CN113372884A - Expanded graphite composite inorganic hydrated salt phase-change material and preparation method thereof - Google Patents

Expanded graphite composite inorganic hydrated salt phase-change material and preparation method thereof Download PDF

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CN113372884A
CN113372884A CN202110740489.6A CN202110740489A CN113372884A CN 113372884 A CN113372884 A CN 113372884A CN 202110740489 A CN202110740489 A CN 202110740489A CN 113372884 A CN113372884 A CN 113372884A
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expanded graphite
hydrated salt
inorganic hydrated
change material
surfactant
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李金洪
白云冰
黄凯越
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China University of Geosciences Beijing
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    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
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Abstract

The application provides an expanded graphite composite inorganic hydrated salt phase-change material and a preparation method thereof, which relate to the field of heat exchange or heat storage materials, and the preparation method comprises the following raw materials: anhydrous ethanol, a surfactant, expanded graphite and inorganic hydrated salt; the preparation method specifically comprises the steps of dissolving a surfactant by using absolute ethyl alcohol, modifying the hydrophilic power of the expanded graphite by using the hydrophilic-lipophilic characteristics of the surfactant, and finally packaging inorganic hydrated salt by using the modified expanded graphite by using a vacuum ultrasonic method to obtain the modified expanded graphite. The integral preparation method has the advantages of simple process, high packaging efficiency, convenient application, no potential safety hazard in the operation process and suitability for large-scale industrial production and preparation. The obtained composite phase-change energy storage material has high heat storage capacity, and can be widely applied to the fields of solar energy storage, building temperature regulation and control, power battery heat management, heating, industrial waste heat utilization, electronic device heat dissipation and the like.

Description

Expanded graphite composite inorganic hydrated salt phase-change material and preparation method thereof
Technical Field
The invention belongs to the field of heat exchange or heat storage materials, and particularly relates to an expanded graphite composite inorganic hydrated salt phase-change material.
Background
With the development of society and economy, the demand for energy of human beings is rapidly increasing. The traditional fossil energy sources have limited quantity and are often accompanied by CO emission in use2And SO2Wait for harmful gas, furtherAggravate climate change and environmental pollution. Therefore, the method improves the energy utilization rate and has important significance in the fields of energy shortage relief and ecological environment protection.
The phase change energy storage material is a substance which changes the state of a substance and can provide latent heat under the condition of constant temperature; the process of converting physical properties is called a phase transition process. At this point, the phase change material will absorb or release a large amount of latent heat. Phase change energy storage materials can be divided into two broad categories, inorganic materials and organic materials.
The inorganic hydrated salt has the characteristics of high phase change latent heat, simplicity, easy obtaining, no toxicity, no harm and the like, but cannot be directly applied due to poor stability, easy phase separation, easy leakage and corrosion of surrounding media.
Expanded graphite is a vermicular porous carbon-based material produced by rapidly heating or microwave treating expandable graphite, and is widely used due to excellent properties of unique reticular pore structure, high thermal conductivity, low cost and the like. Because the surface of the expanded graphite has oleophilic and hydrophobic characteristics, the expanded graphite is generally suitable for encapsulating organic phase change materials, but is not beneficial to encapsulating inorganic hydrated salts with hydrophilic characteristics.
Therefore, how to improve the oleophylic and hydrophobic properties of the expanded graphite, and under the condition of ensuring the high heat storage capacity of the composite material, the inorganic hydrated salt is encapsulated by utilizing the properties of the expanded graphite porous medium, so as to improve the stability of the material is a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an expanded graphite composite inorganic hydrated salt phase-change material, which is characterized in that the oleophylic and hydrophobic characteristics of expanded graphite are modified by dissolving a surfactant in absolute ethyl alcohol, and the surfactant is modified on the pore wall of the expanded graphite, so that the hydrophilic capacity of the expanded graphite can be improved, the encapsulation rate and the adsorption capacity of the inorganic hydrated salt can be further improved, the high heat storage capacity can be kept, and the phase-change material can be prevented from leaking. Simple and safe components, low price and obvious modification effect.
In order to achieve the aim, the invention provides an expanded graphite composite inorganic hydrated salt phase-change material which comprises the following raw materials: anhydrous ethanol, a surfactant, expanded graphite and inorganic hydrated salt; the anhydrous ethanol is dissolved in the surfactant, and the hydrophilic and lipophilic characteristics of the surfactant are utilized to modify the hydrophilic force of the expanded graphite and improve the encapsulation rate and the adsorption capacity of the inorganic hydrated salt.
In a preferred embodiment, the surfactant is selected from one or more of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and sodium dodecyl sulfate.
In a preferred embodiment, the method for preparing the expanded graphite comprises the following steps: and (3) expanding the expandable graphite with the particle size of 200 meshes for 10min under 800W microwave power to obtain the graphite.
In a preferred embodiment, the inorganic hydrated salt is disodium hydrogen phosphate dodecahydrate.
In a preferred embodiment, the weight ratio of the anhydrous ethanol, the surfactant and the expanded graphite is in the range of 79:1:3 to 79:18: 3.
The invention also aims to provide a preparation method of the expanded graphite composite inorganic hydrated salt phase-change material, which adopts the surfactant and the absolute ethyl alcohol to modify the expanded graphite, applies a vacuum ultrasonic method to package the inorganic hydrated salt, and then adsorbs the redundant inorganic hydrated salt, so as to ensure that the obtained expanded graphite-based composite phase-change energy storage material has good packaging effect and good material stability. The integral preparation method has the advantages of simple process, high packaging efficiency, convenient application, no potential safety hazard in the operation process and suitability for large-scale industrial production and preparation.
In order to achieve the aim, the invention provides a preparation method of an expanded graphite composite inorganic hydrated salt phase-change material, which is characterized by comprising the following steps:
1) modified expanded graphite: dispersing surfactant in anhydrous ethanol, and performing ultrasonic treatment at room temperature for 10min until the solution is clear; completely immersing the expanded graphite into the clear solution under the vacuum condition, standing for 10-15min, drying and cooling to room temperature to obtain a modified expanded graphite matrix material;
2) encapsulation of inorganic hydrated salts: and (2) carrying out ultrasonic treatment on excessive inorganic hydrated salt under the condition of water bath until the excessive inorganic hydrated salt is completely clarified, slowly dripping the modified expanded graphite base material until the excessive inorganic hydrated salt is completely immersed, then putting the modified expanded graphite base material into a vacuum environment for ultrasonic treatment for 5min, taking the modified expanded graphite base material out of the inorganic hydrated salt liquid, adsorbing excessive hydrated salt outside the base material by using filter paper, and cooling to zero degree to obtain the expanded graphite-based composite phase change energy storage material.
In a preferred embodiment, in step 1), the drying conditions are: drying for 0.5-1h at 80 ℃, wherein the ultrasonic power is 360W, and the anhydrous ethanol in the modified expanded graphite can be removed in the drying step.
In a preferred embodiment, in step 2), the water bath conditions are 50-60 ℃, the ultrasonic power is 360W, and the ultrasonic temperature is 50 ℃ for water bath heating.
In a preferred embodiment, in step 2), the specific method of ultrasound in the vacuum environment is: and placing the vacuum device in an ultrasonic cleaning machine, and vacuumizing and carrying out ultrasonic treatment simultaneously.
The invention also aims to provide an expanded graphite composite inorganic hydrated salt phase-change material and a preparation method thereof, and the expanded graphite composite inorganic hydrated salt phase-change material can be applied to the fields of solar energy storage, building temperature regulation and control, power battery thermal management, heating, industrial waste heat utilization, electronic device heat dissipation and the like.
Compared with the prior art, the expanded graphite composite inorganic hydrated salt phase-change material and the preparation method thereof have the following advantages:
1. because only four components of absolute ethyl alcohol, a surfactant, expanded graphite and inorganic hydrated salt are adopted, the components are simple and safe, the price is low, the raw materials are easy to purchase, the modification effect is obvious, and the practicability is strong. The absolute ethyl alcohol is used for replacing the conventional aqueous solution to dissolve the surfactant, so that the modification effect of the surfactant on the expanded graphite can be greatly enhanced, the adsorption capacity of the expanded graphite is further improved, the adsorption capacity of the expanded graphite on the inorganic hydrated salt phase-change material is remarkably improved, the energy storage density of the composite phase-change material can be improved, and the leakage problem of the phase-change material is reduced.
2. The inorganic hydrated salt is adopted to replace the traditional organic hydrated salt phase change material, has low cost, high phase change latent heat, is simple and easy to obtain, is nontoxic and harmless, and is more beneficial to preparation, popularization and use. However, in the traditional process, after the phase change cycle times of the adopted disodium hydrogen phosphate dodecahydrate are increased, water molecules can be separated until the water molecules become solid anhydrous particles, so that the heat storage performance of the inorganic hydrated salt is greatly weakened. Therefore, the modified graphite material is adopted for packaging. The modified graphite material has excellent performances such as high thermal conductivity, low cost and the like, and after inorganic hydrated salt is packaged, water molecules are difficult to flow out while high heat storage capacity is kept, so that the phase change heat storage performance of the graphite material is recovered, the phase separation and layering phenomena of the inorganic hydrated salt material are avoided, and the adsorption capacity of the inorganic hydrated salt is enhanced.
3. Experimental results show that the enthalpy value of the composite phase change material prepared by the invention can reach more than 230J/g and can reach 299J/g at most. Meanwhile, the stability of the expanded graphite composite inorganic hydrated salt phase-change material is improved, leakage in the process of multiple phase-change recycling is prevented, the performance is almost not attenuated after the phase-change material is recycled for 500 times, and the uniformity of the phase-change material is kept.
4. The preparation method disclosed by the invention is simple in preparation process, convenient and fast to package, low in requirement on the capability of operators, free of potential safety hazard in the preparation process, and especially suitable for large-scale industrial production and preparation.
5. The material prepared by the invention can be widely applied to the fields of solar energy storage, building temperature regulation and control, power battery heat management, heating, industrial waste heat utilization, electronic device heat dissipation and the like.
Drawings
Fig. 1 shows the contact angle of the modified expanded graphite in example 1, and the modified expanded graphite has high hydrophilicity and is suitable for encapsulating a hydrated salt phase-change material.
FIG. 2 shows the modified expanded graphite of example 1, in which a surfactant is attached to the walls of the pores of the expanded graphite to increase the hydrophilicity of the expanded graphite.
Fig. 3 shows the micro morphology of the modified expanded graphite encapsulated hydrous salt composite phase-change material in example 1, in which hydrous salt is uniformly adsorbed on the pore wall of the expanded graphite, and the heat storage capacity of the composite phase-change material is increased.
Fig. 4 is DSC images and data of the modified expanded graphite encapsulated hydrous salt composite phase change material of example 1 according to the present invention, wherein the composite phase change material has a high heat capacity.
Fig. 5 is a DSC image and data of the modified expanded graphite-encapsulated hydrous salt composite phase change material after 500 cycles in example 1 of the present invention, where the composite phase change material has good cycle stability and no decay in heat storage performance after 500 cycles.
Detailed Description
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In the present invention, the parts by weight may be in the units of μ g, mg, g, kg, etc. known in the art, or may be multiples thereof, such as 1/10, 1/100, 10, 100, etc.
Example 1
(1) Dispersing 0.3g of sodium dodecyl sulfate in 10mL of absolute ethyl alcohol, and carrying out ultrasonic treatment at room temperature and 360W power for 10min until the solution is clear, thereby obtaining a soaking solution for modification;
(2) placing 0.3g of expanded graphite in a soaking solution for modification, standing for 10min in a vacuum environment, taking out, drying for 30min at 80 ℃, and cooling to room temperature to obtain a modified expanded graphite matrix material;
(3) and (2) carrying out ultrasonic treatment on excessive liquid disodium hydrogen phosphate dodecahydrate under the condition of 50 ℃ water bath until the excessive liquid disodium hydrogen phosphate is completely clarified, slowly dropwise adding the excessive liquid disodium hydrogen phosphate into the modified expanded graphite base material until the excessive liquid disodium hydrogen phosphate is completely immersed, placing a vacuum device in an ultrasonic cleaning machine under the condition of 50 ℃ water bath, carrying out ultrasonic treatment while heating in the water bath and vacuumizing, carrying out vacuum ultrasonic treatment for 5min, taking out, repeatedly adsorbing with filter paper to remove the excessive liquid disodium hydrogen phosphate on the surface, and cooling to 0 ℃ to obtain the modified expanded graphite base material.
The first heat storage capacity of the high heat storage capacity expanded graphite composite hydrated salt phase-change material is 260J/g, the heat storage capacity after 500 cycles is 259J/g, and the heat storage temperature is 34 ℃.
Example 2
(1) Dispersing 0.1g of hexadecyl trimethyl ammonium chloride in 10mL of absolute ethyl alcohol, and carrying out ultrasonic treatment at room temperature and 360W power for 10min until the solution is clear, thereby obtaining a soaking solution for modification;
(2) placing 0.3g of expanded graphite in a soaking solution for modification, standing for 10min in a vacuum environment, taking out, drying for 30min at 80 ℃, and cooling to room temperature to obtain a modified expanded graphite matrix material;
(3) and (2) carrying out ultrasonic treatment on excessive liquid disodium hydrogen phosphate dodecahydrate under the condition of 50 ℃ water bath until the excessive liquid disodium hydrogen phosphate is completely clarified, slowly dropwise adding the excessive liquid disodium hydrogen phosphate into the modified expanded graphite base material until the excessive liquid disodium hydrogen phosphate is completely immersed, placing a vacuum device in an ultrasonic cleaning machine under the condition of 50 ℃ water bath, carrying out ultrasonic treatment while heating in the water bath and vacuumizing, carrying out vacuum ultrasonic treatment for 5min, taking out, repeatedly adsorbing with filter paper to remove the excessive liquid disodium hydrogen phosphate on the surface, and cooling to 0 ℃ to obtain the modified expanded graphite base material.
The high heat storage capacity expanded graphite composite hydrous salt phase-change material has the first heat storage capacity of 299J/g, the heat storage capacity after 500 cycles of 284J/g and the heat storage temperature of 38 ℃.
Example 3
(1) Dispersing 0.1g of dodecyl trimethyl ammonium bromide in 10mL of absolute ethyl alcohol, and carrying out ultrasonic treatment at the room temperature with the power of 360W for 10min until the solution is clear, thereby obtaining a soak solution for modification;
(2) placing 0.3g of expanded graphite in a soaking solution for modification, standing for 10min in a vacuum environment, taking out, drying for 30min at 80 ℃, and cooling to room temperature to obtain a modified expanded graphite matrix material;
(3) and (2) carrying out ultrasonic treatment on excessive liquid disodium hydrogen phosphate dodecahydrate under the condition of 50 ℃ water bath until the excessive liquid disodium hydrogen phosphate is completely clarified, slowly dropwise adding the excessive liquid disodium hydrogen phosphate into the modified expanded graphite base material until the excessive liquid disodium hydrogen phosphate is completely immersed, placing a vacuum device in an ultrasonic cleaning machine under the condition of 50 ℃ water bath, carrying out ultrasonic treatment while heating in the water bath and vacuumizing, carrying out vacuum ultrasonic treatment for 5min, taking out, repeatedly adsorbing with filter paper to remove the excessive liquid disodium hydrogen phosphate on the surface, and cooling to 0 ℃ to obtain the modified expanded graphite base material.
The first heat storage capacity of the high heat storage capacity expanded graphite composite hydrous salt phase-change material is 236J/g, the heat storage capacity after 500 cycles is 230J/g, and the heat storage temperature is 37 ℃.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (9)

1. The expanded graphite composite inorganic hydrated salt phase-change material is characterized by comprising the following raw materials: anhydrous ethanol, a surfactant, expanded graphite and inorganic hydrated salt; firstly, absolute ethyl alcohol is used for dissolving a surfactant, and the hydrophilic and lipophilic characteristics of the surfactant are utilized to modify the hydrophilic force of the expanded graphite and improve the encapsulation rate and the adsorption capacity of the inorganic hydrated salt.
2. The expanded graphite composite inorganic hydrated salt phase change material of claim 1, wherein the surfactant is selected from one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, and sodium dodecyl sulfate.
3. The expanded graphite composite inorganic hydrated salt phase change material of claim 1, wherein the inorganic hydrated salt is disodium hydrogen phosphate dodecahydrate.
4. The expanded graphite composite inorganic hydrated salt phase-change material as claimed in any one of claims 1 to 3, wherein the weight ratio of the anhydrous ethanol, the surfactant and the expanded graphite is in the range of 79:1:3 to 79:18: 3.
5. The preparation method of the expanded graphite composite inorganic hydrated salt phase-change material is characterized by comprising the following steps of:
1) modified expanded graphite: dispersing surfactant in anhydrous ethanol, and performing ultrasonic treatment at room temperature for 10min until the solution is clear; completely immersing the expanded graphite into the clear solution under the vacuum condition, standing for 10-15min, drying and cooling to room temperature to obtain a modified expanded graphite matrix material;
2) encapsulation of inorganic hydrated salts: and (2) carrying out ultrasonic treatment on excessive inorganic hydrated salt under the condition of water bath until the excessive inorganic hydrated salt is completely clarified, slowly dripping the modified expanded graphite base material until the excessive inorganic hydrated salt is completely immersed, then putting the modified expanded graphite base material into a vacuum environment for ultrasonic treatment for 5min, taking the modified expanded graphite base material out of the inorganic hydrated salt liquid, adsorbing excessive hydrated salt outside the base material by using filter paper, and cooling to zero degree to obtain the expanded graphite-based composite phase change energy storage material.
6. The method for preparing the expanded graphite composite inorganic hydrous salt phase-change material as claimed in claim 5, wherein in the step 1), the drying conditions are as follows: drying at 80 ℃ for 0.5 h.
7. The method for preparing the expanded graphite composite inorganic hydrous salt phase-change material as claimed in claim 5, wherein in the step 2), the water bath condition is 50-60 ℃, the ultrasonic power is 360W, and the ultrasonic temperature is 50 ℃ for water bath heating.
8. The method for preparing the expanded graphite composite inorganic hydrous salt phase-change material as claimed in claim 5, wherein in the step 2), the specific ultrasonic method in the vacuum environment comprises the following steps: and placing the vacuum device in an ultrasonic cleaning machine, and vacuumizing and carrying out ultrasonic treatment simultaneously.
9. The expanded graphite composite inorganic hydrous salt phase-change material as claimed in claim 1 and the preparation method of the expanded graphite composite inorganic hydrous salt phase-change material as claimed in claim 5 are applied to the fields of solar energy storage, building temperature regulation and control, power battery thermal management, heating, industrial waste heat utilization, electronic device heat dissipation and the like.
CN202110740489.6A 2021-06-30 2021-06-30 Expanded graphite composite inorganic hydrated salt phase-change material and preparation method thereof Pending CN113372884A (en)

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CN114214039A (en) * 2022-01-07 2022-03-22 中国建筑材料科学研究总院有限公司 Hydrated salt porous material composite phase-change plate and preparation method thereof
CN115724630A (en) * 2022-11-18 2023-03-03 中国地质大学(北京) Phase-change energy-storage plastering mortar and preparation method thereof
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CN113637461A (en) * 2021-09-17 2021-11-12 中国地质大学(北京) Method for enhancing stability of expanded graphite-based inorganic hydrated salt composite phase-change material
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WO2023159996A1 (en) * 2022-02-28 2023-08-31 华南理工大学 Hydrated salt thermochemical heat storage composite material, preparation method therefor and application thereof
CN115724630A (en) * 2022-11-18 2023-03-03 中国地质大学(北京) Phase-change energy-storage plastering mortar and preparation method thereof
CN115724630B (en) * 2022-11-18 2024-05-28 中国地质大学(北京) Phase-change energy-storage plastering mortar and preparation method thereof

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Application publication date: 20210910