CN111662686A - Expanded graphite-binary organic low-temperature nano phase change energy storage material and preparation method and application thereof - Google Patents
Expanded graphite-binary organic low-temperature nano phase change energy storage material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an expanded graphite-binary organic low-temperature nano phase change energy storage material and a preparation method and application thereof, n-tetradecane and dodecanol organic phase change material are stirred by a high-shear dispersion emulsion homogenizer to form the binary organic low-temperature nano phase change energy storage material, then the binary organic low-temperature nano phase change energy storage material is added into the expanded graphite at normal temperature and normal pressure to obtain a composite material, and a thermal conductivity meter is used for measuring the thermal conductivity of the energy storage material to be 2.027-2.407W/(m.K); the phase change temperature of the energy storage material measured by a differential scanning calorimeter is 3.8-4.5 ℃, the latent heat of phase change is 201.8-210.2J/g, the expanded graphite only plays a role in heat conduction in the energy storage process, and the expanded graphite-binary organic low-temperature nano phase change energy storage material has good compatibility, so that the super-cooling degree is almost avoided, and the melting process and the solidification process are shortened.
Description
Technical Field
The invention relates to the technical field of composite functional materials, in particular to an expanded graphite-binary organic low-temperature nano phase change energy storage material and a preparation method and application thereof.
Background
The phase-change material technology is a high and new technology based on phase-change energy storage materials, because the phase-change material technology has high energy storage density and quite stable output temperature and energy, the phase-change material technology has the advantage that sensible heat energy storage is difficult to compare, so the research on the phase-change materials is more and more extensive, some phase-change materials are commercialized, but people have no breakthrough progress on the research on the stability and reliability problems of the phase-change materials with high latent heat, at present, organic phase-change materials and inorganic phase-change materials are widely applied, the inorganic phase-change materials have higher latent heat density and wide selectable melting point range and are phase-change materials with application prospect, but in the research and experimental processes, after multiple solidification-melting cycles, the mixture has phase separation and supercooling phenomena, so that the phase-change performance is deteriorated, and the heat conductivity coefficient of the organic phase-change materials is low, the rate of energy storage is affected, thus limiting its application in industry.
In recent years, scholars at home and abroad strive to improve the heat conductivity coefficient of the organic phase change material, and the adopted methods mainly comprise:
1) adding high-thermal-conductivity nano metal particles such as nano copper, nano silicon dioxide, carbon nano tubes and the like into an organic phase change material to improve the heat transfer capacity of the organic phase change material, adding the nano copper, the carbon nano tubes and the nano aluminum oxide into the organic phase change material by Huangyan and the like, wherein the thermal conductivity coefficients of the nano copper, the nano carbon tubes and the nano aluminum oxide are improved to different degrees, and the organic phase change material added with the carbon nano tubes has the highest thermal conductivity coefficient;
2) the composite phase-change energy storage material is prepared by the energy storage material and a pure heat conduction material, although the heat conduction material can rapidly store/release energy in the composite phase-change process, the commonly used heat conduction material is metal, foam metal and the like, and the energy storage material is melted and immersed into the support material or immersed into the support material under a vacuum condition to prepare the composite phase-change energy storage material. Silver halide and the like are used as matrixes to enhance the heat conductivity coefficient of the phase-change material.
The two methods both greatly improve the heat conductivity of the energy storage material, but have some defects: although the heat conductivity coefficient of the phase-change material can be increased by adding the nano metal particles, the density of the energy storage material is different from that of the heat conduction material, and the dispersing agent is required to be added in the use process to fully disperse the heat conduction material, along with the circulation of the energy storage-release process, the function of the dispersing agent is gradually lost, the energy storage material and the heat conduction material are layered due to the different densities, the heat conduction performance is gradually weakened, the energy storage density is reduced by adding the dispersing agent, and the phase-change latent heat of the energy; the foam metal is high in cost, the pore size of the foam metal is large, the phase change material is easy to leak in the melting process, so that the phase change latent heat is reduced, the phase change material and the metal foam cannot be 100% fused, and the energy storage density is further reduced.
Therefore, the problem to be solved by those skilled in the art is how to provide a high-performance and long-life organic low-temperature nano phase change energy storage material and a preparation method thereof.
Disclosure of Invention
In view of the above, the invention provides an expanded graphite-binary organic low-temperature nano phase change energy storage material and a preparation method thereof, which not only improve the heat conductivity of the organic energy storage material, but also reduce the reduction of the energy storage capacity of the composite material, and achieve the purposes of enhancing the heat conductivity and increasing the heat storage capacity of the organic energy storage material.
In order to achieve the purpose, the invention adopts the following technical scheme:
firstly, the invention provides a preparation method of an expanded graphite-binary organic low-temperature nano phase change energy storage material, which specifically comprises the following steps:
(1) weighing expanded graphite, adding ethylene glycol, carrying out ultrasonic treatment, heating in a constant-temperature water bath, finally adding deionized water, cleaning, putting into a forced air drying oven, completely drying, taking out, standing, and naturally cooling to room temperature;
(2) weighing n-tetradecane and dodecanol according to a molar mass ratio of 0.737:0.263, adding into a beaker, and fully stirring the n-tetradecane and the dodecanol for 4min by using a high-shear dispersion emulsification homogenizer to form the binary organic low-temperature nano phase change energy storage material;
(3) and (3) dropwise adding the binary organic low-temperature nano phase change energy storage material prepared in the step (2) into the expanded graphite treated in the step (1) at normal temperature and normal pressure to form the expanded graphite-binary organic low-temperature nano phase change energy storage material.
Preferably, the mass ratio of the expanded graphite to the binary organic low-temperature nano phase change energy storage material is (0.6:19.4) - (1.4: 18.6).
Preferably, the ultrasonic power in the step (1) is 45HZ, and the ultrasonic treatment time is 30 min.
Preferably, the temperature of the constant-temperature water bath in the step (1) is 68-72 ℃, and the heating time is 1-1.5 h.
Preferably, the drying temperature in the step (1) is 110-130 ℃.
Preferably, the rotation speed of the high shear dispersion emulsification homogenizer in the step (2) is 10000-12000 r/min.
The invention also provides an expanded graphite-binary organic low-temperature nano phase change energy storage material which is prepared by the preparation method of the scheme.
The invention also limits the application of the expanded graphite-binary organic low-temperature nano phase change energy storage material, and applies the expanded graphite-binary organic low-temperature nano phase change energy storage material to cold storage in the low-temperature field of 3.8-4.5 ℃.
Through the technical scheme, compared with the prior art, the invention provides the expanded graphite-binary organic low-temperature nano phase change energy storage material and the preparation method thereof, because the expanded graphite-binary organic low-temperature nano phase change energy storage material has better compatibility, the expanded graphite-binary organic low-temperature nano phase change energy storage material does not generate phase separation after multiple condensation-melting cycles, the supercooling degree of organic matters is smaller, the condensation-melting time is shortened, the material not only has high thermal conductivity, but also has larger energy storage density and phase change latent heat, and is not easy to leak in the melting process, the thermal conductivity coefficient of the binary organic low-temperature nano phase change energy storage material measured by a thermal conductivity coefficient instrument is 0.219W/(m.K), the thermal conductivity coefficient of the expanded graphite-binary organic low-temperature nano phase change energy storage material measured by the thermal conductivity coefficient instrument is 2.027-2.407W/(m.K), the phase change temperature of the expanded graphite-binary organic low-temperature nano phase change energy storage material measured by a differential scanning calorimeter is 3.8-4.5 ℃, the phase change latent heat is 201.8-210.2J/g, and the phase change temperature and the phase change latent heat of the phase change temperature are basically unchanged after multiple times of solidification-melting.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Weighing 0.6g of expanded graphite, adding ethylene glycol to submerge the expanded graphite, carrying out ultrasonic treatment for 30min at the power of 45HZ, heating for 1h in a constant-temperature water bath tank at 70 ℃, finally adding deionized water, cleaning, putting into a forced air drying oven, completely drying at 110 ℃, taking out, standing, and naturally cooling to room temperature;
(2) weighing 19.4g of n-tetradecane and dodecanol, wherein the molar mass of the n-tetradecane and the dodecanol is 0.737:0.263, adding into a beaker, and fully stirring the n-tetradecane and the dodecanol for 4min under the condition of 10000r/min by using a high-shear dispersion emulsification homogenizer to form the binary organic low-temperature nano phase change energy storage material;
(3) and (3) dropwise adding the binary organic low-temperature nano phase change energy storage material prepared in the step (2) into the expanded graphite treated in the step (1) at normal temperature and normal pressure to form the expanded graphite-binary organic low-temperature nano phase change energy storage material.
And (3) measuring the thermal conductivity of the sample prepared in the step (3) by using a thermal conductivity meter to be 2.027W/(m.K), measuring the phase transition temperature of the sample prepared in the step (3) by using a differential scanning calorimeter to be 3.8 ℃, and measuring the latent heat of phase transition to be 210.2J/g.
Example 2
(1) Weighing 1.0g of expanded graphite, adding ethylene glycol to submerge the expanded graphite, carrying out ultrasonic treatment for 30min at the power of 45HZ, heating for 1h in a constant-temperature water bath tank at 70 ℃, finally adding deionized water, cleaning, putting into a forced air drying oven, completely drying at 120 ℃, taking out, standing, and naturally cooling to room temperature;
(2) weighing 19.0g of n-tetradecane and dodecanol, wherein the molar mass of the n-tetradecane and the dodecanol is 0.737:0.263, adding the n-tetradecane and the dodecanol into a beaker, and fully stirring the n-tetradecane and the dodecanol for 4min under the condition of 11000r/min by using a high-shear dispersion emulsifying homogenizer to form the binary organic low-temperature nano phase change energy storage material;
(3) and (3) dropwise adding the binary organic low-temperature nano phase change energy storage material prepared in the step (2) into the expanded graphite treated in the step (1) at normal temperature and normal pressure to form the expanded graphite-binary organic low-temperature nano phase change energy storage material.
And (3) measuring the thermal conductivity of the sample prepared in the step (3) by using a thermal conductivity meter to be 2.208/(m.K), and measuring the phase change temperature of the sample prepared in the step (3) by using a differential scanning calorimeter to be 4.1 ℃ and the phase change latent heat to be 205.9J/g.
Example 3
(1) Weighing 1.4g of expanded graphite, adding ethylene glycol to submerge the expanded graphite, carrying out ultrasonic treatment for 30min at the power of 45HZ, heating for 1h in a constant-temperature water bath tank at 70 ℃, finally adding deionized water, cleaning, putting into a forced air drying oven, completely drying at the temperature of 130 ℃, taking out, standing and naturally cooling to room temperature;
(2) weighing 18.6g of n-tetradecane and dodecanol, wherein the molar mass of the n-tetradecane and the dodecanol is 0.737:0.263, adding into a beaker, and fully stirring the n-tetradecane and the dodecanol for 4min under the condition of 12000r/min by using a high-shear dispersion emulsifying homogenizer to form the binary organic low-temperature nano phase change energy storage material;
(3) and (3) dropwise adding the binary organic low-temperature nano phase change energy storage material prepared in the step (2) into the expanded graphite treated in the step (1) at normal temperature and normal pressure to form the expanded graphite-binary organic low-temperature nano phase change energy storage material.
Measuring the thermal conductivity of the sample prepared in the step (3) by using a thermal conductivity meter to be 2.407W/(m.K), measuring the phase change temperature of the sample prepared in the step (3) by using a differential scanning calorimeter to be 4.5 ℃, and measuring the phase change latent heat to be 201.8J/g
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of an expanded graphite-binary organic low-temperature nano phase change energy storage material is characterized by comprising the following steps:
(1) weighing expanded graphite, adding ethylene glycol, carrying out ultrasonic treatment, heating in a constant-temperature water bath, finally adding deionized water, cleaning, putting into a forced air drying oven, completely drying, taking out, standing, and naturally cooling to room temperature;
(2) weighing n-tetradecane and dodecanol according to a molar mass ratio of 0.737:0.263, adding into a beaker, and fully stirring the n-tetradecane and the dodecanol for 4min by using a high-shear dispersion emulsification homogenizer to form the binary organic low-temperature nano phase change energy storage material;
(3) and (3) dropwise adding the binary organic low-temperature nano phase change energy storage material prepared in the step (2) into the expanded graphite treated in the step (1) at normal temperature and normal pressure to form the expanded graphite-binary organic low-temperature nano phase change energy storage material.
2. The preparation method of the expanded graphite-binary organic low-temperature nano phase-change energy storage material as claimed in claim 1, wherein the mass ratio of the expanded graphite to the binary organic low-temperature nano phase-change energy storage material is (0.6:19.4) - (1.4: 18.6).
3. The preparation method of the expanded graphite-binary organic low-temperature nano phase-change energy storage material as claimed in claim 1, wherein the ultrasonic power in the step (1) is 45HZ, and the ultrasonic treatment time is 30 min.
4. The preparation method of the expanded graphite-binary organic low-temperature nano phase-change energy storage material as claimed in claim 1, wherein the temperature of the constant-temperature water bath in the step (1) is 68-72 ℃, and the heating time is 1-1.5 h.
5. The preparation method of the expanded graphite-binary organic low-temperature nano phase change energy storage material as claimed in claim 1, wherein the drying temperature in the step (1) is 110-130 ℃.
6. The method as claimed in claim 1, wherein the rotation speed of the high shear dispersing emulsifying homogenizer in step (2) is 10000-12000 r/min.
7. An expanded graphite-binary organic low-temperature nano phase change energy storage material as claimed in any one of claims 1 to 6.
8. The application of the expanded graphite-binary organic low-temperature nano phase change energy storage material is characterized by being applied to cold storage in the low-temperature field of 3.8-4.5 ℃.
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