CN113861942A - Organic-microcapsule phase change material, preparation method thereof and application thereof in battery thermal management system - Google Patents
Organic-microcapsule phase change material, preparation method thereof and application thereof in battery thermal management system Download PDFInfo
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- CN113861942A CN113861942A CN202111072370.2A CN202111072370A CN113861942A CN 113861942 A CN113861942 A CN 113861942A CN 202111072370 A CN202111072370 A CN 202111072370A CN 113861942 A CN113861942 A CN 113861942A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the application field of a microcapsule composite material design synthesis technology in battery thermal safety science and engineering, and particularly relates to preparation of a microcapsule composite phase change material, which is practically applied to a thermal management system of a new energy automobile power battery. The preparation method comprises the steps of taking phase-change material paraffin as a core material, taking a methanol modified melamine formaldehyde prepolymer MMF as a shell material, and carrying out emulsion polymerization reaction under the action of a dispersant styrene-maleic anhydride copolymer SMA to obtain a target product. The battery and the heat sink arrangement mode developed by combination design can be directly applied to a commercial battery thermal management system. The invention has the advantages that: the preparation process is simple, the cost is low, the scientific and technological achievements are easy to convert, the potential economic value is high, and the social and ecological benefits are outstanding.
Description
Technical Field
The invention belongs to the technical field of composite phase change material design synthesis and battery safety science and engineering, and particularly relates to an organic-microcapsule phase change material, a preparation method thereof and application thereof in a battery thermal management system.
Background
During the use of electronic devices, a large amount of heat is often accumulated inside the battery due to the influence of factors such as changes in ambient temperature and heat release from reactions inside the battery. The problem of overheating of an electronic device not only affects its functionality, but also creates challenges for its security. Therefore, it is highly desirable to develop effective thermal management techniques for electronic devices.
At present, phase-change materials are generally adopted to absorb heat generated by electronic devices, so that the electronic devices are maintained at almost constant optimal working temperature for a long time, the thermal safety hidden danger is reduced, and the service life is prolonged. The phase-change material is divided into three categories of inorganic, organic and mixed phase-change materials, wherein the organic phase-change material has the advantages of good chemical stability, high thermal reliability, small supercooling degree, reasonable cost and the like. However, when the organic phase-change material is directly used, the defects of easy leakage, corrosion of devices, easy phase separation and the like exist, and the current single phase-change material compound does not have comprehensive and excellent physical, chemical, kinetic, thermodynamic and economic properties, and the problems can be effectively solved by means of structural modification, additive addition, storage system optimization and the like, so that the composite phase-change material with high comprehensive performance is prepared.
Nanometer microencapsulation is an effective technology, which can improve the thermal conductivity of the composite material, improve the leakage problem of the phase-change material in the melting process, and slow down the possible interaction between the active substance and the surrounding matrix. Therefore, the nano microcapsule composite phase change material can be applied to electronic products, particularly battery thermal management systems, and can maintain the stability of energy storage and release chemical reactions.
Disclosure of Invention
The invention provides an organic-microcapsule phase change material, a preparation method thereof and application thereof in a battery thermal management system, aiming at solving the problems in the design and synthesis of the existing microcapsule composite phase change material.
The invention is realized by the following technical scheme: an organic-microcapsule phase change material is prepared by taking a phase change material as a core material, taking a methanol modified melamine formaldehyde prepolymer (MMF) as a shell material, adding a heat-conducting filler additive, and carrying out emulsion polymerization reaction under the action of a dispersing agent to obtain a target product, namely the organic-microcapsule phase change material; wherein: the phase-change material is paraffin, twelveAny one of alcohol, tetradecanol or octadecane; the heat-conducting filler is carbon nano tube CNT and nano aluminum oxide Al2O3And/or nano zinc oxide (ZnO); the dispersing agent is styrene-maleic anhydride copolymer SMA.
Further, the core material is Paraffin Paraffin, the shell material is a methanol-modified melamine formaldehyde prepolymer MMF, the dispersing agent is styrene-maleic anhydride copolymer SMA, and the mass ratio of the core material to the shell material to the dispersing agent is as follows: 1: 0.7-1: 1.
Further, the organic-microcapsule phase change material is in a powder shape, the particle size is 1-10 mu m, the phase change enthalpy is 100-200 kJ/kg, and the phase change temperature is 30-60 ℃.
The invention also provides a preparation method of the organic-microcapsule phase change material, which comprises the following specific steps:
(1) preparation of MMF shell material: adding melamine into a urotropine and formaldehyde solution, stirring at a high speed to fully dissolve the substances, heating in a water bath to 80 ℃, continuously stirring for reacting for 1 hour, adding triethanolamine to adjust the pH value to 9 after the solution is clarified, and uniformly stirring to obtain a product, namely a melamine-formaldehyde prepolymer MF; adding methanol into the MF solution, and modifying to obtain MMF;
(2) preparing an SMA solution: adding deionized water into a 250 mL three-neck flask provided with a high-speed stirrer, slowly adding SMA powder under the stirring state, continuously stirring until suspension without visible particles is formed, then quickly adding 10wt% NaOH solution, adjusting the pH value to 8, and continuously stirring for 1 hour, wherein the process is always carried out in a water bath kettle at 50 ℃;
(3) preparing a microcapsule emulsion: adding 115 g of phase change material into the SMA solution, and mechanically stirring in a high-speed dispersion machine for 10 minutes, wherein the liquid is in a milky emulsion state; adding 20 g of the MMF shell material prepared in the step (1) and 5 g of heat-conducting filler, accelerating stirring, setting the temperature rise rate of an instrument to be 2 ℃/min, raising the heating temperature to 80 ℃, keeping the temperature, and continuously stirring for 1.5 hours to obtain an emulsion liquid product, namely microcapsule emulsion;
(4) preparation of the final product organic-microencapsulated phase change material: and (3) washing the emulsion liquid product obtained in the step (3) by using deionized water, filtering, drying the obtained substance in an oven at 40 ℃ for 12 hours, and grinding the dried substance into powder to obtain the final product, namely the organic-microcapsule phase change material.
After the melamine is added in the step (1) for reaction, clarifying the solution, detecting whether a cloud point appears, dripping a drop of reactant into deionized water to obtain a white precipitate which is the cloud point, and adding triethanolamine to adjust the pH value after the cloud point does not appear.
The application of the organic-microcapsule phase change material in a battery thermal management system comprises the following specific application methods: grinding the prepared organic-microcapsule phase change material to obtain fine powder with the diameter of 100-phase and 200 mu m; filling the powder into a battery thermal management mold, and completely wrapping the battery; and monitoring the temperature change of the battery in the charging and discharging process by using a thermocouple temperature measuring device to obtain the real-time temperature, the average temperature and the temperature difference of the battery in different working environments. The packaging material in the battery thermal management system is any one of aluminum alloy, copper or iron, and the heat radiating fins are foamed nickel or foamed copper.
The appearance of the microcapsule is observed by a scanning electron microscope, and the result shows that the microcapsule is in a uniform microcapsule-shaped sphere structure, and the heat-conducting filler is uniformly dispersed around the microcapsule without influencing the whole structure. The paraffin core composite phase change material is characterized by utilizing Fourier transform infrared spectroscopy, and the result shows that: the substances are only purely physically crosslinked, new chemical substances are not generated, and the properties of the phase-change material are not influenced. Differential Scanning Calorimetry (DSC) results show that the measured value of the melting enthalpy of the composite phase-change material in the heating/cooling process is obviously higher than the theoretical value, and the increment percentage of the melting enthalpy is respectively improved by 48.7 percent, 59.4 percent and 84.9 percent. In addition, through the battery charge and discharge test and leakage test results, compared with aluminum oxide and zinc oxide, the heat storage and heat dissipation performance of the material is obviously improved by adding the CNT. In addition, thermal stability experiments show that the thermal stability performance of the battery is excellent, and the battery has wide application prospects in battery thermal management systems and energy storage.
According to the invention, the phase-change material enables the highest temperature of the battery during working to be reduced by more than 2 ℃, has an obvious heat dissipation effect, has good functions of heat conduction, temperature regulation, energy storage and the like, and can be applied to the fields of heat storage, heat dissipation of electronic equipment and the like.
Drawings
FIG. 1 is a schematic diagram of a synthetic reaction of MF;
FIG. 2 is a schematic diagram of the reaction of MMF synthesis;
fig. 3 is a schematic diagram of a battery thermal management system, in which: the left figure is a schematic diagram of the battery arrangement; the numbers 1, 2, 3 and 4 in the left figure are four different placing position distributions of the battery; (a) the (b) and (c) are respectively different battery arrangement modes;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the organic-microcapsule phase-change material obtained in example 1-example 3; in the figure: (a) and (b) Paraffin-MMF obtained in comparative example 1; (c) and (d) Paraffin-MMF-Al from example 22O3(ii) a (e) And (f) is Paraffin-MMF-ZnO from example 3; (g) and (h) is the Paraffin-MMF-CNT obtained in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of the organic-microcapsule phase-change material obtained in example 1-example 3;
FIG. 6 is an infrared spectrum of the organic-microcapsule phase-change material obtained in example 1-example 3;
FIG. 7 is a Differential Scanning Calorimeter (DSC) curve of the organic-microcapsule phase-change material obtained in example 1-example 3;
FIG. 8 is a Thermogravimetric (TG) curve and a Differential Thermogravimetric (DTG) curve of the organic-microcapsule phase change material obtained in example 1-example 3; in the figure: a is a TG curve; b is a DTG curve;
FIG. 9 is a graph showing the thermal conductivity of the organic-microcapsule phase change materials obtained in examples 1 to 3;
FIG. 10 shows the results of a leakage test of pure paraffin and the organic-microcapsule phase change materials obtained in examples 1 to 3;
FIG. 11 is a graph showing the leakage rate of pure paraffin and the organic-microcapsule phase change materials obtained in examples 1 to 3;
fig. 12 is a heat dissipation performance test chart; in the figure: a is a heat dissipation performance test chart of Paraffin-MMF-CNT; b is Paraffin-MMF-Al2O3The heat radiation performance test chart; c is the heat dissipation performance of Paraffin-MMF-ZnOAnd (6) testing the graph.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that preferred examples in the following description are only examples, and the described embodiments are some, but not all, embodiments of the present invention; 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.
Materials: paraffin as phase change material (phase change temperature 46 deg.C, Shanghai Joule wax Co., Ltd.); carbon nanotubes (L = 10-20 μm, d > 50 nm, alatin); melamine (99%, alatin); methanol (AR, 99.5%, alatin); formaldehyde (AR, purity: 37.0-40.0 wt%, Chinese medicine); triethanolamine (AR, alatin); glacial acetic acid (AR, 99.5%, alatin); the dispersant is Styrene-maleic anhydride (SMA) copolymer (Shanghai Sancheng international trade Co., Ltd.); nonionic surfactant Span-80 (alatin); sodium hydroxide (AR, 96%, granular, alatin); nano zinc oxide (99.8% metals basis, 50 ± 10 nm); nanometer alumina (99.99% metals basis, crystal form gamma, less than or equal to 20 nm); urotropin (AR, ≧ 99%, alatin); three-star 18650 cells (with a capacity of 2500 mAh).
The preparation method of the MMF comprises the following steps: adding 0.15 g of urotropine and 50 mL of formaldehyde solution into a 250 mL three-necked flask provided with a stirrer, a condenser tube and a thermometer, stirring at a high speed to fully dissolve the substances, adding 10 g of melamine, continuously stirring, heating in a water bath to 80 ℃, continuously stirring for reacting for 1 hour, after the solution is clarified, dripping a drop of reactant into deionized water, if no white precipitate appears, detecting that the cloud point does not appear any more, adding triethanolamine to adjust the pH value to be 9, and uniformly stirring to obtain a product MF. And adding 60 mL of methanol into the MF reaction liquid, and modifying the mixture to obtain the MMF, wherein the synthetic reaction principle of the MF is shown in a figure 1, and the synthetic reaction principle of the MMF is shown in a figure 2.
Preparation of SMA solution: deionized water is added into a 250 mL three-neck flask with a high-speed stirrer, 10 g of SMA powder is slowly added under the stirring state, the stirring is continued until suspension without visible particles is formed, then 10wt% NaOH solution is quickly added, the stirring is continued for 1 hour after the pH value is adjusted to be 8, the process is always carried out in a water bath kettle at 50 ℃, and 5wt% of SMA solution is obtained.
Specific examples of organic-microcapsule phase change materials are as follows:
example 1: preparation of Paraffin-MMF-CNT
150 mL of SMA solution is weighed into a three-neck flask, 115 g of paraffin is added, and mechanical stirring is carried out for 10 minutes at 500r/min under the strong stirring of a high-speed dispersion machine until the paraffin is completely dissolved, so that milky liquid is presented. Subsequently 20 g of MMF was added and stirring was continued for 5 minutes, followed by 5 g of CNT, accelerated stirring, increasing the temperature to 80 ℃ with a temperature increase rate of 2 ℃/min, and stirring was continued for 1.5 hours while maintaining the temperature to obtain an emulsion. Washing the product with deionized water for 3 times, drying and grinding to obtain target product powder.
Application of the obtained Paraffin-MMF-CNT in a battery thermal management system: the design of the battery thermal management system and the application method of the phase change material are shown in fig. 3. The specific application method comprises the following steps: grinding the prepared Paraffin-MMF-CNT into powder with the diameter of 100-; and monitoring the temperature change of the battery in the charging and discharging process by using a thermocouple temperature measuring device to obtain the average temperature of batteries (numbered as 1, 2, 3 and 4) in different working environments and placing positions. As can be seen from the top view of fig. 3, in addition to the phase change material, heat sinks (black lines) are added, and the two are combined to form a composite thermal management system.
The step needs to be described, the purpose of adding the SMA solution is to emulsify the paraffin droplets to the particle size of 100-200 nm, so that the paraffin droplets are charged with negative charges, which is favorable for forming a stable oil-in-water structure; the MMF solution is positively charged, and the positive and negative charges attract each other under the action of high-speed stirring, so that a stable core-shell structure is formed.
Example 2: Paraffin-MMF-Al2O3The preparation of (1): 5 g of nano Al was used for 5 g of CNT in example 12O3Alternatively, the remaining methods are as described in example 1.
The obtained Paraffin-MMF-Al2O3Application in a battery thermal management system: Paraffin-MMF-Al was used for Paraffin-MMF-CNT in example 12O3Alternatively, the other methods were the same as those described in example 1.
Example 3: preparation of Paraffin-MMF-ZnO: the 5 g CNTs from example 1 were replaced with 5 g nano ZnO and the rest of the procedure was as described in example 1.
The application of the obtained Paraffin-MMF-ZnO in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with Paraffin-MMF-ZnO, and the procedure was otherwise as described in example 1.
Example 4: preparing dodecanol-MMF-ZnO: the 115 g of paraffin wax from example 1 was replaced with 115 g of dodecanol; the 5 g CNTs from example 1 were replaced with 5 g nano ZnO and the rest of the procedure was as described in example 1.
The obtained dodecanol-MMF-ZnO can be applied to a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with dodecanol-MMF-ZnO as in example 1, and the procedure was otherwise the same as that described in example 1.
Example 5: dodecanol-MMF-Al2O3The preparation of (1): the 115 g of paraffin wax from example 1 was replaced with 115 g of dodecanol; 5 g of nano Al was used for 5 g of CNT in example 12O3Alternatively, the remaining methods are as described in example 1.
The obtained dodecanol-MMF-Al2O3Application in a battery thermal management system: Paraffin-MMF-CNT in example 1 was treated with dodecanol-MMF-Al2O3Alternatively, the other methods were the same as those described in example 1.
Example 6: preparation of octadecane-MMF-CNT: the 115 g of paraffin wax in example 1 was replaced with 115 g of octadecane; the rest of the procedure is as described in example 1.
The obtained dodecanol-MMF-Al2O3In a batteryApplication in thermal management systems: Paraffin-MMF-CNT in example 1 was treated with dodecanol-MMF-Al2O3Alternatively, the other methods were the same as those described in example 1.
Example 7: preparation of tetradecanol-MMF-CNT: the 115 g of paraffin wax from example 1 was replaced with 115 g of tetradecanol; the rest of the procedure is as described in example 1.
Use of the resulting tetradecanol-MMF-CNT in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with tetradecanol-MMF-CNT, and the procedure was otherwise as described in example 1.
Comparative example 1: preparation of Paraffin-MMF: the same procedure as described in example 1 was followed except that 5 g of CNT thermal conductive filler was not added.
Characterization of relevant properties was performed on the organic-microcapsule phase change materials obtained in examples 1 to 3 and comparative example 1:
example 1: the appearance of the sample is observed on a JEOL JSM-7001F type SEM, the result is shown in figure 4, and the result shows that: the appearance of the sample is a spherical structure, and the particle size is as follows: Paraffin-MMF-ZnO and Paraffin-MMF-Al2O3The particle size of the nano-Al particle is 200-500 nm, the particle size of the Paraffin-MMF-CNT is 300-500 nm, and CNT and nano-Al are added2O3And nano ZnO has little influence on the overall appearance of the shell layer.
Fig. 4(a) shows that the pure Paraffin-MMF material has spherical particles with a relatively smooth surface, whereas in (b) (c) (d) the surface of the spherical particles is found to be rough. The formation of the microcapsule structure mainly depends on the interfacial tension among the phase-change material, the shell material and the surfactant. From fig. 4(c) it is observed that the microcapsules show an aggregation behavior, which may result in a slight increase of the size of some neighboring particles. Some exposed tubes are clearly visible in fig. 4(d), indicating the presence of CNTs in the microcapsules. CNTs have a large aspect ratio and a length greater than the grain size of the microcapsules, so that carbon nanotubes may not be completely encapsulated in the microcapsules and a portion of the nanotubes may protrude from the microcapsules. Nevertheless, nano Al is added2O3Morphology of Paraffin-MMF of Nano ZnO and CNT and of Paraffin-MMF without any filler additionThe appearance is similar, which shows that the addition of the heat-conducting fillers in the shell layer has little influence on the overall appearance.
Example 2: the XRD spectrum of the sample (instrument model: Bruker D8 ADVANCE Germany, Cu K alpha radiation) shows as shown in figure 5, the main characteristic peak is almost consistent with the phase-change paraffin of the core material, which shows that the core-shell material is only physically combined and does not generate chemical reaction to generate new substances.
The XRD pattern of pure Paraffin-MMF at room temperature shows the expected characteristic diffraction peaks located on the (100) and (110) crystal planes at 2 theta =21.77 ° and 24.08 °. In addition, nano Al can be obviously found2O3Are located on (121) and (131) planes of a β -crystal phase of 2 θ =30.27 ° and 36.52 °, characteristic diffraction peaks of nano ZnO are located on (100), (002) and (101) crystal planes of 2 θ =31.85 °, 34.50 ° and 36.36 °, and characteristic diffraction peaks of CNT are located on (131) crystal plane of 2 θ =25.96 °. No other characteristic peaks than the above were found, indicating that these fillers were stably bound to the microcapsules. Furthermore, the characteristic peaks of pure Paraffin-MMF show broad peaks in the region 2 θ =15-30 °, indicating that the material is largely amorphous in nature, i.e. it is verified that the lack of a highly crystalline structure is caused by microencapsulation between the phase change material and the shell material. The characteristic peaks of the composite Paraffin-MMF-filler, apart from the pure Paraffin-MMF, only remain the peaks of the corresponding filler, indicating that there is only a physical bond between them and no chemical reaction takes place.
FIG. 6 shows an infrared spectrum of the above sample. 2916 and 2850cm in Paraffin-MMF microcapsules without any filler-1The absorption peak at (A) belongs to the group at-CH3and-CH2Stretching vibration of CH in-1468 cm-1The absorption peak at (A) belongs to-CH3and-CH2C-H bending vibration of-C-H. 1032cm-1The absorption peak at (a) corresponds to the tensile vibration of C-OH. They are characteristic peaks of paraffin. 700cm-1The peak at is-NH2Out-of-plane bending vibration of N-H. 3413cm-1Peak at 1738cm is the overlap of the tensile oscillations of N-H and O-H-1The peak at (b) is C = O tensile vibration of — CHO. 1179cm-1The absorption peak is C-O-C stretching vibrationAnd (6) moving. The above peaks are characteristic peaks of MMF resins. Notably, Paraffin-MMF and nano Al-containing2O3The spectra of the composite phase-change material of the nano ZnO and CNT hybrid filler are similar, which shows that the chemical structure of the microcapsule is not greatly influenced by the added filler. In addition, no characteristic peak of other substances except the characteristic peak of the material shows that the core-shell material is only physically combined and does not generate chemical combination to generate a new substance.
Example 3: thermal stability is a key parameter for checking the performance of the phase change material, and fig. 8 is a TG curve and a DTG curve of the organic-microcapsule phase change material obtained in examples 1 to 3.
As shown in graph A, the thermogravimetric curves of all samples were divided into two steps, the first stage being associated with paraffin pyrolysis in the temperature range of 100-350 ℃ and the second stage being associated with MMF shell degradation in the temperature range of 350-600 ℃. Paraffin-MMF without any filler begins to degrade at about 120 deg.C, with the fastest loss of Paraffin mass at 280 deg.C and the fastest loss of MMF shell mass at 456 deg.C (in FIG (B)), while Paraffin-MMF-Al after the addition of filler2O3The two peak weight loss rate temperatures of Paraffin-MMF-ZnO and Paraffin-MMF-CNT are 303 ℃, 318 ℃, 320 ℃, 460 ℃, 470 ℃ and 550 ℃ respectively. The results show that the addition of different fillers can significantly slow down the thermal decomposition rate, Al2O3ZnO, CNT and MMF form an inorganic/organic composite shell which can be used as a protective layer to resist heat for damaging a shell structure, and the nanofiller is tightly combined with the MMF shell, so that the physical and mechanical properties of the nanofiller are improved, the pyrolysis of the polymer shell is delayed, and the nanofiller has more stable performance than the MMF shell.
To further understand the effect of the phase change material on the temperature driven phase change, samples of the organic-microcapsule phase change material obtained in examples 1-3 were characterized by differential scanning calorimetry. The phase transition temperature and the phase transition latent heat of the material are measured by DSC (model: METTLER TOLEDO DSC 2), and the measuring method comprises the following steps: 5-8 mg of the sample was sealed in an aluminum crucible at a temperature rise rate of 5 deg.C/min with a constant nitrogen flow of 20 mL/min, and differential scanning calorimetry characterized the latent heat storage capacity of the material by comparing the temperature of the exothermic (crystallization, positive signal) or endothermic (melting, negative signal) transition.
The experimental results are shown in FIG. 7, where pure Paraffin-MMF has an enthalpy of phase transition of 93.93J/g and a melting point of 48.96 ℃; the enthalpy of phase transition of the Paraffin-MMF-CNT is 173.68J/g, the melting point is 49.86 ℃; Paraffin-MMF-Al2O3The enthalpy of phase change of (a) is 139.67J/g, the melting point is 48.70 ℃; the enthalpy of phase change of the Paraffin-MMF-ZnO is 149.72J/g, and the melting point is 49.80 ℃; both higher than the melting point of pure paraffin at 46 ℃; has good thermal stability.
As shown in FIG. 7, it can be seen that the differential scanning calorimetry curves for the pure Paraffin-MMF and composite Paraffin-MMF filler materials have substantially the same trend, with their T's being substantially the samemThe values are 48.96 deg.C, 48.70 deg.C, 49.80 deg.C and 49.86 deg.C, respectively, but there is still some deviation between them. It is generally believed that T of the composite Paraffin-MMFmT with Paraffin-MMFmThe small deviations in (a) are caused by the interaction between the materials. The curve analysis results of the four samples show that a single melting peak, namely only one endothermic peak appears in the melting process, indicates that the material is a stable phase transfer material, so that the four materials can be used as a potential heat storage material and have excellent thermal stability.
In addition, enthalpy of fusion (. DELTA.H)m) Is an important parameter directly related to the storage and release of latent heat, indicating the heat storage capacity. Paraffin-MMF-Al2O3Paraffin-MMF-ZnO and Paraffin-MMF-CNT have similar phase transition properties to Paraffin-MMF, because the phase transition material (Paraffin) microencapsulation does not chemically react with the shell material or the emulsifier, which still retains its original heat absorbing capacity in the shell. They have high melting enthalpy values of 93.93, 139.67, 149.72 and 173.68J/g, respectively, indicating their excellent ability to store and release energy generated during phase transition. Microencapsulation of phase change materials, particularly with the addition of CNTs and nano-metal particles, improves heat transfer efficiency by reducing the barrier to paraffin nucleation within the microcapsules and inhibiting undercooling, indicating that they are potentially excellent energy storage materials.
Example 4: thermal conductivity is reflective of phase change material heat transferAn important parameter for efficiency, the higher thermal conductivity, means that the phase change material has a relatively fast heat absorption-release capacity during the phase change process. Nano inorganic filler (Al)2O3ZnO and CNT) has higher thermal conductivity, and the composite phase-change material prepared by the invention is expected to improve the thermal conductivity of the matrix. Figure 9 shows the thermal conductivity of the microcapsules. Wherein the thermal conductivity of the paraffin is only 0.12W/m.k when Al is used2O3The thermal conductivity of the composite Paraffin-MMF-filler is 0.2874W/m.k, 0.2821W/m.k and 0.4988W/m.k respectively when the amount of ZnO and CNT is 10wt%, which are respectively improved by 30.9%, 28.5% and 127.2% compared with the pure Paraffin-MMF (0.2195W/m.k). It can be seen that the addition of the CNT multiplies the thermal conductivity of the phase-change material matrix, which is attributed to the excellent thermal conductivity of the CNT itself, and at the same time, the CNT forms a composite shell with the MMF, and the CNTs interconnected outside the shell indirectly form a high thermal conductivity network, thereby significantly improving the heat transfer capability of the interface, and rapidly enhancing the thermal conductivity of the microcapsule.
Example 5: and (3) detecting the leakage prevention performance: easy leakage is another major defect affecting the performance of phase change materials, so the invention is at the melting temperature (T) of pure paraffinmThe leakage test was carried out above =46 ℃). The sample block was placed on a piece of filter paper and heated in an oven at 25, 40, 60, 80 and 100 ℃ for 1h, respectively, and the change in the surface of the filter paper over time was recorded. As shown in FIG. 10, after heating at 60 ℃ for 1h, the Paraffin wax sample had melted over a large area, and the surface of the Paraffin-MMF sample, although intact, had partially leaked, as compared to Paraffin-MMF, Paraffin-MMF-Al2O3And the Paraffin-MMF-ZnO sample both leaked to different degrees, and only the Paraffin-MMF-CNT sample left no trace of leakage on the filter paper surface throughout the 1h test at 60 ℃, indicating that the presence of CNT inhibited its leakage.
After further increasing the temperature to 80 ℃ and heating for 1h, the samples containing Paraffin-MMF-CNT had a small amount of liquid leakage, indicating that the MMF shell had been thermally broken at this temperature, causing the Paraffin wax in the liquid state to leak out, and we found that the coating rate of the microcapsules was not 100% through electron micrographs thereof, and thus it was possible that the microcapsules were not coatedSome of the paraffin leaks out of the MMF shell. The remaining composites all developed some Paraffin leakage, interestingly, Paraffin-MMF-Al at different temperatures2O3The leakage degree of the sample is always larger than that of the Paraffin-MMF-ZnO sample, which is caused by the nano Al2O3That is, the smaller the size of the nano particles, the more easily agglomeration occurs, and although the dispersant has been added, Al is added2O3The agglomeration phenomenon of the particles is more common than that of ZnO, so that the particles are unevenly dispersed outside the microcapsule shell, a second shell cannot be effectively formed, and the MMF shell is perfectly coated, so that the second shell cannot effectively slow down the leakage phenomenon when the MMF shell is cracked and the liquid core material leaks in the temperature rise and heat absorption process. Due to the large length-diameter ratio of the CNT, a CNT network can be formed, a shell in a shape of a wool ball is generated, and when the MMF shell is broken, the leakage of the CNT shell can be effectively slowed down, so that the performance of the CNT shell is improved. At 100 ℃, leakage phenomena occur to different degrees in all samples, so the material is only suitable for being used under medium and low temperature conditions. The results of the leak test confirm that CNTs provide a mechanical strength and a thermally conductive structural network to the Paraffin-MMF and inhibit its leakage. It is clear from leakage experiments that microencapsulation techniques are crucial for the preparation of shape-stable phase change materials and further contribute to the extension of the range of applications of phase change materials. When the core-shell structure microcapsule composite phase change material is applied to a battery thermal management system, the normal working temperature of a battery is maintained, and the fire risk caused by organic matter leakage is reduced.
In addition, the data of the leakage experiment are collated, and the leakage rate of different samples is calculated. As shown in fig. 11, the microencapsulation technique can effectively inhibit the leakage of paraffin, and the degree of inhibition varies among different fillers. At 100 ℃, the leakage rate of pure paraffin is 98%, which may be due to impurities in the paraffin raw material; whereas the leakage rate of the Paraffin-MMF is 30%, inhibiting the leakage of part of the Paraffin to a certain extent, among the samples of three different fillers, CNT is undoubtedly the best choice, the maximum leakage rate of which is only 12.5%, and the leakage rate of the samples increases significantly with increasing ambient temperature.
Example 6: the organic-microcapsule phase change materials obtained in examples 1 to 3 adopt the arrangement mode shown in fig. 3(a), the heat dissipation performance test result is shown in fig. 12, and through test and research, the average temperature of the battery in four different environments is obviously reduced by about 2 ℃ compared with that of pure paraffin, which shows that the sample has an obvious heat dissipation effect on the working environment of the battery, so that the normal working temperature of the battery can be effectively protected, and the possibility of fire occurrence of the battery is reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. An organic-microencapsulated phase change material characterized by: taking a phase change material as a core material, taking a methanol modified melamine formaldehyde prepolymer MMF as a shell material, adding a heat-conducting filler additive, and carrying out emulsion polymerization reaction under the action of a dispersing agent to obtain a target product, namely an organic-microcapsule phase change material; wherein: the phase-change material is any one of paraffin, dodecanol, tetradecanol or octadecane; the heat-conducting filler is carbon nano tube CNT,Nano alumina Al2O3And/or nano zinc oxide (ZnO); the dispersing agent is styrene-maleic anhydride copolymer SMA; the raw materials in percentage by mass are as follows: 70-85wt% of a phase change material; 5-10wt% of a thermally conductive filler; 5-15wt% shell material; 5wt% of a dispersant.
2. The organic-microcapsule phase-change material according to claim 1, wherein: the core material is paraffin, the shell material is a methanol modified melamine formaldehyde prepolymer, the dispersing agent is styrene-maleic anhydride copolymer SMA, and the mass ratio of the core material to the shell material to the dispersing agent is as follows: 1: 0.7-1: 1.
3. The organic-microcapsule phase-change material according to claim 1, wherein: the organic-microcapsule phase change material is in a powder shape, the particle size is 1-10 mu m, the phase change enthalpy is 100-200 kJ/kg, and the phase change temperature is 30-60 ℃.
4. A method for preparing the organic-microcapsule phase change material according to any one of claims 1 to 3, characterized in that: the method comprises the following specific steps:
(1) preparation of MMF shell material: adding melamine into urotropine and formaldehyde solution, stirring at a high speed to fully dissolve the substances, heating in a water bath to 80 ℃, continuously stirring for reacting for 1 hour, adding triethanolamine to adjust the pH value to 9 after the solution is clarified, and uniformly stirring to obtain a product melamine-formaldehyde prepolymer MF; adding methanol into the MF solution, and modifying to obtain MMF;
(2) preparing an SMA solution: adding deionized water into a 250 mL three-neck flask provided with a high-speed stirrer, slowly adding SMA powder under the stirring state, continuously stirring until suspension without visible particles is formed, then quickly adding 10wt% NaOH solution, adjusting the pH value to 8, and continuously stirring for 1 hour, wherein the process is always carried out in a water bath kettle at 50 ℃;
(3) preparing a microcapsule emulsion: adding 115 g of phase change material into the SMA solution, and mechanically stirring in a high-speed dispersion machine for 10 minutes, wherein the liquid is in a milky emulsion state; adding 20 g of MMF shell material prepared in the step (1) and 5 g of heat-conducting filler, accelerating stirring, setting the temperature rise rate of an instrument to be 2 ℃/min, raising the heating temperature to 80 ℃, keeping the temperature, and continuously stirring for 1.5 hours to obtain an emulsion liquid product, namely microcapsule emulsion;
(4) preparation of the final product organic-microencapsulated phase change material: and (3) washing the emulsion liquid product obtained in the step (3) by using deionized water, filtering, drying the obtained substance in an oven at the temperature of 40 ℃ for 12 hours, and grinding the dried substance into powder to obtain the final product, namely the organic-microcapsule phase change material.
5. A process for the preparation of MMF according to claim 4, wherein: after the melamine is added in the step (1) for reaction, clarifying the solution, detecting whether a cloud point appears, dripping a drop of reactant into deionized water to obtain a white precipitate which is the cloud point, and adding triethanolamine to adjust the pH value after the cloud point does not appear.
6. The use of the organic-microencapsulated phase change material of claim 1 in a battery thermal management system, wherein: the specific application method comprises the following steps: grinding the prepared organic-microcapsule phase change material into powder to obtain powder with the diameter of 100-phase and 200 mu m; filling the powder into a battery thermal management mold, and completely wrapping the battery; and monitoring the temperature change of the battery in the charging and discharging process by using a thermocouple temperature measuring device to obtain the real-time temperature, the average temperature and the temperature difference of the battery in different working environments.
7. Use according to claim 6, characterized in that: the packaging material in the battery thermal management system is any one of aluminum alloy, copper or iron, and the heat radiating fins are foamed nickel or foamed copper.
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