CN111187599B - Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof - Google Patents

Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof Download PDF

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CN111187599B
CN111187599B CN202010114256.0A CN202010114256A CN111187599B CN 111187599 B CN111187599 B CN 111187599B CN 202010114256 A CN202010114256 A CN 202010114256A CN 111187599 B CN111187599 B CN 111187599B
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manganese oxide
oxide nanorod
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张焕芝
朱钰漕
黄朝玮
张青峰
季蓉
夏永鹏
魏胜
孙立贤
徐芬
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Guilin University of Electronic Technology
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Abstract

The invention discloses a three-dimensional basic manganese oxide nanorod foam composite phase change material which is prepared by compounding three-dimensional basic manganese oxide nanorod foam and polyethylene glycol by a vacuum impregnation method, wherein the three-dimensional basic manganese oxide nanorod foam is prepared by preparing basic manganese oxide nanorod hydrogel from manganese chloride tetrahydrate, sodium hydroxide and potassium permanganate and then freeze-drying the basic manganese oxide nanorod hydrogel. The micro-morphology of the three-dimensional basic manganese oxide nanorod foam is a three-dimensional pore channel structure formed by stacking basic manganese oxide nanorods with the average diameter range of 150nm-260 nm; the polyethylene glycol has a molecular long-chain structure and is wound with the basic manganese oxide nanorod to form a stable structure. The photo-thermal conversion efficiency of the obtained composite phase change material is 89-98%, the phase change temperature is 39-60 ℃, and the phase change latent heat is 122-163J/g. The invention has the following advantages: 1. the highest photothermal conversion efficiency reaches 98 percent; 2. the leakage problem in the phase change process is effectively solved; 3. high phase change latent heat and thermal stability performance; 4. the cost is low.

Description

Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof
Technical Field
The invention relates to the field of phase change energy storage materials, in particular to a three-dimensional basic manganese oxide nanorod foam composite phase change material and a preparation method and application thereof.
Background
With the increase of economy and population, the problem of energy supply is increasingly highlighted. On the one hand, solar energy, as the most abundant and available renewable energy source, is expected to replace fossil fuels by developing reliable and efficient energy conversion and storage devices and systems, thereby reducing the mismatch of energy supply and demand. On the other hand, the collection and utilization of thermal energy from solar irradiance is also of vital importance for the future of greener and sustainable energy sources. One of the most promising methods for converting, storing and utilizing solar and thermal energy is to develop Phase Change Materials (PCMs) that can provide high energy storage density, absorb and release constant temperature thermal energy in the form of melting or solidifying during phase change.
Phase Change Materials (PCMs) are materials that absorb or release heat during Phase change and have thermal energy storage and temperature regulation functions, and play a crucial role in solar energy conversion, waste heat collection, and electronic system thermal management. The phase-change material can be divided into solid-liquid, solid-gas, liquid-gas and solid-solid phase-change materials according to the phase state transformation form in the working process. The solid-gas and liquid-gas phase change materials absorb heat to generate phase change, the state of the solid-gas and liquid-gas phase change materials is changed into a gas state to cause the volume to expand rapidly, and the volume work generated by the volume change causes the phase change materials to have higher heat storage density; however, the volume change is too large and the generated phase change material vapor is harsh on the container and the use condition, so the practical use and related research of the phase change material are few. The solid-liquid phase change material may be classified into an organic phase change material and an inorganic phase change material according to chemical components. The inorganic phase-change material has the defects of poor reversibility, serious supercooling phenomenon, phase separation, strong corrosivity and the like due to the change of crystal water in the phase-change process. Organic phase change materials, including polyethylene glycol (PEG), paraffin (or normal paraffin) and fatty acids, have been extensively studied for their advantages of high energy storage density, convenient use, low or low supercooling degree, good chemical and thermal stability, abundant natural resources, etc. However, the current organic phase-change materials have the problem that the materials cannot absorb energy from the nature, so that the application range of the phase-change materials is greatly limited; and the problem of easy leakage also needs to be solved.
Among the energy that can be absorbed from nature, solar energy has the most abundant, most renewable and most environmentally friendly characteristics. However, the use of solar radiation presents intermittent and discontinuous problems. The photo-thermal conversion is an effective method for solving the problem of discontinuity of solar energy time and space, and the photo-thermal conversion effect is given to the composite phase change material, so that the problems can be effectively solved at the same time.
The above effects can be achieved by directly selecting a composite phase change material having a photothermal conversion effect. Boyuan Mu et al take lauric acid (La) as a phase change material, and graft lauric acid on Graphene Aerogel (GA) as a support material through an esterification reaction and a reduction process to prepare a composite phase change material with stable form (Boyuan Mu, Min Li, Z (2019), Synthesis of non-stable composite phase change Materials with modified graphene aerogels for solar Energy conversion and storage, solar Energy Materials), infrared light and visible light can be captured by the black surface of La-GA in the photothermal process, and the photothermal conversion efficiency of the composite phase change material is up to 80.6%. However, the conversion efficiency is not high, and there is a large waste in the aspect of solar energy utilization.
Analysis of the basic mechanism of photothermal conversion reveals that electrons can be excited by light, and thus the electrons are hopped to an excited state; the excited electrons then release energy back to the ground state by non-radiative relaxation, energy transfer, or quenching. Based on the above principle, research results in the field of photothermal conversion show that by using metal oxide or metal nanomaterial as photothermal conversion material, solar energy can be effectively collected and conversion efficiency can be improved.
Therefore, by compounding the photothermal conversion material into the phase change material, the photothermal conversion efficiency of the composite phase change material can be improved. Weiwei Wang et al by coating n-eicosane onto titanium oxide Ti2O3A novel ultra-light Flexible Carbon Foam (CF) Based Phase Change composite material (Weiwei Wang, Yibing Cai, Mingyue Du, Xuebin Hou, Jingyan Liu, Huizhen Ke, Qufu Wei, Z (2019), ultra light and Flexible Carbon Foam-Based Phase Change Composites with High tension-Heat Capacity and Photo-Thermal Conversion Capacity ACS Applied materials) is prepared in a nano particle pre-coated CF framework, and the photothermal Conversion efficiency is improved by 7.6% compared with that of the composite Phase Change material prepared by Boyuan Mu.
Because the composite phase-change material with photo-thermal conversion is still in the initial stage of research and the related research is less, the technical problem in the prior art is how to further improve the photo-thermal conversion efficiency of the composite phase-change material.
Based on the photo-thermal efficiency related theoretical research and the inventor research results, the photo-thermal conversion efficiency of the composite phase-change material can be improved by the following method:
1. the influence of the atomic structure of the metal element on the photothermal effect is obvious, so that the metal element suitable for the chemical environment of the phase-change material is selected and is a feasible method for improving the photothermal conversion efficiency;
2. the microscopic morphology of the metal oxide has a significant influence on the photo-thermal conversion efficiency, so that the controllable synthesis of the metal oxide with a specific morphology, such as nanoparticles (0 dimension), nanorods (1 dimension) and nanosheets (two dimensions), is a feasible method for improving the photo-thermal conversion efficiency;
3. when the photothermal conversion material metal oxide and the phase change material are compounded, a three-dimensional network structure should be formed, which is beneficial to improving the heat energy transmission efficiency and further improving the photothermal conversion efficiency;
4. the inventor researches and finds that the thermal stability of the composite phase-change material is reduced when the photothermal conversion material metal oxide is compounded with the phase-change material, so that the influence on the thermal stability of the composite phase-change material is minimized when the metal oxide is selected;
5. in addition, the photothermal conversion requires absorption of light, and the organic phase-change material generally has the characteristics of good light reflectivity, poor thermal conductivity and the like, that is, the photothermal conversion efficiency is also affected by the self-performance of the phase-change material.
Therefore, the method selects proper elements to prepare a specific micro-morphology to be compounded with a specific phase-change material, is a feasible method for improving the photo-thermal efficiency of the composite phase-change material, and has application prospects and commercial values in the fields of heat energy storage and heat management.
Disclosure of Invention
The invention aims to provide a three-dimensional basic manganese oxide nanorod foam composite phase-change material, wherein a photo-thermal conversion material of the composite phase-change material has the characteristics of specific morphology and stable morphology, the phase-change material has the characteristics of low light reflectivity and good heat conductivity, and the final composite phase-change material has high phase-change latent heat, proper phase-change temperature, high photo-thermal conversion efficiency, excellent thermal cycle stability and leakage prevention performance.
Based on the above object, the inventors have found that:
among transition metal elements, manganese has variable oxidation numbers and obvious crystal structure defects, so that electrons are easy to transfer, and the photo-thermal conversion efficiency is improved;
in the micro morphology of the nano material, the nanorod structure can increase electron transfer ways, and the nanorod structure can effectively form a three-dimensional network structure, so that the energy transfer rate and the photo-thermal conversion efficiency are improved.
Therefore, the prepared three-dimensional network structure metal oxide nanorod composite phase-change material has the advantages of large specific surface area, high porosity and adsorption capacity, and realizes the technical effect of further improving the photothermal conversion efficiency.
The invention also aims to provide a preparation method of the phase-change material, which combines the solution dripping method, the sol-gel method and the vacuum impregnation method and has simple and convenient process.
The invention realizes the purpose, and adopts the technical scheme that:
the three-dimensional basic manganese oxide nanorod foam composite phase change material is prepared by compounding three-dimensional basic manganese oxide nanorod foam and polyethylene glycol by a vacuum impregnation method, wherein the three-dimensional basic manganese oxide nanorod foam is prepared by taking manganese chloride tetrahydrate, sodium hydroxide and potassium permanganate as raw materials, preparing basic manganese oxide nanorod hydrogel and then freezing and drying the basic manganese oxide nanorod hydrogel.
The micro-morphology of the three-dimensional basic manganese oxide nanorod foam is a three-dimensional pore channel structure formed by stacking basic manganese oxide nanorods, and the average diameter range of the basic manganese oxide nanorods is 150nm-260 nm.
Weight average molecular mass (M) of polyethylene glycolw) Is 2000-10000, has a molecular long-chain structure, and can be wound with the basic manganese oxide nano-rod to form a stable structure.
A preparation method of a three-dimensional basic manganese oxide nanorod foam composite phase-change material comprises the following steps:
step 1) preparing three-dimensional basic manganese oxide nanorod foam, namely preparing 0.4-0.8mol/L sodium hydroxide and 0.08-0.15mol/L potassium permanganate into a mixed solution and 0.2-0.8mol/L manganese chloride tetrahydrate solution, measuring the mixed solution and the manganese chloride tetrahydrate solution with the volume ratio of 0.7-1.1 by using a measuring cylinder, then dropwise adding the manganese chloride tetrahydrate solution into the mixed solution at the speed of 2-4mL/min, fully stirring, reacting for 8-12h at the temperature of 150-200 ℃ to obtain basic manganese oxide nanorod hydrogel, and finally performing freeze drying for 48-72h at the temperature of-52 ℃ to-47 ℃ to obtain the three-dimensional basic manganese oxide nanorod foam;
step 2) preparing the three-dimensional basic manganese oxide nanorod foam composite phase-change material, weighing polyethylene glycol according to the mass ratio of 75-88%, and soaking the molten polyethylene glycol into the three-dimensional basic manganese oxide nanorod foam for 10-12 hours in a vacuum oven at 60-90 ℃ by adopting a vacuum impregnation method to obtain the three-dimensional basic manganese oxide nanorod foam composite phase-change material.
The photo-thermal conversion efficiency of the application of the three-dimensional basic manganese oxide nanorod foam composite phase-change material as a phase-change material is 89-98%.
The phase change temperature of the application of the three-dimensional basic manganese oxide nanorod foam composite phase change material as a phase change material is 39-60 ℃, and the phase change latent heat is 122-163J/g.
The experimental detection result of the three-dimensional basic manganese oxide nanorod foam composite phase-change material obtained by the invention is as follows:
according to infrared spectrum (FT-IR) tests, the three-dimensional basic manganese oxide nanorod foam composite phase change material disclosed by the invention has been successfully synthesized.
As can be seen from the test of a Scanning Electron Microscope (SEM), the three-dimensional basic manganese oxide nanorod foam composite phase change material has a pore channel structure formed by stacking a large number of nanorods, and the phase change material with a high molecular chain segment is wound on the nanorods after adsorbing the phase change material.
The X-ray diffractometer (XRD) tests show that the diffraction peaks of the three-dimensional basic manganese oxide nanorod foam composite phase change material prepared by the invention are almost completely the same as those of PEG6000 and MnOOH.
Differential Scanning Calorimetry (DSC) tests show that the phase change temperature of the three-dimensional basic manganese oxide nanorod foam composite phase change material prepared by the invention is 39-60 ℃, and the phase change latent heat is 122-163J/g.
The thermal cycle stability of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is good through 100 DSC cycle tests.
Through the test of a photo-thermal conversion system, the three-dimensional basic manganese oxide nanorod foam composite phase change material has high photo-thermal conversion efficiency, and the photo-thermal conversion efficiency is 89-98%.
Compared with the prior art, the invention has the following advantages:
1. the microscopic morphology of the basic manganese oxide nanorod foam prepared by the method is a nanorod structure with the average diameter range of 150nm-260nm, and the basic manganese oxide nanorod foam is stacked to form a three-dimensional network structure, so that the transmission of heat energy and the improvement of photo-thermal efficiency are facilitated, the photo-thermal conversion efficiency is up to 98% at most, and is improved by nearly 10% compared with the prior art;
2. the three-dimensional network structure formed by stacking the nanorods of the basic manganese oxide nanorod foam is also beneficial to winding polyethylene glycol with a high molecular chain segment on the nanorods to form a stable structure, so that the problem of leakage of the polyethylene glycol in the phase change process can be effectively solved;
3. the composition of the basic manganese oxide nanorod foam and the polyethylene glycol is a physical action rather than a chemical action, so that the high phase change latent heat of the phase change material is effectively maintained;
4. on the basis of obtaining high light thermal efficiency, the composite phase-change material keeps good thermal stability, can keep the characteristics of the phase-change material for a long time under the condition of high temperature, has small change of phase-change temperature and phase-change latent heat, and meets the requirements of practical application;
5. the manganese element as the raw material is low in cost, particularly the Guangxi Zhuang autonomous region is the province with the largest manganese storage capacity in the whole country, the storage capacity accounts for 38.4 percent of the whole country, and the method has obvious advantage in reducing the production cost.
Therefore, the three-dimensional basic manganese oxide nanorod foam composite phase change material provided by the invention is stable in shape, high in phase change latent heat, good in thermal cycle stability, proper in phase change temperature, good in leakage-proof performance, high in photo-thermal conversion efficiency, and wide in application prospect in the field of phase change heat storage.
Description of the drawings:
FIG. 1 is a graph of the infrared spectrum (FT-IR) of PEG6000, MnOOH, CPCM-75%, CPCM-80%, CPCM-86%, CPCM-88%, CPCM-90% of example 1, example 2, example 3, example 4, comparative example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the three-dimensional basic manganese oxide nanorod foam prepared in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of CPCM-86% of example 1;
FIG. 4 is an X-ray diffraction (XRD) pattern of PEG6000, MnOOH, CPCM-75%, CPCM-80%, CPCM-86%, CPCM-88%, CPCM-90% of example 1, example 2, example 3, example 4, comparative example 1;
FIG. 5 is a Differential Scanning Calorimetry (DSC) curve of PEG6000, CPCM-75%, CPCM-80%, CPCM-86%, CPCM-88%, CPCM-90% in example 1, example 2, example 3, example 4, comparative example 1;
FIG. 6 is a chart of a CPCM-86% Differential Scanning Calorimetry (DSC) cycle of example 1;
FIG. 7 is a photothermal plot of PEG6000, CPCM-75%, CPCM-80%, CPCM-86%, CPCM-88%, CPCM-90% in example 1, example 2, example 3, example 4, comparative example 1;
FIG. 8 is a comparison of PEG6000 in example 1 before and after heating;
FIG. 9 is a comparison of CPCM-86% of example 1 before and after heating.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a three-dimensional basic manganese oxide nanorod foam composite phase-change material comprises the following steps:
step 1) preparing three-dimensional basic manganese oxide nanorod foam, preparing 25mL of 0.5mol/L tetrahydrate manganese chloride solution, 30mL of 0.625mol/L sodium hydroxide solution, adding 0.59g of potassium permanganate, fully stirring to form a mixed solution, then slowly and completely dropwise adding the tetrahydrate manganese chloride solution into the mixed solution at the speed of 2mL/min, transferring the mixed solution to a high-temperature reaction kettle after fully stirring, placing the high-temperature reaction kettle into a forced air drying box at 180 ℃ for reaction for 10 hours to obtain basic manganese oxide nanorod hydrogel, and then performing freeze drying for 72 hours between 52 ℃ below zero and 47 ℃ below zero to obtain the three-dimensional basic manganese oxide nanorod foam;
step 2) preparation of the three-dimensional basic manganese oxide nanorod foam composite phase change material, wherein polyethylene glycol accounting for 86% of the total mass of the composite phase change material is weighed and completely melted, and then the melted polyethylene glycol is soaked in the three-dimensional basic manganese oxide nanorod foam for 12 hours in a vacuum oven at 80 ℃ to obtain the three-dimensional basic manganese oxide nanorod foam composite phase change material, wherein a sample is named as CPCM-86%.
In order to prove that the three-dimensional basic manganese oxide nanorod foam composite phase change material is successfully prepared, an infrared spectrum (FT-IR) test is carried out. The result is shown in figure 1, the three-dimensional basic manganese oxide nanorod foam composite phase change material of the invention has been successfully synthesized, and it can be seen that the spectrum of the composite phase change material is completely composed of the absorption peaks of the polyethylene glycol and the basic manganese oxide nanorods, no new groups are generated, which indicates that no chemical action occurs, and the composite phase change material is purely physical action, and is beneficial to maintaining the high phase change latent heat of the polyethylene glycol.
In order to prove the micro-morphological structure of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Scanning Electron Microscope (SEM) test is carried out. As shown in FIGS. 2 and 3, the three-dimensional basic manganese oxide nanorod foam composite phase change material of the invention has a channel structure formed by stacking a large number of nanorods, and the phase change material with a high molecular chain segment is wound on the nanorods after adsorbing the phase change material.
In order to prove the change of the crystal structure of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, XRD test is carried out. As shown in FIG. 4, the diffraction peaks of the composite phase change material are almost identical to those of PEG6000 and MnOOH.
In order to prove the phase change performance of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Differential Scanning Calorimetry (DSC) test is carried out, and the test conditions are as follows: the nitrogen flow rate is 20 mL/min, and the heating and cooling rates are as follows: 5 ℃/min, and the temperature test range is as follows: -15-115 ℃. The result is shown in FIG. 5, the melting temperature of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is 58.56 ℃, and the crystallization temperature is 39.51 ℃; the latent heat of phase change was found to be 156.07J/g and 151.64J/g.
In order to prove the thermal cycle stability of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, 100 DSC cycle performance tests are carried out. As shown in FIG. 6, after 100 times of thermal cycles, the three-dimensional basic manganese oxide nanorod foam composite phase change material has small phase change temperature fluctuation and basically unchanged phase change latent heat, shows good thermal cycle performance in the phase change process, and can be widely applied to the field of heat storage.
In order to prove the photothermal conversion effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, photothermal test is carried out. The results are shown in FIG. 7:
firstly, a temperature platform appears between 42 ℃ and 53 ℃ in the three-dimensional basic manganese oxide nanorod foam composite phase-change material, which shows that the composite phase-change material has a phase-change effect therein and can absorb and release heat, and a pure PEG curve has no platform, which means that the pure PEG has poor light absorption capacity and cannot reach the phase-change temperature;
after simulated sunlight irradiates for 20 minutes, the peak value of the composite phase-change material is obviously higher than that of pure PEG, the CPCM-86% photothermal conversion efficiency is 92% through calculation, and the composite phase-change material is comprehensively shown to have high photothermal conversion efficiency.
In order to prove the leakage-proof effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase-change material, a leakage-proof test is carried out. Placing pure PEG6000 and prepared sample CPCM-86% in an 80 ℃ oven for 30min, photographing and observing the sample before and after heating, wherein the experimental result is shown in figures 8 and 9, and no leakage is observed after the sample CPCM-86% is placed in the 80 ℃ oven for 30 min; pure PEG6000 is heated to become liquid. The CPCM-86% of the composite phase-change material has better anti-leakage performance after phase change.
In order to study the effect of the content of polyethylene glycol on the enthalpy and the photothermal effect of the composite phase change material, examples 2, 3, and 4 and comparative example 1 were provided, the composite phase change material having the content of polyethylene glycol of 75%, 80%, 88%, and 90%, respectively.
Example 2
A preparation method of a three-dimensional basic manganese oxide nanorod foam composite phase change material (the content of polyethylene glycol is 75%, and a sample is named as CPCM-75%), and steps which are not particularly described are the same as those in example 1.
In order to prove the phase change performance of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Differential Scanning Calorimetry (DSC) test is carried out. The result is shown in FIG. 5, the melting temperature of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is 58.60 ℃, and the crystallization temperature is 42.30 ℃; the observed latent heat of phase change is 125.35J/g and 122.56J/g, and the enthalpy value of phase change is reduced to a certain degree relative to the enthalpy value of CPCM-86%.
In order to prove the photothermal conversion effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase-change material, photothermal test is carried out, and the photothermal conversion efficiency of CPCM-75% is calculated to be 98%. The results are shown in fig. 7, and compared with example 1, the photothermal effect is greatly improved with the reduction of polyethylene glycol; n-eicosane coated Ti prepared in accordance with the aforementioned prior art Weiwei Wang2O3Compared with the nano particle composite phase change material, the photo-thermal conversion efficiency is greatly improved by 9.8 percent.
Example 3
A preparation method of a three-dimensional basic manganese oxide nanorod foam composite phase change material (the content of polyethylene glycol is 80%, and a sample is named as CPCM-80%), and steps which are not particularly described are the same as those in example 1.
In order to prove the phase change performance of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Differential Scanning Calorimetry (DSC) test is carried out. The result is shown in FIG. 5, the melting temperature of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is 58.60 ℃, and the crystallization temperature is 40.10 ℃; the observed latent heat of phase change is 137.53J/g and 133.89J/g, and the enthalpy value of phase change is reduced relative to the enthalpy value of CPCM-86%.
In order to prove the photothermal conversion effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase-change material, photothermal test is carried out, and the photothermal conversion efficiency of CPCM-80% is 96% through calculation. As shown in FIG. 7, the photothermal effect was improved with the decrease of polyethylene glycol as compared with example 1.
Example 4
A preparation method of a three-dimensional basic manganese oxide nanorod foam composite phase change material (the content of polyethylene glycol is 88%, and a sample is named as CPCM-88%), and steps which are not particularly described are the same as those in example 1.
In order to prove the phase change performance of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Differential Scanning Calorimetry (DSC) test is carried out. The result is shown in FIG. 5, the melting temperature of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is 58.60 ℃, and the crystallization temperature is 40.10 ℃; the observed latent heat of phase change is 162.88J/g and 155.11J/g, and the enthalpy value of phase change is increased relative to the enthalpy value of CPCM-86%.
In order to prove the photothermal conversion effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, photothermal test is carried out, and the photothermal conversion efficiency of CPCM-88% is 89% through calculation. As shown in FIG. 7, the photothermal effect was reduced with the addition of polyethylene glycol as compared with example 1.
Comparative example 1
Preparation method of three-dimensional basic manganese oxide nanorod foam composite phase change material (the content of polyethylene glycol is 90%, and a sample is named as CPCM-90%), and the steps which are not particularly described are the same as those in example 1
In order to prove the phase change performance of the prepared three-dimensional basic manganese oxide nanorod foam composite phase change material, a Differential Scanning Calorimetry (DSC) test is carried out. The result is shown in FIG. 5, the melting temperature of the three-dimensional basic manganese oxide nanorod foam composite phase-change material is 56.02 ℃, and the crystallization temperature is 39.21 ℃; the observed latent heat of phase change is 164.86J/g and 158.27J/g, and the enthalpy value of phase change is increased relative to the enthalpy value of CPCM-88%.
In order to prove the photothermal conversion effect of the prepared three-dimensional basic manganese oxide nanorod foam composite phase-change material, photothermal test is carried out, and the photothermal conversion efficiency of CPCM-90% is 88.4% through calculation. As a result, as shown in FIG. 7, the photothermal effect was little changed when the amount of polyethylene glycol was added to a certain amount.
Combining the experimental results of examples 1-4 and comparative example 1, the following conclusions can be drawn:
1. the three-dimensional basic manganese oxide nanorod foam composite phase change material can be realized within the range of 75-88% of polyethylene glycol, and has a leakage-proof effect;
2. the DSC test result shows that the enthalpy value of the composite material integrally shows a rising trend due to the increase of the relative content of the phase-change material polyethylene glycol; when the relative content of polyethylene glycol is increased to 90%, the photothermal conversion efficiency is lower than 89%;
3. the photothermal effect test result shows that the photothermal effect of the composite material shows a descending trend along with the increase of the relative content of the polyethylene glycol, namely the reduction of the content of the basic manganese oxide nanorod, because the three-dimensional basic manganese oxide nanorod has the phenomena of light absorption performance and light reflection of the polyethylene glycol.
By combining various properties, the content of polyethylene glycol is 86 percent, namely the sample is named CPCM-86 percent as the best condition of the properties.

Claims (10)

1. A three-dimensional basic manganese oxide nanorod foam composite phase-change material is characterized in that: the three-dimensional basic manganese oxide nanorod foam is compounded with polyethylene glycol by a vacuum impregnation method, and is prepared by preparing basic manganese oxide nanorod hydrogel from manganese chloride tetrahydrate, sodium hydroxide and potassium permanganate and then freeze-drying the basic manganese oxide nanorod hydrogel.
2. The three-dimensional basic manganese oxide nanorod foam composite phase change material of claim 1, wherein: the micro-morphology of the three-dimensional basic manganese oxide nanorod foam is a three-dimensional pore channel structure formed by stacking basic manganese oxide nanorods, and the average diameter range of the basic manganese oxide nanorods is 150nm-260 nm.
3. The three-dimensional basic manganese oxide nanorod foam composite phase change material of claim 1, wherein: weight average molecular mass (M) of polyethylene glycolw) Is 2000-10000, has a molecular long-chain structure, and can be wound with the basic manganese oxide nano-rod to form a stable structure.
4. The preparation method of the three-dimensional basic manganese oxide nanorod foam composite phase change material according to claim 1, characterized by comprising the following steps:
step 1) preparing three-dimensional basic manganese oxide nanorod foam, namely preparing a mixed solution with a certain concentration from sodium hydroxide and potassium permanganate, then dropwise adding a manganese chloride tetrahydrate solution with a certain concentration into the mixed solution at a certain speed, fully stirring, reacting under certain conditions to obtain basic manganese oxide nanorod hydrogel, and finally freeze-drying to obtain the three-dimensional basic manganese oxide nanorod foam;
and step 2) preparing the three-dimensional basic manganese oxide nanorod foam composite phase-change material, weighing polyethylene glycol according to a certain mass ratio, and soaking the molten polyethylene glycol into the three-dimensional basic manganese oxide nanorod foam in a vacuum oven by adopting a vacuum impregnation method to obtain the three-dimensional basic manganese oxide nanorod foam composite phase-change material.
5. The method of claim 4, wherein: in the mixed solution in the step 1, the concentration of the sodium hydroxide solution is 0.4-0.8mol/L, and the concentration of the potassium permanganate solution is 0.08-0.15 mol/L; the concentration of the manganese chloride tetrahydrate solution is 0.2-0.8mol/L, the volume ratio of the mixed solution to the manganese chloride tetrahydrate solution is 0.7-1.1, and the dropping speed is 2-4 mL/min.
6. The method of claim 4, wherein: the reaction conditions of the step 1 are that the reaction temperature is 150-200 ℃, and the reaction time is 8-12 h; the freeze drying condition is that the freeze drying temperature is from minus 52 ℃ to minus 47 ℃, and the freeze drying time is 48-72 h.
7. The method of claim 4, wherein: and in the step 2, the mass ratio of the polyethylene glycol is 75-88% of the total mass of the composite phase change material.
8. The method of claim 4, wherein: the vacuum impregnation in the step 2 is carried out at the temperature of 60-90 ℃ for 10-12 h.
9. The application of the three-dimensional basic manganese oxide nanorod foam composite phase-change material as a phase-change material according to claim 1, wherein the three-dimensional basic manganese oxide nanorod foam composite phase-change material is characterized in that: the photothermal conversion efficiency is 89% -98%.
10. The application of the three-dimensional basic manganese oxide nanorod foam composite phase-change material as a phase-change material according to claim 1, wherein the three-dimensional basic manganese oxide nanorod foam composite phase-change material is characterized in that: the phase change temperature is 39-60 ℃, and the phase change latent heat is 122-163J/g.
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