuate the container to 0.05 MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 60°C while stirring until the solidified material in the container disappears, and continue stirring at this temperature for 25 minutes; then heat the material in the container to 120°C and continue stirring for 2.5 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2 minutes, then place it in a cold trap to cool for 10 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0028] The solidification point of the obtained liquid alloy is -45.7℃.

[0029] Example 5: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 86 parts of gallium, 6.4 parts of indium, 3.8 parts of tin, 3.63 parts of zinc, 0.08 parts of copper, and 0.02 parts of silver by weight fraction, place them in a vacuum container, and add 0.2% sodium chloride by weight of the total mass of the raw materials to the container. S2: Evacuate the container to 0.1MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas that fills 85% of the container volume and place the container in a silicone oil bath. S3: Heat the material in the container to 60°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 20 minutes; then heat the material in the container to 120°C and continue stirring for 3 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 3 minutes, then place it in a cold trap to cool for 8 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0030] The solidification point of the obtained liquid alloy is -46.2℃.

[0031] Example 6: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 85.2 parts of gallium, 7.0 parts of indium, 3.5 parts of tin, 4.23 parts of zinc, 0.1 parts of copper, and 0.01 parts of silver by weight, place them in a vacuum container, and add 0.25% calcium chloride and 0.03% 1-butyl-3-methylimidazole chloride by weight of the total raw material mass to the container; S2: Evacuate the container to 0.07 MPa, introduce argon gas and evacuate again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 40 minutes; then heat the material in the container to 120°C and continue stirring for 2.5 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2 minutes, then place it in a cold trap to cool for 6 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0032] The solidification point of the obtained liquid alloy is -45.5℃.

[0033] Example 7: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 85.4 parts of gallium, 6.7 parts of indium, 3.8 parts of tin, 3.94 parts of zinc, 0.15 parts of copper, and 0.04 parts of silver by weight, place them in a vacuum container, and add 0.2% sodium chloride by weight of the total mass of the raw materials to the container. S2: Evacuate the container to 0.09 MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 35 minutes; then heat the material in the container to 120°C and continue stirring for 2 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2 minutes, then place it in a cold trap to cool for 5 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0034] The solidification point of the obtained liquid alloy is -45.0℃.

[0035] Example 8: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 79 parts gallium, 13 parts indium, 5.5 parts tin, 2.3 parts zinc, 0.04 parts copper, and 0.1 parts silver by weight fraction, place them in a vacuum container, and add 0.3% sodium chloride and 0.02% 1-butyl-3-methylimidazole chloride by weight fraction of the total raw material mass to the container. S2: Evacuate the container to 0.06 MPa, introduce argon gas and evacuate again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 60°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 25 minutes; then heat the material in the container to 115°C and continue stirring for 3 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 3 minutes, then place it in a cold trap to cool for 3 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0036] The solidification point of the obtained liquid alloy is -40.7℃.

[0037] Example 9: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 80.5 parts of gallium, 11.2 parts of indium, 4.5 parts of tin, 3.52 parts of zinc, 0.2 parts of copper, and 0.08 parts of silver by weight fraction, place them in a vacuum container, and add 0.35% sodium chloride and 0.05% 1-butyl-3-methylimidazolium tetrafluoroborate by weight fraction of the total raw materials to the container; S2: Evacuate the container to 0.03 MPa, introduce argon gas and evacuate again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 60°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 25 minutes; then heat the material in the container to 125°C and continue stirring for 2 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 3 minutes, then place it in a cold trap to cool for 10 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0038] The solidification point of the obtained liquid alloy is -40.8℃.

[0039] Example 10: A method for preparing the above-mentioned gallium-based liquid alloy material with a low freezing point includes the following steps: S1: Weigh out 83.8 parts of gallium, 9.0 parts of indium, 6.0 parts of tin, 1 part of zinc, 0.15 parts of copper, and 0.01 parts of silver by weight, place them in a vacuum container, and add calcium chloride at 0.3% of the total mass of the raw materials to the container. S2: Evacuate the container to 0.04 MPa, introduce argon gas and then evacuate it again. Repeat this process three times. Then fill the container with argon gas to 85% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55°C, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 30 minutes; then heat the material in the container to 120°C and continue stirring for 2.5 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2 minutes, then place it in a cold trap to cool for 5 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

[0040] The solidification point of the obtained liquid alloy is -42.5℃.

[0041] Figures 1-10 The figures are DSC curves of the liquid metals obtained in Examples 1-10, where the peak temperature corresponds to the solidification point of the alloy material. The experimental results show that the raw material ratio and process of the present invention can obtain liquid metal alloy materials with low solidification points.

[0042] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A gallium-based liquid alloy material with a low freezing point, characterized in that, It is composed of the following raw materials in parts by weight: gallium 79-86 parts, indium 6-14 parts, tin 3.5-6.0 parts, zinc 1-4.5 parts, copper 0-0.2 parts, and silver 0-0.1 parts.

2. The gallium-based liquid alloy material with a low freezing point according to claim 1, characterized in that, The purity of the gallium, indium, tin, zinc, copper, and silver elements is all above 99.9%.

3. A method for preparing the low-freezing-point gallium-based liquid alloy material according to claim 1, characterized in that, Includes the following steps: S1: Weigh out the elements gallium, indium, tin, zinc, copper, and silver according to their weight fractions, place them in a vacuum container, and add 0.1-0.5% of the total mass of the raw materials to the container as an ionic compound; S2: Evacuate the container to 0.03-0.1 MPa, introduce argon gas and evacuate again. Repeat this process three times. Then fill the container with argon gas to 80-90% of its volume and place the container in a silicone oil bath. S3: Heat the material in the container to 55-65℃, stirring continuously until the solidified material in the container disappears, and continue stirring at this temperature for 20-40 minutes; then heat the material in the container to 115-125℃ and continue stirring for 2-3 hours. S4: Remove the container from the silicone oil bath, place it at room temperature for 2-5 minutes, then place it in a cold trap to cool for 5-10 minutes. Remove the container and wait for the product to melt at room temperature to obtain a gallium-based liquid alloy material with a low freezing point.

4. The method for preparing gallium-based liquid alloy materials with low freezing points according to claim 3, characterized in that, The ionic compound in step S1 is one or a mixture of more than one of calcium chloride, sodium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, and 1-butyl-3-methylimidazolium tetrafluoroborate.

5. The method for preparing gallium-based liquid alloy materials with low freezing points according to claim 3, characterized in that, The amount of ionic compound used in step S1 is 0.2-0.4%.

6. The method for preparing gallium-based liquid alloy materials with low freezing points according to claim 3, characterized in that, In step S2, the container is evacuated to 0.05-0.08 MPa.

7. The method for preparing gallium-based liquid alloy materials with low freezing points according to claim 3, characterized in that, In step S3, the argon gas introduced occupies 85-88% of the container volume.

8. The method for preparing gallium-based liquid alloy materials with low freezing points according to claim 2, characterized in that, In step S4, the cold trap is liquid nitrogen, a dry ice-acetone mixture, or a dry ice-ethanol mixture.

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