CN110804301A - Polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material and preparation method thereof - Google Patents
Polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material which is prepared by chemical grafting reaction of polyethylene glycol (PEG), isocyanate (MDI) and hydroxypropyl cellulose (HPC), wherein the phase change material is subjected to phase change at the temperature of 80-120 ℃, is kept in a stable solid state after being kept for 1-2 hours and has no leakage of small molecules; the phase change material has solid-solid phase change, phase change temperature of 32-54 deg.c, phase change enthalpy of 99.5-130.8J/g and heat conductivity of 0.2494-0.5239W/m.K. The preparation method comprises the following steps: 1) preparing NCO-PEG prepolymer; 2) preparing a cross-linked polymer; 3) and (3) preparing the composite phase-change material. The invention has the following advantages: 1. the problem of leakage in the phase change process is solved; 2. the synthetic route is simple and pollution-free; 3. the thermal energy storage characteristic and the thermal stability are good; 4. the thermal conductivity of the phase-change material is effectively improved, the thermal conductivity is improved from 0.2494W/m.K to 0.5239W/m.K, and the utilization rate of heat is improved.
Description
Technical Field
The invention relates to the technical field of phase change energy storage materials, in particular to a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material and a preparation method thereof.
Background
With the development of economy in recent years, the problem of environmental pollution is gradually increased, the energy crisis is increasingly prominent, and the search for efficient and environment-friendly energy storage devices is urgent. The phase-change materials are used as one of high-efficiency thermal energy storage modes, and can absorb the heat of the environment in the process of converting the physical state or the molecular structure and release the heat to the environment when needed, so that the aim of controlling the temperature of the surrounding environment is fulfilled. The solar heat collecting and storing device is used in the fields of solar energy utilization, waste heat recovery, intelligent air conditioning buildings, agricultural greenhouses, battery heat management, clothing heat preservation, energy storage cookers, military camouflage and the like, and the application range is continuously expanded in recent years. The phase-change material can be divided into four materials of solid-solid, solid-liquid, solid-gas and liquid-gas according to the change of the state of the phase-change material in the phase-change process, and compared with the solid-gas and solid-liquid phase-change materials, the solid-solid phase-change material has the advantages of small volume change and no liquid generation in the phase-change process, and does not need to be packaged by special packaging materials, so the phase-change material has obvious advantages in the aspects of new energy development, secondary energy recycling and the like, and becomes a research hotspot of the phase-change material.
Polyethylene glycol is a non-toxic phase-change material with high phase-change enthalpy value, low supercooling degree and moderate phase-change temperature, but the development of polyethylene glycol is limited due to the two defects of the polyethylene glycol, namely the typical solid-liquid phase-change material, the need of a special packaging device for storage and low heat conduction. In order to effectively solve the above problems, a phase change material and a support material (skeleton) are compositely modified by physical entanglement or chemical crosslinking, and the phase change material is allowed to maintain its original shape (solid state) before and after phase change, that is, a so-called shape-stabilized phase change material is formed. Li Boqi discloses a preparation method of polyethylene glycol grafted white carbon black composite phase change material (Li Boqi, preparation method of polyethylene glycol/white carbon black grafted composite phase change material, Chinese invention patent, CN106554478A [ P ], 2017.04.05), but the amino group of white carbon black needs to be modified first, the synthetic route is complex, and the catalyst action is needed, which is not beneficial to industrial production.
Liujie, etc. prepares cellulose sponge by using microcrystalline cellulose, and then combines the prepared cellulose sponge with a molecular chain of polyethylene glycol by the action of a hydrogen bond (Liujie, Liuqing, preparation and performance characterization of polyethylene glycol/cellulose phase change material [ J ]. biomass chemical engineering, 2018, v.52; No.353(04): 5-10.), has long time consumption for preparing the cellulose sponge, and has low efficiency and does not improve the heat-conducting property of the polyethylene glycol.
According to the old wintersweet and the like, hydroxypropyl methylcellulose is used as a macromolecule to be grafted on a macromolecular chain of polyethylene glycol (the old wintersweet, a polyethylene glycol/hydroxypropyl methylcellulose solid-solid phase change material and a preparation method thereof, Chinese invention patent, CN 108276544A, 2018.07.13), the reaction time is long, the phase change enthalpy value is 89-95J/g, the thermal conductivity of the phase change material is not improved, and the application in the industry is limited.
Özgül Gök and the like utilize chemical grafting to invent a polyethylene glycol/cellulose phase change reaction composite material as a latent heat cold storage material (Ö. Gök, C. Alkan, Y. Konuklu, Developing a poly (ethylene glycol)/cellulose phase change reactive composite for coating application, and Solar Energy Materials and Solar Cells 191 (2019) 345 and 349.), the phase change enthalpy value of the material is 78-92J/G, the thermal conductivity of the phase change material has a larger promotion space, and the application in industry is limited.
Therefore, the hydroxypropyl cellulose is selected as a macromolecular chain to be grafted with the polyethylene glycol and then grafted with the carbon nano tube, so that the phase change enthalpy value and the heat conductivity of the phase change composite material can be improved, and the synthesized novel phase change material has wide application prospects in heat management and heat energy storage systems.
Disclosure of Invention
The invention aims to provide a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material and a preparation method thereof, and the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is applied as a phase change heat storage material. The problems of liquid leakage and low heat conduction of the current polyethylene glycol in the phase change process are solved by providing a new curing agent to modify the polyethylene glycol solid-liquid phase change material.
Provides a new curing agent, which prevents the polyethylene glycol from leaking during phase change and is environment-friendly.
In order to achieve the purpose, the invention adopts the technical scheme that polyethylene glycol (PEG) is used as a phase change material, 4, 4-diphenylmethane diisocyanate (MDI) is used as a cross-linking agent, hydroxypropyl methylcellulose (HPMC) is used as a curing agent, and a carbon nano tube is used as a heat conduction enhancer, and the method comprises the steps of stirring and dissolving according to a certain proportion, carrying out oil bath at a constant temperature, carrying out condensation reflux ultrasonic synthesis, drying and grinding under the condition of introducing inert gas by adopting a two-step condensation reaction method. As a solid-solid phase change material, HPC is used as a curing agent to play a role in restraining PEG liquid in the phase change process, and carbon nano tubes are used as a heat conduction enhancer to improve the heat conductivity.
The specific technical scheme for realizing the purpose of the invention is as follows:
a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is prepared by chemical grafting reaction of polyethylene glycol (PEG), isocyanate (MDI) and hydroxypropyl cellulose (HPC), the obtained phase change material has phase change at 80-120 ℃, and the phase change material still keeps stable solid state after heat preservation for 1-2 hours without leakage of small molecules; the phase change process of the phase change material is solid-solid phase change, the phase change temperature is 32-54 ℃, the phase change enthalpy value is 99.5-130.8J/g, and the thermal conductivity is 0.2494-0.5239W/m.K.
A preparation method of a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material comprises the following steps:
step 1) preparing an NCO-PEG prepolymer, namely respectively adding polyethylene glycol (PEG 4000) and isocyanate (4, 4-diphenylmethane diisocyanate, MDI) into a solvent N-N Dimethylformamide (DMF) to dissolve and prepare a solution, and mixing and reacting the polyethylene glycol solution and the isocyanate solution under certain conditions to obtain the NCO-PEG prepolymer, wherein the mass ratio of the polyethylene glycol to the isocyanate is 1: 2;
the mixing reaction condition is that under the condition of inert gas, the polyethylene glycol solution is slowly dripped into the isocyanate solution, oil bath is carried out at the constant temperature of 80-90 ℃, stirring reaction and condensation reflux are carried out for 2.5-3.5 hours;
step 2) preparing a cross-linked polymer, namely adding hydroxypropyl cellulose into a solvent to be dissolved to prepare a solution, adding the hydroxypropyl cellulose and an NCO-PEG prepolymer to the NCO-PEG prepolymer in the step 1 according to a certain mass ratio, and reacting under a certain condition to obtain the cross-linked polymer;
the mass ratio of the hydroxypropyl cellulose to the polyethylene glycol is 1 (1-4), and the reaction condition of the step 2 is that the mixture is subjected to oil bath at a constant temperature of 80-90 ℃, stirred for reaction and condensed and refluxed for 6-8 hours;
step 3) preparing a composite phase-change material, namely adding carbon nanotubes into a solvent for uniform ultrasonic dispersion, adding the carbon nanotubes into the crosslinked polymer prepared in the step 2 according to a certain mass ratio of the carbon nanotubes to the crosslinked polymer, and performing ultrasonic treatment, drying and grinding to obtain the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase-change material;
the ultrasonic condition is ultrasonic for 2-4 hours under the ultrasonic power of 70-80W, and the drying condition is that the sample is dried by blowing air for 24-48 hours under the condition of 75-85 ℃ and then dried in vacuum for 1-2 weeks under the condition of 35-50 ℃ until the sample is completely dried.
The thermal analysis of the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is performed by a Seney ev TG-DSC produced by SETARAM of France, the thermal stability is performed by an SDTQ600 produced by TA of America, the thermal conductivity is measured by a thermal bridge method thermal conductivity coefficient tester produced by Shanghai Duoqin instrument Limited, and the morphological analysis is performed by a JSM-6360LV produced by JEOL Ltd of Japan.
The polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is tested by infrared, and the results show that 3439 cm and 1111cm are observed in the composite phase change material-1The peak is the absorption peak of the stretching vibration of the hydroxyl and the ether bond. The new peaks appearing at 1350 and 1220cm-1 are probably the synthesized ester and amino absorption peaks, while the characteristic peak for the isocyanate group at 2887 cm-1 disappeared. The results show that the desired crosslinked copolymer was obtained.
The invention is tested by Differential Scanning Calorimetry (DSC), 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: -10-100 ℃. The result shows that the phase transition temperature of the composite phase change material is 32-54 ℃, and the phase transition enthalpy value is 99.5-130.8J/g.
The polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is subjected to thermogravimetric test, and the test conditions are as follows: the nitrogen flow rate is 100 ml/min, the heating rate is 10 ℃/min, and the temperature test range is 25-800 ℃. The result shows that the solid-solid phase change material still has higher stability before 300 ℃.
The polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is tested by a scanning electron microscope, and the magnification is 5 k. The result shows that the solid-solid phase change material has a laminar crystal structure with smooth surface, and the laminar crystal structure is the same as the crystal structure of PEG 4000.
Therefore, the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material has the following advantages compared with the prior art:
the invention provides a new curing agent for solid-liquid phase change material polyethylene glycol, so that the polyethylene glycol becomes a material with typical solid-solid phase change characteristics after being compounded, and the problem of liquid leakage of the polyethylene glycol in the phase change process is successfully solved;
the synthetic route is simple, a catalyst is not needed in the preparation process, the preparation condition is controllable, other byproducts are not generated, the application range of the curing agent is wide, and the curing agent is green, clean and environment-friendly and is beneficial to realizing industrial production;
thirdly, the material is kept in a stable solid state when heated to 120 ℃, and the material has better solid-solid phase change characteristics. The phase transition temperature is 32-54 ℃, the phase transition enthalpy is 99.5-130.8J/g, and the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase transition material still has good thermal stability before 300 ℃.
The carbon nano tube is added, so that the thermal conductivity of the phase-change material is effectively improved, the thermal conductivity is improved from 0.2494W/m.K to 0.5239W/m.K, and the utilization rate of heat is improved.
Therefore, the invention has wide application prospect in the field of solid-solid phase change material heat storage materials.
Description of the drawings:
FIG. 1 is a graph of the infrared spectra of SSPCM, PEG4000, MDI, HPC and CNT in example 1;
FIG. 2 is a comparison of SSPCM-75% before and after heating in example 1;
FIG. 3 is a graph comparing PEG4000 before and after heating in example 1;
FIG. 4 is a differential scanning calorimetry curve for PEG4000, SSPCM-75%, SSPCM-60%, SSPCM-80% in example 1, example 2, example 3;
FIG. 5 is the thermogravimetric curves of PEG4000, SSPCM-75%, SSPCM-60%, SSPCM-80% and HPC in example 1, example 2, example 3;
FIG. 6 is a scanning electron micrograph of PEG4000 in example 1;
FIG. 7 is a scanning electron micrograph of SSPCM-75% of example 1;
FIG. 8 is a comparison of SSPCM-60% before and after heating in example 2;
FIG. 9 is a comparison of SSPCM-80% in example 3 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
The preparation method of the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material comprises the following steps:
step 1) preparation of NCO-PEG prepolymer, adding 8g of PEG4000 and 1g of MDI into MDF respectively to be dissolved to prepare solution, slowly dripping the PEG4000 solution into the MDI solution under the condition of introducing inert gas, stirring and reacting under a constant temperature oil bath at 85 ℃, and condensing and refluxing for 3 hours to obtain the NCO-PEG prepolymer.
Step 2) preparing a cross-linked polymer, namely adding 1.5560g of hydroxypropyl cellulose into DMF (dimethyl formamide) for stirring and dissolving, adding into NCO-PEG prepolymer, carrying out oil bath at a constant temperature of 85 ℃, stirring for reaction, and carrying out condensation reflux for 7 hours to obtain the cross-linked polymer;
and 3) preparing the composite phase change material, namely adding 0.1067g of carbon nano tube into DMF (dimethyl formamide) for uniform ultrasonic dispersion, adding the mixture into the prepared cross-linked polymer, performing ultrasonic treatment for 2 hours in an ultrasonic machine with the power of 70W, performing forced air drying for 48 hours at 80 ℃, performing vacuum drying for 1 week at 50 ℃, and finally grinding a sample to obtain the composite solid-solid phase change material, wherein the sample is named SSPCM-75%.
To demonstrate that the expected crosslinked copolymer of the present invention was obtained, an infrared test analysis was performed, the infrared spectrum of which is shown in FIG. 1, and 3439 and 1111cm were observed in the composite phase change material-1The peak is the absorption peak of the stretching vibration of the hydroxyl and the ether bond. The new peaks appearing at 1350 and 1220cm-1 were the synthesized ester and amino absorption peaks, while the characteristic peak of the isocyanate group at 2887 cm-1 disappeared, the characteristic peak of the isocyanate group disappeared and the amino and ester groups were formed, indicating that the intended crosslinked copolymer was obtained.
In order to demonstrate the leakage prevention effect of the present invention, a heating comparative experiment was performed. Putting the SSPCM-75% obtained in example 1 and pure PEG4000 into an 80 ℃ oven at the same time, keeping the SSPCM-75% and pure PEG4000 for 2 hours, and observing the melting leakage condition of the sample before and after heating, wherein the experimental result is shown in figures 2 and 3, the sample SSPCM-75% is a stable solid at normal temperature, is put into the 80 ℃ oven, and keeps the solid state after keeping for 2 hours; whereas pure PEG4000 is solid at room temperature, but has become liquid upon heating. The SSPCM-75% of the composite phase change material still keeps stable solid after phase change, and no small molecule leaks, and the generation of the crosslinking prepolymer can be proved to solidify the sample.
In order to prove that the thermal performance of the prepared SSPCM-75% phase change is good, differential scanning calorimetry test analysis 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: -10-100 ℃. The result is shown in figure 4, the phase transition temperature of the composite phase change material is 36.4-53.5 ℃, the phase transition break value is 125.2-130.8J/g, which indicates that the SSPCM-75% has higher phase transition enthalpy value and proper phase transition temperature, and meets the application requirements.
To demonstrate that the SSPCM-75% obtained is thermally stable, thermogravimetric analysis was carried out under the following test conditions: the nitrogen flow rate is 100 ml/min, the heating rate is 10 ℃/min, and the temperature test range is 25-800 ℃. The result is shown in fig. 5, which shows that the solid-solid phase change material still has higher stability before 300 ℃, and meets the application value of the material at higher temperature.
In order to prove the influence of the modification method on the micro-morphology, the scanning electron microscope micro-morphology analysis is carried out on pure PEG4000 and SSPCM-75%, and the magnification is 5 k. The results of the experiment are shown in FIG. 6, SSPCM-75% is the same as PEG4000 in crystal structure, and is a layered crystal structure, however, the two materials are different in that: PEG4000 is a smooth lamellar crystalline structure; SSPCM-75% lamellar crystalline structure delamination is more pronounced. The improvement of the layering effect of the layered structure is beneficial to the solidification of PEG in the phase change process, namely the material of the invention solves the root cause of the leakage problem.
In order to demonstrate the influence of the carbon nanotubes on the performance of the composite material, a solid-solid phase change material without adding the carbon nanotubes was prepared, and a preparation method of the solid-solid phase change material without adding the carbon nanotubes in comparative example 1 was provided.
Comparative example 1
A method for preparing a solid-solid phase change material without adding carbon nanotubes, wherein the steps not specifically described in the specific steps are the same as the method for preparing the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material in the embodiment, except that: in the step 2, the content of the hydroxypropyl cellulose was 1.6627g, and the carbon nanotube was not added in the step 3.
In order to prove that the addition of the carbon nano tubes has influence on the thermal conductivity of the composite phase change material, the thermal conductivity of the composite phase change material without the carbon nano tubes is 0.2494W/m.K, and the result shows that under the same preparation conditions, the thermal conductivity of the solid-solid phase change material with the carbon nano tubes is improved to 0.5029W/m.K, so that the thermal conductivity of the solid-solid phase change material can be obviously improved by adding the carbon nano tubes.
In order to investigate the effect of the content of polyethylene glycol on the enthalpy value and solid-solid phase denaturation of the composite solid-solid phase change material, examples 2 and 3 were provided, the content of polyethylene glycol was 60% and 80%, respectively.
Example 2
A method for preparing a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material (the content of polyethylene glycol is 60%, and a sample is named as SSPCM-60%), which comprises the following steps: in the step 2, the content of hydroxypropyl cellulose was 4.2g, and the mass of the carbon nanotubes added in the step 3 was 0.133 g.
In order to prove that the prepared SSPCM-60% phase change thermal property is good, a Differential Scanning Calorimetry (DSC) test is carried out, the test method is the same as that of the example 1, the phase change temperature and the enthalpy of phase change of the obtained SSPCM-60% are shown in figure 4, the phase change temperature is 33.7-51.5 ℃, the enthalpy of phase change is 99.7-101.2J/g, and the enthalpy of phase change is reduced relative to the enthalpy of the SSPCM-75%.
In order to prove the leakage-proof effect of the invention, a heating comparison experiment is carried out, the experimental results before and after the composite phase-change material is heated are shown in fig. 8, and the phase-change material still belongs to a solid state after the composite phase-change material is heated, which shows that SSPCM-60% has a shaping phase-change effect.
Example 3
A method for preparing a polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material (the content of polyethylene glycol is 80%, and a sample is named as SSPCM-80%), which comprises the following steps: in the step 2, the content of hydroxypropyl cellulose is 0.9 g, and the mass of the carbon nanotube added in the step 3 is 0.1 g.
In order to prove that the prepared SSPCM-80% phase change thermal property is good, a Differential Scanning Calorimetry (DSC) test is carried out, the test method is the same as that of the example 1, the phase change temperature and the phase change enthalpy of the obtained SSPCM-80% are shown in figure 4, the phase change temperature of the phase change material is 35.6-51.7 ℃, the phase change enthalpy is 131.1-134.6J/g, and the phase change enthalpy is increased relative to the enthalpy of the SSPCM-75%.
In order to prove the leakage prevention effect of the invention, a heating comparison experiment is carried out, the experimental results before and after the composite phase change material is heated are shown in fig. 9, and the composite phase change material has part of small molecules leaked after being heated, which shows that although the enthalpy value of the composite phase change material is improved by adding too much polyethylene glycol, the shaping effect of the composite phase change material is also reduced.
Claims (6)
1. A polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material is characterized in that: the phase-change material is prepared by polyethylene glycol (PEG), isocyanate (MDI) and hydroxypropyl cellulose (HPC) through chemical grafting reaction, the phase-change material is subjected to phase change at the temperature of 80-120 ℃, and the phase-change material still keeps stable solid state after heat preservation for 1-2 hours and has no small molecule leakage.
2. The polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material according to claim 1, wherein: the phase change process of the phase change material is solid-solid phase change, the phase change temperature is 32-54 ℃, the phase change enthalpy value is 99.5-130.8J/g, and the thermal conductivity is 0.2494-0.5239W/m.K.
3. The preparation method of the polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material according to claim 1, which is characterized by comprising the following steps:
step 1) preparing an NCO-PEG prepolymer, namely respectively adding polyethylene glycol (PEG 4000) and isocyanate (4, 4-diphenylmethane diisocyanate, MDI) into a solvent N-N Dimethylformamide (DMF) to dissolve and prepare a solution, and mixing and reacting the polyethylene glycol solution and the isocyanate solution under certain conditions to obtain the NCO-PEG prepolymer, wherein the mass ratio of the polyethylene glycol to the isocyanate is 1: 2;
step 2) preparing a cross-linked polymer, namely adding hydroxypropyl cellulose into a solvent to be dissolved to prepare a solution, adding the hydroxypropyl cellulose and an NCO-PEG prepolymer to the NCO-PEG prepolymer in the step 1 according to a certain mass ratio, and reacting under a certain condition to obtain the cross-linked polymer;
and 3) preparing the composite phase-change material, namely adding the carbon nano tube into a solvent for uniform ultrasonic dispersion, adding the carbon nano tube into the crosslinked polymer prepared in the step 2 by using the carbon nano tube and the crosslinked polymer to meet a certain mass ratio, and performing ultrasonic treatment, drying and grinding to obtain the polyethylene glycol/hydroxypropyl cellulose carbon nano tube composite solid-solid phase-change material.
4. The production method according to claim 3, characterized in that: the mixing reaction condition of the step 1 is that under the condition of inert gas, the polyethylene glycol solution is slowly dripped into the isocyanate solution, oil bath is carried out at the constant temperature of 80-90 ℃, stirring reaction and condensation reflux are carried out for 2.5-3.5 hours.
5. The method of claim 4, wherein: the mass ratio of the hydroxypropyl cellulose to the polyethylene glycol in the step 2 is 1 (1-4), and the reaction condition in the step 2 is that the mixture is subjected to oil bath at a constant temperature of 80-90 ℃, stirred for reaction and condensed and refluxed for 6-8 hours.
6. The method of claim 4, wherein: the step 3 ultrasonic treatment is carried out for 2-4 hours under the ultrasonic power of 70-80W, and the step 3 drying condition is that the sample is dried by blowing air at 75-85 ℃ for 24-48 hours and then dried in vacuum at 35-50 ℃ for 1-2 weeks until the sample is completely dried.
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| CN115260771B (en) * | 2022-06-28 | 2023-09-15 | 安徽省煤炭科学研究院 | Mining high-flexibility phase-change cold storage material and preparation method thereof |
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