Shaped phase change thermal management material as well as preparation method and application thereof
By preparing a shaped phase change thermal management material that combines highly graphitized heterogeneous carbon material with phase change material, the problem of low thermal conductivity of phase change material is solved, achieving efficient thermal management and stability, which is suitable for high-power electronic components.
Patent Information
- Application Number
- CN202411636272.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-15
- Publication Date
- 2026-05-15
AI Technical Summary
Existing phase change materials have low thermal conductivity in electronic components, resulting in low heat transfer efficiency and affecting thermal management performance. Furthermore, traditional structural improvement schemes may lead to increased complexity and cost.
By pretreating fresh grapefruit peel, ZIF-67 is grown in situ and calcined at high temperature to form a highly graphitized heterogeneous carbon material. Combined with phase change materials, a shaped phase change thermal management material with high thermal conductivity and high heat storage is formed. The thermal conductivity is improved by the catalytic effect of Co nanoparticles.
It achieves efficient thermal management and rapid heat dissipation, avoiding short-term thermal shock to electronic components. It has good adaptability, operability, and stability, and is suitable for high-power electronic components, reducing maintenance costs.
Smart Images
Figure CN122037875A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a phase change material, its preparation method, and its application, specifically to a shaped phase change thermal management material, its preparation method, and its application, belonging to the field of functional composite materials. Background Technology
[0002] With the rapid development of microelectronics technology, the integration level of electronic devices is constantly increasing, their size is gradually decreasing, while their power density is increasing significantly. This trend leads to electronic components generating a large amount of heat during operation. If this heat cannot be dissipated in a timely and effective manner, the device temperature will rise, affecting its normal operation and lifespan. Research reports indicate that once the temperature of electronic components rises to a certain threshold, their failure rate increases exponentially. Therefore, thermal management has become a crucial issue that must be addressed in the design and application of electronic components.
[0003] Phase change materials (PCMs) are used in the thermal management of electronic components due to their high energy density and ability to absorb large amounts of heat during phase change. However, most PCMs have relatively low thermal conductivity; for example, pure paraffin has a thermal conductivity of approximately 0.2 W / m·K. This results in low heat transfer efficiency in electronic component thermal management systems, and some PCMs may not be able to fully utilize their heat absorption capacity, thus affecting the thermal management effect. A common solution is to design various structural forms of phase change thermal management modules, such as PCM heat sinks, heat pipes, and fluid loops, to improve thermal management efficiency. However, this strategy may lead to problems such as structural complexity, increased weight, and higher costs. In contrast, improving the thermal conductivity of composite PCMs by adding fillers with high thermal conductivity (such as metal particles, carbon fibers, carbon nanotubes, and graphene) shows greater promise. Summary of the Invention
[0004] In view of this, in order to improve the thermal management efficiency of electronic components, this invention provides a shaped phase change thermal management material, its preparation method and application. The prepared phase change thermal management material has the advantages of excellent thermal conductivity and heat storage properties, good adaptability and operability, long-lasting stability and reliability, wide application range and reusability, providing a new idea for the development of high-performance phase change thermal management materials.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A method for preparing a shaped phase change heat management material, comprising the following steps:
[0007] (1) Take the white part of fresh grapefruit peel and pre-treat it with alkalization and hydrothermal treatment, and freeze-dry it for the first time to obtain Pre-PP;
[0008] (2) Pre-PP was immersed in a methanol solution of cobalt nitrate hexahydrate and dimethylimidazole for in-situ growth. After washing and a second freeze-drying, Pre-PP@ZIF-67 was obtained.
[0009] (3) Pre-PP@ZIF-67 was calcined at high temperature in an inert atmosphere to obtain a highly graphitized heterocarbon material. During the high-temperature calcination process, under the efficient catalytic effect of Co nanoparticles, the Pre-PP skeleton was transformed into a graphene-like high thermal conductivity carbon skeleton, and the organic ligands of ZIF-67 were transformed into highly graphitized thermal conductivity carbon material. The two carbon materials worked together to achieve efficient heat conduction, and the encapsulated phase change material achieved efficient heat storage. The two worked together to achieve efficient thermal management of electronic components, which can quickly dissipate heat and avoid irreversible damage to electronic components caused by short-term thermal shock.
[0010] (4) The highly graphitized heterogeneous carbon material is dispersed in a solution containing phase change material, heated and stirred, and then dried to obtain a shaped phase change heat management material.
[0011] Based on the above technical solution, the present invention has the following further limitations:
[0012] Furthermore, the alkalization pretreatment method in step (1) is to soak the white part of the fresh grapefruit peel in an alkaline solution at 80°C for 2-4 hours, and then wash it with deionized water until it is neutral.
[0013] The hydrothermal pretreatment method involves reacting the white part of the washed, alkalized grapefruit peel with hydrothermal heat at 160–180°C for 8–12 hours.
[0014] The first freeze-drying temperature is -50 to -65℃, and the time is 8 to 15 hours.
[0015] Preferably, the concentration of the sodium hydroxide solution is 2 mol / L;
[0016] The mass ratio of the white part of the grapefruit peel to the sodium hydroxide solution is 1:10 to 100.
[0017] Furthermore, the in-situ growth operation in step (2) involves immersing Pre-PP in the solution and mechanically stirring for 15-20 hours, followed by washing with methanol and deionized water 3-5 times.
[0018] The second freeze-drying temperature is -50 to -65℃, and the time is 8 to 15 hours.
[0019] Furthermore, the mass ratio of Pre-PP, cobalt nitrate hexahydrate, dimethylimidazole, and methanol is 1:1~2:3~6:140~200;
[0020] Furthermore, in step (3), the high-temperature calcination temperature is 800-1000℃, the time is 3-6h, and the heating rate is 2-10℃ / min;
[0021] The inert atmosphere is either nitrogen or argon.
[0022] Furthermore, in step (4), the heating and stirring temperature is 60-80℃, and the time is 1-3 hours;
[0023] Drying is carried out at 80-100℃ with forced air for 8-15 hours.
[0024] Furthermore, the solution containing the phase change material is an alcohol solution or a hexane solution of any one of polyols, fatty acids, and alkanes.
[0025] The loading of highly graphitized heterocarbon materials is 50–75 wt.%.
[0026] The present invention also provides a shaped phase change thermal management material prepared by the above preparation method.
[0027] The present invention also provides the application of the above-mentioned shaped phase change thermal management material or the shaped phase change thermal management material prepared by the above-mentioned preparation method as a thermal management material in high-power electronic components.
[0028] The beneficial effects of this invention are as follows:
[0029] (1) During the calcination process, due to the efficient catalytic effect of Co nanoparticles, the Pre-PP skeleton is transformed into a graphene-like high thermal conductivity carbon skeleton, and the organic ligand of ZIF-67 is transformed into a highly graphitized thermal conductivity carbon material. The two carbon materials work together to achieve efficient heat conduction, and the encapsulated phase change material achieves efficient heat storage.
[0030] (2) The phase change thermal management material of the present invention achieves efficient thermal management of electronic components through the synergistic effect of high thermal conductivity and high thermal storage, which can quickly dissipate heat and avoid irreversible damage to electronic components caused by short-term thermal shock.
[0031] (3) High thermal conductivity: It can change from solid to liquid or semi-liquid when the temperature rises, effectively filling tiny gaps, quickly conducting heat and reducing thermal resistance.
[0032] (4) High heat storage performance: It can effectively absorb a large amount of heat generated by high-power devices in a short time and cannot dissipate it in time, thereby avoiding irreversible damage caused by overheating.
[0033] (5) Good adaptability and operability, easy to install and use; long-lasting stability and high reliability, not easy to age or fail after long-term use, and will not produce "inflating" effect.
[0034] (6) It is widely used in various high-power heating components, can be reused, reduces maintenance costs, and does not produce glue overflow during use. Attached Figure Description
[0035] Figure 1 This is a SEM image of the shaped phase change thermal management material obtained in Example 1 of the present invention.
[0036] Figure 2 The image shows the XRD pattern of the shaped phase change heat management material obtained in Example 1 of this invention.
[0037] Figure 3 The image shows the FTIR diagram of the shaped phase change heat management material obtained in Example 1 of this invention.
[0038] Figure 4 This is a DSC diagram of the shaped phase change heat management material obtained in Embodiment 1 of the present invention. Detailed Implementation
[0039] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0040] In the following embodiments, thermal conductivity and thermal storage density were measured using a thermal conductivity meter and a differential scanning calorimeter, respectively.
[0041] Example 1
[0042] The preparation method of shaped phase change heat management materials includes the following steps:
[0043] (1) Preparation of Pre-PP
[0044] Cut white grapefruit peel was soaked in a 2 mol / L sodium hydroxide solution at 80°C for 2 hours, and then rinsed with deionized water until neutral. The rinsed PP was placed in a hydrothermal reactor at 180°C for 10 hours, and after cooling to room temperature, it was dried in a freeze dryer at -60°C for 12 hours to obtain pretreated Pre-PP.
[0045] (2) Preparation of Pre-PP@ZIF-67
[0046] The Pre-PP prepared in step (1) was immersed in a 90 mL methanol solution containing 580 mg cobalt nitrate hexahydrate and 1640 mg dimethylimidazole, mechanically stirred for 18 h, then washed three times with methanol and deionized water, and dried in a freeze dryer at -60 °C for 10 h to obtain Pre-PP@ZIF-67.
[0047] (3) Preparation of graphitized heterocarbon support
[0048] The Pre-PP@ZIF-67 prepared in step (2) was placed in a vacuum tube furnace and calcined at 1000℃ for 3 hours at a heating rate of 5℃ / min under N2 atmosphere. Then it was naturally cooled to prepare a graphitized heterocarbon support.
[0049] (4) Preparation of shaped phase change heat management materials
[0050] Take 200 mg of the graphitized heterocarbon support prepared in step (3), disperse it in 50 mL of n-hexane solution containing 600 mg of paraffin, stir at 70 °C for 2 h, and finally place the mixture in an 80 °C forced-air drying oven to dry for 12 h to obtain the shaped phase change heat management material.
[0051] The obtained shaped phase change heat management material has a thermal conductivity of 0.73 W / m·K and a heat storage density of 121.4 J / g.
[0052] Example 2
[0053] The preparation method of shaped phase change heat management materials includes the following steps:
[0054] (1) Preparation of Pre-PP
[0055] Cut white grapefruit peel was soaked in a 2 mol / L sodium hydroxide solution at 80°C for 3 hours, and then rinsed with deionized water until neutral. The rinsed PP was placed in a hydrothermal reactor at 170°C for 11 hours, and after cooling to room temperature, it was dried in a freeze dryer at -60°C for 10 hours to obtain pre-treated Pre-PP.
[0056] (2) Preparation of Pre-PP@ZIF-67
[0057] The Pre-PP prepared in step 1 was immersed in an 80 mL methanol solution containing 600 mg cobalt nitrate hexahydrate and 1540 mg dimethylimidazole, mechanically stirred for 16 h, then washed four times with methanol and deionized water, and dried in a freeze dryer at -60 °C for 12 h to obtain Pre-PP@ZIF-67.
[0058] (3) Preparation of graphitized heterocarbon support
[0059] The Pre-PP@ZIF-67 prepared in step 2 was placed in a vacuum tube furnace and calcined at 800℃ for 4 hours under N2 atmosphere at a heating rate of 2℃ / min. Then it was naturally cooled to prepare a graphitized heterocarbon support.
[0060] (4) Preparation of shaped phase change heat management materials
[0061] Take 200 mg of the graphitized heterocarbon support prepared in step 3, disperse it in 50 mL of anhydrous ethanol solution containing 500 mg of tetradecanoic acid, stir at 75 °C for 2 h, and finally place the mixture in a 90 °C forced-air drying oven to dry for 10 h to obtain the shaped phase change heat management material.
[0062] The obtained shaped phase change heat management material has a thermal conductivity of 0.80 W / m·K and a heat storage density of 112.1 J / g.
[0063] Example 3
[0064] The preparation method of shaped phase change heat management materials includes the following steps:
[0065] (1) Preparation of Pre-PP
[0066] Cut white grapefruit peel was soaked in a 2 mol / L sodium hydroxide solution at 80°C for 4 hours, and then rinsed with deionized water until neutral. The rinsed PP was placed in a hydrothermal reactor at 160°C for 12 hours, and after cooling to room temperature, it was dried in a freeze dryer at -60°C for 15 hours to obtain pre-treated Pre-PP.
[0067] (2) Preparation of Pre-PP@ZIF-67
[0068] The Pre-PP prepared in step 1 was immersed in an 85 mL methanol solution containing 720 mg cobalt nitrate hexahydrate and 1640 mg dimethylimidazole, mechanically stirred for 20 h, then washed five times with methanol and deionized water, and dried in a freeze dryer at -60 °C for 12 h to obtain Pre-PP@ZIF-67.
[0069] (3) Preparation of graphitized heterocarbon support
[0070] The Pre-PP@ZIF-67 prepared in step 2 was placed in a vacuum tube furnace and calcined at 900℃ for 6 hours at a heating rate of 10℃ / min under an argon atmosphere. Then it was naturally cooled to prepare graphitized heterocarbon.
[0071] (4) Preparation of shaped phase change heat management materials
[0072] Take 200 mg of the graphitized heterocarbon support prepared in step 3, disperse it in 50 mL of anhydrous ethanol solution containing 400 mg tetradecyl alcohol, stir at 80 °C for 2 h, and finally place the mixture in a 100 °C forced-air drying oven to dry for 8 h to obtain the shaped phase change heat management material.
[0073] The obtained shaped phase change heat management material has a thermal conductivity of 0.75 W / m·K and a heat storage density of 124.5 J / g.
[0074] Comparative Example 1
[0075] The preparation method of phase change heat management materials includes the following steps:
[0076] (1) Preparation of Pre-PP
[0077] Cut white grapefruit peel was soaked in a 2 mol / L sodium hydroxide solution at 80°C for 2 hours, and then rinsed with deionized water until neutral. The rinsed PP was placed in a hydrothermal reactor at 180°C for 10 hours, and after cooling to room temperature, it was dried in a freeze dryer at -60°C for 12 hours to obtain pre-treated Pre-PP.
[0078] (2) Preparation of ZIF-67
[0079] 580 mg of cobalt nitrate hexahydrate and 1640 mg of dimethylimidazole were dissolved in 90 mL of methanol and mechanically stirred for 18 h. The mixture was then washed three times with methanol and deionized water and dried in a freeze dryer at -60 °C for 10 h to obtain ZIF-67.
[0080] (3) Preparation of heterogeneous carbon supports
[0081] The Pre-PP prepared in step 1 and the ZIF-67 prepared in step 2 were placed in a vacuum tube furnace and calcined at 1000℃ for 3 hours at a heating rate of 5℃ / min under N2 atmosphere. Then, they were naturally cooled. The Pre-PP and ZIF-67 derivatives were then physically blended by grinding to prepare a heterogeneous carbon support.
[0082] (4) Preparation of phase change heat management materials
[0083] Take 200 mg of the highly graphitized heterocarbon support prepared in step 3, disperse it in 50 mL of n-hexane solution containing 600 mg of paraffin, stir at 70 °C for 2 h, and finally place the mixture in an 80 °C forced-air drying oven to dry for 12 h to obtain the phase change thermal management material.
[0084] The obtained phase change heat management material has a thermal conductivity of 0.57 W / m·K and a heat storage density of 110.5 J / g.
Claims
1. A method for preparing a shaped phase change heat management material, characterized in that, The steps are as follows: (1) Take the white part of fresh grapefruit peel and pre-treat it with alkalization and hydrothermal treatment, and freeze-dry it for the first time to obtain Pre-PP; (2) Pre-PP was immersed in a methanol solution of cobalt nitrate hexahydrate and dimethylimidazole for in-situ growth. After washing and a second freeze-drying, Pre-PP@ZIF-67 was obtained. (3) Pre-PP@ZIF-67 was calcined at high temperature under an inert atmosphere to obtain highly graphitized heterocarbon material; (4) The highly graphitized heterogeneous carbon material is dispersed in a solution containing phase change material, heated and stirred, and then dried to obtain a shaped phase change heat management material.
2. The preparation method according to claim 1, characterized in that, In step (1), the alkalization pretreatment method is to soak the white part of the fresh grapefruit peel in an alkaline solution at 80°C for 2-4 hours, and then wash it with deionized water until it is neutral. The hydrothermal pretreatment method involves reacting the white part of the washed, alkalized grapefruit peel with hydrothermal heat at 160–180°C for 8–12 hours. The first freeze-drying temperature is -50 to -65℃, and the time is 8 to 15 hours.
3. The preparation method according to claim 2, characterized in that, The concentration of the sodium hydroxide solution is 2 mol / L; The mass ratio of the white part of the grapefruit peel to the sodium hydroxide solution is 1:10 to 100.
4. The preparation method according to claim 1, characterized in that, In step (2), the in-situ growth operation involves immersing Pre-PP in the solution and mechanically stirring for 15-20 hours, followed by washing with methanol and deionized water 3-5 times. The second freeze-drying temperature is -50 to -65℃, and the time is 8 to 15 hours.
5. The preparation method according to claim 1, characterized in that, The mass ratio of Pre-PP, cobalt nitrate hexahydrate, dimethylimidazole, and methanol is 1:1~2:3~6:140~200.
6. The preparation method according to claim 1, characterized in that, In step (3), the high-temperature calcination temperature is 800-1000℃, the time is 3-6h, and the heating rate is 2-10℃ / min; The inert atmosphere is either nitrogen or argon.
7. The preparation method according to claim 1, characterized in that, In step (4), the heating and stirring temperature is 60-80℃, and the time is 1-3 hours; Drying is carried out at 80-100℃ with forced air for 8-15 hours.
8. The preparation method according to claim 1, characterized in that, The solution containing the phase change material is an alcohol solution or a hexane solution of any one of polyols, fatty acids, and alkanes. The loading of highly graphitized heterocarbon materials is 50–75 wt.%.
9. A shaped phase change heat management material prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the shaped phase change thermal management material of claim 9 or the shaped phase change thermal management material prepared by any one of claims 1 to 8 as a thermal management material in high-power electronic components.