CN113861942B - 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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- CN113861942B CN113861942B CN202111072370.2A CN202111072370A CN113861942B CN 113861942 B CN113861942 B CN 113861942B CN 202111072370 A CN202111072370 A CN 202111072370A CN 113861942 B CN113861942 B CN 113861942B
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- 239000012782 phase change material Substances 0.000 title claims abstract description 75
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- 239000012188 paraffin wax Substances 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 6
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
-
- 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 field of application of microcapsule composite material design and 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 new energy automobile power battery thermal management system. The preparation method is that phase-change material paraffin is used as a nuclear material, melamine formaldehyde prepolymer MMF modified by methanol is used as a shell material, and emulsion polymerization reaction is carried out under the action of a dispersing agent styrene-maleic anhydride copolymer SMA, so that a target product is obtained. The battery and the radiating fin arrangement mode developed by combining the 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, scientific and technological achievements are easy to transform, the potential economic value is high, and the social and ecological benefits are outstanding.
Description
Technical Field
The invention belongs to the technical fields of composite phase change material design synthesis, 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 of the internal reaction of the battery. The overheating problem of electronic devices not only affects their functionality, but also creates challenges for their safety. Therefore, it is highly necessary to develop efficient thermal management techniques for electronic devices.
At present, a phase change material is generally adopted to absorb heat generated by an electronic device, so that the electronic device is kept at an almost constant optimal working temperature for a long time, the potential thermal safety hazard is reduced, and the working life is prolonged. The phase change materials are divided into three categories of inorganic phase change materials, organic phase change materials and mixed phase change materials, wherein the organic phase change materials have the advantages of good chemical stability, high thermal reliability, small supercooling degree, reasonable cost and the like. However, the organic phase change material has the defects of easy leakage, easy corrosion to devices, easy phase separation and the like when being directly used, and the current single phase change material compound does not have comprehensive excellent physical, chemical, dynamic, 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 higher comprehensive properties is prepared.
Nano-microencapsulation is an effective technique to increase the thermal conductivity of the composite material, improve the leakage problem of the phase change material during the melting process, and slow down the possible interaction between the active material and the surrounding matrix. Therefore, the nano microcapsule composite phase change material can be applied to electronic products, especially battery thermal management systems, and can maintain the stability of energy storage and release chemical reaction.
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 existing 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 takes a phase change material as a core material, takes melamine formaldehyde prepolymer MMF modified by methanol as a shell material, adds a heat conducting filler additive, and performs 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 any one of paraffin, dodecanol, tetradecyl alcohol or octadecane; the heat conduction filler is any one of carbon nano tube CNT, nano aluminum oxide Al 2O3 and nano zinc oxide ZnO; the dispersing agent is styrene-maleic anhydride copolymer SMA.
Further, the core material is Paraffin Paraffin, the shell material is melamine formaldehyde prepolymer MMF modified by methanol, the dispersing agent is styrene-maleic anhydride copolymer SMA, and the mass ratio of the core material, the shell material and the dispersing agent is: 1:0.7 to 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) Preparing MMF shell material: adding melamine into urotropine and formaldehyde solution, stirring at high speed to fully dissolve substances, heating to 80 ℃ in water bath, continuously stirring and 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 the solution to obtain MMF;
(2) Preparing an SMA solution: adding deionized water into a 250 mL three-neck flask with a high-speed stirrer, slowly adding SMA powder in a stirring state, continuously stirring until a suspension without visible particles is formed, then rapidly 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 microcapsule emulsion: adding 115 g phase change material into the SMA solution, and mechanically stirring in a high-speed dispersing machine for 10 minutes, wherein the liquid is in a milky emulsion; adding the MMF shell material 20 g prepared in the step (1), the heat-conducting filler 5g, accelerating stirring, setting the instrument heating rate to be 2 ℃/min, keeping stirring for 1.5 hours at the temperature after the heating temperature is increased to 80 ℃, and obtaining an emulsion product, namely microcapsule emulsion;
(4) Preparing an end product organic-microcapsule phase change material: washing the emulsion product obtained in the step (3) with deionized water, filtering, drying the obtained substance in a baking oven at 40 ℃ for 12 hours, and grinding the dried substance into powder to obtain the final product of the organic-microcapsule phase change material.
And (3) adding melamine to react in the step (1), clarifying the solution, detecting whether a cloud point appears, dripping a drop of reactant into deionized water, wherein white precipitation appears to be the cloud point, and adding triethanolamine to adjust the pH value after the cloud point does not exist.
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 100-200 mu m; filling the powder into a battery thermal management mould to completely wrap the battery; and monitoring the temperature change of the battery in the charging and discharging processes by using a thermocouple temperature measuring device, and obtaining 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 radiating fin is foam nickel or foam copper.
The morphology of the microcapsules is observed by a scanning electron microscope, and the results show that the structure of the microcapsules is uniform microcapsule-shaped spheres, and the heat conducting filler is uniformly dispersed around the microcapsules without affecting the whole structure of the microcapsules. The paraffin core composite phase change material is characterized by utilizing Fourier transform infrared spectrum, and the result shows that: the substances are only purely physically crosslinked, no new chemical substances are generated, and the properties of the phase change material are not affected. Differential Scanning Calorimetry (DSC) results show that the melting enthalpy measured value of the composite phase change material is obviously higher than the theoretical value in the heating/cooling process, and the melting enthalpy increment percentages are respectively increased by 48.7%, 59.4% and 84.9%. In addition, according to the battery charge and discharge test and leakage test results, compared with aluminum oxide and zinc oxide, the addition of the CNT obviously improves the heat storage and radiation performance of the material. In addition, the thermal stability experiment shows that the thermal stability of the battery is excellent, and the battery has wide application prospect in the aspects of battery thermal management system and energy storage.
In the invention, the highest temperature of the battery is reduced by more than 2 ℃ when the phase-change material works, the phase-change material has obvious heat dissipation effect, has good heat conduction, temperature adjustment, energy storage and other functions, 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 the synthetic reaction of MF;
FIG. 2 is a schematic diagram of the synthetic reaction of MMF;
Fig. 3 is a schematic diagram of a battery thermal management system, in which: the left diagram is a schematic diagram of the battery arrangement; the numbers 1,2,3 and 4 in the left graph are distributed at four different placement positions of the battery; (a), (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) are Paraffin-MMF obtained in comparative example 1; (c) And (d) Paraffin-MMF-Al 2O3 obtained in example 2; (e) And (f) Paraffin-MMF-ZnO obtained in example 3; (g) And (h) Paraffin-MMF-CNT obtained in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of the organic-microcapsule phase change materials obtained in examples 1-3;
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 organo-microcapsule phase change material obtained in example 1-example 3;
FIG. 8 is a Thermogravimetric (TG) curve and Differential Thermogravimetric (DTG) curve of the organic-microcapsule phase change material obtained in examples 1-3; in the figure: a is a TG curve; b is a DTG curve;
FIG. 9 shows the thermal conductivity of the organic-microcapsule phase change materials obtained in examples 1-3;
FIG. 10 shows the leakage test results of pure paraffin wax and the organic-microcapsule phase-change materials obtained in examples 1-3;
FIG. 11 shows the leakage rate of pure paraffin wax from the organic-microcapsule phase change materials obtained in examples 1-3;
FIG. 12 is a heat dissipation performance test chart; in the figure: a is a heat radiation performance test chart of Paraffin-MMF-CNT; b is a heat radiation performance test chart of Paraffin-MMF-Al 2O3; c is a heat radiation performance test chart of Paraffin-MMF-ZnO.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the preferred examples in the following description are only examples, and the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Materials: paraffin wax as phase change material (phase change temperature 46 ℃, shanghai Joule wax Co., ltd.); carbon nanotubes (l=10-20 μm, d > 50 nm, aledine); melamine (99%, aladine); methanol (AR, 99.5%, aledine); formaldehyde (AR, purity: 37.0-40.0 wt%, national medicine); triethanolamine (AR, aledine); glacial acetic acid (AR, 99.5%, aledine); the dispersant is styrene-maleic anhydride (STYRENE MALEIC ANHYDRIDE SMA) copolymer (Shanghai Cheng Jiguo national trade Co., ltd.); nonionic surfactant Span-80 (aledine); sodium hydroxide (AR, 96%, granular, aladine); nano zinc oxide (99.8% metalsbasis,50±10 nm); nano alumina (99.99 percent metals basis, crystal form gamma, less than or equal to 20 nm); urotropin (AR, 99% or more), allatin; samsung 18650 battery (2500 mAh capacity).
The preparation method of the MMF comprises the following steps: adding urotropine of 0.15 g and formaldehyde solution of 50mL into a 250 mL three-neck flask with a stirrer, a condenser pipe and a thermometer, stirring at a high speed to fully dissolve substances, adding melamine of 10 g, continuously stirring, heating to 80 ℃ in a water bath, continuously stirring for reaction for 1 hour, taking a drop of reactant to drop into deionized water after the solution is clarified, detecting that cloud point does not appear any more if white precipitation does not appear, adding triethanolamine to adjust the pH value to 9, and stirring uniformly to obtain a product MF. 60 mL methanol is added into the MF reaction solution, and the MF reaction solution is modified to obtain MMF, wherein the synthetic reaction principle of the MF is shown in figure 1, and the synthetic reaction principle of the MMF is shown in figure 2.
Preparation of SMA solution: deionized water was added to a 250 mL three-necked flask equipped with a high-speed stirrer, 10 g SMA powder was slowly added under stirring, stirring was continued until a suspension free of visible particles was formed, then 10wt% NaOH solution was rapidly added, pH was adjusted to 8, and stirring was continued for 1 hour, the process was always performed in a water bath at 50 ℃ to obtain a 5wt% SMA solution.
Specific examples of organic-microcapsule phase change materials are as follows:
Example 1: paraffin-MMF-CNT preparation
The SMA solution of 150mL was weighed into a three-necked flask, then 115 g paraffin wax was added and mechanically stirred at 500r/min for 10 minutes under vigorous stirring in a high speed disperser until the paraffin wax was completely dissolved, at which point a milky emulsion was present. Then, 20 g MMF was added, stirring was continued for 5 minutes, then, 5g CNT was added, stirring was accelerated, the heating rate was set at 2 ℃/min, the temperature was raised to 80 ℃, and stirring was continued at that temperature for 1.5 hours, to obtain an emulsion. Washing the product with deionized water for 3 times, drying and grinding to obtain target product powder.
Use of the resulting 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 100-200 mu m, filling the powder into a battery thermal management mould, and placing the powder in a blank of FIG. 3 so as to completely wrap the battery; the thermocouple temperature measuring device is used for monitoring the temperature change in the charging and discharging processes of the battery, and the average temperatures of batteries (numbered 1,2,3 and 4) in different working environments and in different placing positions are obtained. As can be seen from fig. 3 in top view, in addition to the phase change material, a heat sink (black line segment) is added, which is combined into a composite thermal management system.
The steps are to be described, the purpose of adding the SMA solution is to emulsify paraffin liquid droplets to a particle size of 100-200 nm, so that the paraffin liquid droplets are negatively charged, and a stable oil-in-water structure is formed; the MMF solution presents positive charges, and under the action of high-speed stirring, the positive charges and the negative charges are mutually attracted, so that a stable core-shell structure is formed.
Example 2: preparation of Paraffin-MMF-Al 2O3: 5g CNT of example 1 was replaced with 5g nm Al 2O3, and the remainder was as described in example 1.
Application of the obtained Paraffin-MMF-Al 2O3 in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with Paraffin-MMF-Al 2O3, and the other procedures were the same as those described in example 1.
Example 3: paraffin-MMF-ZnO preparation: the remainder of the procedure described in example 1 was followed except that 5g CNT of example 1 was replaced with 5g nm ZnO.
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 other methods were the same as those described in example 1.
Example 4: preparation of dodecanol-MMF-ZnO: the paraffin wax 115 g of example 1 was replaced with dodecanol 115 g; the remainder of the procedure described in example 1 was followed except that 5g CNT of example 1 was replaced with 5g nm ZnO.
Application of the obtained dodecanol-MMF-ZnO in a battery thermal management system: the Paraffin-MMF-CNT from example 1 was replaced with dodecanol-MMF-ZnO from example 1, and the other procedures were the same as those described in example 1.
Example 5: preparation of dodecanol-MMF-Al 2O3: the paraffin wax 115 g of example 1 was replaced with dodecanol 115 g; 5 g CNT of example 1 was replaced with 5 g nm Al 2O3, and the remainder was as described in example 1.
Application of the obtained dodecanol-MMF-Al 2O3 in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with dodecanol-MMF-Al 2O3, and the other procedures were the same as described in example 1.
Example 6: preparation of octadecane-MMF-CNT: the paraffin wax 115 g of example 1 was replaced with octadecane 115 g; the remainder of the procedure is as described in example 1.
Application of the obtained dodecanol-MMF-Al 2O3 in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with dodecanol-MMF-Al 2O3, and the other procedures were the same as described in example 1.
Example 7: preparation of tetradecanol-MMF-CNT: the paraffin wax 115 g of example 1 was replaced with tetradecanol 115 g; the remainder of the procedure is as described in example 1.
Application of the obtained tetradecyl alcohol-MMF-CNT in a battery thermal management system: the Paraffin-MMF-CNT in example 1 was replaced with tetradecanol-MMF-CNT in the same manner as described in example 1.
Comparative example 1: preparation of Paraffin-MMF: the remainder of the procedure was as described in example 1, except that no 5 g CNT thermally conductive filler was added.
Characterization of relevant properties for the organo-microcapsule phase change materials obtained in examples 1-3 and comparative example 1:
Example 1: the morphology of the sample was observed on a JEOL JSM-7001F type SEM, the results are shown in fig. 4, and the results show that: the appearance of the sample is of a spherical structure, and the particle size is as follows: the particle size of the Paraffin-MMF-ZnO and Paraffin-MMF-Al 2O3 is 200-500 nm, the particle size of the Paraffin-MMF-CNT is 300-500 nm, and the addition of the CNT, the nano Al 2O3 and the nano ZnO has little influence on the overall appearance of the shell.
Fig. 4 (a) shows spherical particles of pure Paraffin-MMF material having a relatively smooth surface, whereas the spherical particle surface is found to be rough in (b) (c) (d). The formation of the microcapsule structure mainly depends on interfacial tension among the phase change material, the shell material and the surfactant. From fig. 4 (c), it is observed that the microcapsules exhibit aggregation behavior, which may result in a slight increase in some adjacent particle size. 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 the carbon nanotubes may not be completely encapsulated in the microcapsules and some of the nanotubes may protrude from the microcapsules. Nevertheless, the morphology of Paraffin-MMF with nano Al 2O3, nano ZnO and CNT added was similar to that of Paraffin-MMF without any filler added, indicating that the addition of these thermally conductive fillers to the shell had little effect on the overall morphology.
Example 2: the XRD spectrum of the sample (instrument model: bruker D8 ADVANCE GERMANY, cu K alpha radiation) is shown in figure 5, and the main characteristic peaks of the sample are almost consistent with those of the phase-change paraffin wax serving as a core material, so that the core-shell material is only physically combined, and no chemical reaction occurs to generate new substances.
XRD patterns of pure Paraffin-MMF at room temperature showed expected characteristic diffraction peaks located on (100) and (110) crystal planes of 2θ= 21.77 ° and 24.08 °. It is also apparent that the characteristic diffraction peaks of nano Al 2O3 are located on the (121) and (131) planes of the β -crystalline phases of 2θ=30.27° and 36.52 °, the characteristic diffraction peaks of nano ZnO are located on the (100), (002) and (101) planes of 2θ= 31.85 °, 34.50 ° and 36.36 °, and the characteristic diffraction peaks of CNT are located on the (131) planes of 2θ=25.96 °. No other characteristic peaks were found except for the above characteristic peaks, indicating that these fillers were stably bound to the microcapsules. Furthermore, the characteristic peaks of pure Paraffin-MMF present broad peaks in the 2θ=15-30° region, indicating that the material is largely amorphous in nature, i.e. it is demonstrated that the lack of a highly crystalline structure is due to microencapsulation between the phase change material and the shell material. The characteristic peaks of the composite Paraffin-MMF-filler are other than pure Paraffin-MMF, and only the peaks of the corresponding filler are left, which show that the peaks are only physically combined and do not undergo chemical reaction.
Fig. 6 shows an infrared spectrum of the above sample. In Paraffin-MMF microcapsules without any filler, the absorption peaks at 2916 and 2850cm -1 are for CH stretching vibrations in-CH 3 and-CH 2 -, and the absorption peak at 1468 cm -1 is for C-H bending vibrations in-CH 3 and-CH 2 -. The absorption peak at 1032cm -1 corresponds to the tensile vibration of C-OH. They are characteristic peaks of paraffin wax. The peak at 700cm -1 is the out-of-plane bending vibration of N-H of-NH 2. The peak at 3413cm -1 is the overlap of N-H and O-H stretching vibrations, and the peak at 1738cm -1 is the-CHO C=O stretching vibration. The absorption peak at 1179cm -1 is the tensile vibration of C-O-C. The above peaks are characteristic peaks of MMF resin. Notably, paraffin-MMF is spectrally similar to composite phase change materials containing nano Al 2O3, nano ZnO and CNT hybrid fillers, indicating that the addition of fillers has little effect on the chemical structure of the microcapsules. In addition, there are no other characteristic peaks than those of the above materials, indicating that the core-shell material is only physically bound and no chemical binding occurs to generate new substances.
Example 3: thermal stability is a key parameter for testing 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 1-3.
As shown in figure a, all sample thermal weight loss curves were split equally into two steps, the first stage associated with paraffin pyrolysis in the temperature range 100-350 ℃ and the second stage associated with MMF shell degradation in the temperature range 350-600 ℃. Paraffin-MMF without any filler began to degrade at about 120 ℃, paraffin mass lost was fastest at 280 ℃, MMF shell mass lost was fastest at 456 ℃ (in FIG. (B)), and after filler addition, the two peak weight loss temperatures of Paraffin-MMF-Al 2O3, paraffin-MMF-ZnO and Paraffin-MMF-CNT were 303 ℃, 318 ℃, 320 ℃ and 460 ℃, 470 ℃, 550 ℃, respectively. The result shows that the addition of different fillers can obviously slow down the thermal decomposition rate, al 2O3, znO and CNT form an inorganic/organic composite shell with MMF, the composite shell can be used as a protective layer to resist the heat which damages the shell structure, the nano fillers are tightly combined with the MMF shell, the physical and mechanical properties of the composite shell are improved, the pyrolysis of the polymer shell is delayed, and the composite shell has more stable performance than the MMF shell.
To further understand the effect of phase change materials on temperature driven phase change, samples of the organic-microcapsule phase change materials obtained in examples 1-3 were characterized by differential scanning calorimetry. The phase transition temperature and the latent heat of phase transition of the material are measured by DSC (model: METTLER TOLEDO DSC 2), and the measuring method comprises the following steps: samples 5-8 mg were sealed in an aluminum crucible at a temperature ramp rate of 5 ℃/min and a constant nitrogen flow of 20 mL/min, and differential scanning calorimetry was used to characterize the latent heat storage capacity of the material by comparing the temperatures of the exothermic (crystallization, positive signal) or endothermic (melting, negative signal) transitions.
The experimental results are shown in FIG. 7, wherein the phase transition enthalpy of the pure Paraffin-MMF is 93.93J/g, and the melting point is 48.96 ℃; the phase transition enthalpy of Paraffin-MMF-CNT is 173.68J/g, and the melting point is 49.86 ℃; the phase transition enthalpy of Paraffin-MMF-Al 2O3 is 139.67J/g, and the melting point is 48.70 ℃; the phase transition enthalpy of Paraffin-MMF-ZnO is 149.72J/g, and the melting point is 49.80 ℃; all 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 trends of the differential scanning calorimetric curves of pure Parafin-MMF and composite Parafin-MMF-filler materials are substantially identical, with their T m values of 48.96 ℃, 48.70 ℃, 49.80 ℃ and 49.86 ℃, respectively, but with some deviation therebetween. It is believed that the slight deviation of T m of the composite Paraffin-MMF from T m of Paraffin-MMF is caused by interactions between the materials. The curve analysis results of the four samples show a single melting peak, namely only one endothermic peak appears in the melting process, which indicates that the material is a stable phase transfer material, therefore, all the four materials can be used as a potential heat storage material and have excellent heat stability.
Furthermore, the enthalpy of fusion (Δh m) is an important parameter directly related to the storage and release of latent heat, indicating the heat storage capacity. The phase change properties of Paraffin-MMF-Al 2O3, paraffin-MMF-ZnO and Paraffin-MMF-CNT are similar to Paraffin-MMF in that the phase change material (Paraffin) microencapsulates do not chemically react with the shell material or emulsifier, which still retains its original endothermic capabilities 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 transitions. Microencapsulation of phase change materials, particularly the addition of CNTs and nano-metal particles, improves heat transfer efficiency by reducing the barrier to paraffin nucleation and inhibiting supercooling within the microcapsules, indicating that they are potentially excellent energy storage materials.
Example 4: thermal conductivity is an important parameter reflecting the heat transfer efficiency of a phase change material, a higher thermal conductivity means that the phase change material has a relatively fast heat absorption-release capacity during phase change. The nano inorganic filler (Al 2O3, znO and CNT) has higher heat conductivity, and the composite phase change material prepared by the invention is hopeful to improve the heat conductivity of a matrix. Fig. 9 shows the thermal conductivity of the microcapsules. Wherein the thermal conductivity of Paraffin is only 0.12W/m.k, and when the dosage of Al 2O3, znO and CNT is 10wt%, the thermal conductivity of the composite Paraffin-MMF-filler is 0.2874W/m.k, 0.2821W/m.k and 0.4988W/m.k respectively, which are improved by 30.9%, 28.5% and 127.2% respectively compared with the pure Paraffin-MMF (0.2195W/m.k). It can be seen that the addition of CNT increases the thermal conductivity of the phase change material matrix by a multiple due to the excellent thermal conductivity of the CNT itself, while the CNT forms a composite shell with MMF, and the CNT interconnected outside the shell indirectly forms a high thermal conductivity network, thereby significantly improving the heat transfer capability of the interface and enabling the thermal conductivity of the microcapsule to be rapidly enhanced.
Example 5: leak-proof performance detection: the susceptibility to leakage is another major drawback affecting the performance of phase change materials, and thus the present invention conducted leakage tests above the melting temperature of pure paraffin (T m =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 1 hour, 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 pure Paraffin sample had melted over a large area, the surface of the paraffinmmf sample was intact, but it had partially leaked, compared to the paraffinmmf, paraffinmmf-Al 2O3 and paraffinmmf-ZnO samples, and only the paraffinmmf-CNT sample left no leakage trace on the filter paper surface throughout the 1h test at 60 ℃ indicating that the presence of CNTs inhibited their leakage.
After continuing to raise the temperature to 80 ℃ and heating for 1 hour, the Paraffin-MMF-CNT-containing sample had a small liquid leakage, indicating that the MMF shell had been broken by heating at this temperature, so that the liquid Paraffin therein leaked, and furthermore, by its electron microscopy, we found that the coating ratio of the microcapsule was not 100%, and therefore that it was possible that a part of the Paraffin which was not coated in the MMF shell leaked out. The rest of the composite materials have leakage of partial Paraffin, and interestingly, the leakage degree of the Paraffin-MMF-Al 2O3 sample is always larger than that of the Paraffin-MMF-ZnO sample at different temperatures, because the particle size of nano Al 2O3 is smaller than that of nano ZnO, namely, the smaller-sized nano particles are more easy to agglomerate, although dispersing agents are added, the agglomeration of Al 2O3 particles is more common than that of ZnO, so that the dispersing agents are uneven outside the microcapsule shells, a second shell cannot be effectively formed, the MMF shells are perfectly coated, and therefore, in the heating and heat absorbing processes, the second shell cannot effectively slow down the leakage phenomenon when the liquid nuclear material leaks. The CNT can form a CNT network due to the large length-diameter ratio of the CNT, so that a shell in a shape of a knitting wool sphere is generated, and when the MMF shell breaks, the CNT shell can effectively slow down the leakage of the shell, so that the performance of the shell is improved. All samples developed different degrees of leakage at 100 ℃, so the material was only suitable for use at medium and low temperatures. The results of the leak test confirm that the CNT provides mechanical strength and a network of thermally conductive structures for the Paraffin-MMF and inhibits its leakage. It is clear from leakage experiments that the microencapsulation technique is crucial for the preparation of shape stable phase change materials and further helps to expand the application range of phase change materials. When the microcapsule composite phase change material with the core-shell structure is applied to a battery thermal management system, the normal working temperature of the battery is maintained, and the fire risk caused by leakage of organic matters is reduced.
In addition, the data of the leakage experiment are also collated, and the leakage rate of different samples is calculated. As shown in fig. 11, the microencapsulation technique can effectively inhibit leakage of paraffin wax, and the extent of inhibition varies among different fillers. At 100 ℃, the leakage rate of pure paraffin is 98%, which may be due to impurities present due to the impure paraffin raw material; whereas Paraffin-MMF has a leakage rate of 30% and inhibits to some extent the leakage of part of the Paraffin, among the three different filler samples, CNT is undoubtedly the best choice, its maximum leakage rate is only 12.5%, and the leakage rate of the sample increases significantly with increasing ambient temperature.
Example 6: the organic-microcapsule phase change materials obtained in examples 1-3 adopt the arrangement mode shown in fig. 3 (a), the heat dissipation performance test result is shown in fig. 12, and through test research, the average temperature of the battery in four different environments is obviously reduced by about 2 ℃ compared with pure paraffin, which indicates that the sample has obvious heat dissipation effect on the working environment of the battery, thereby effectively protecting the normal working temperature of the battery and reducing the possibility of fire occurrence of the battery.
It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics 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 for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. An organic-microcapsule phase change material, characterized in that: taking a phase change material as a core material, taking paraffin wax as the core material, taking melamine formaldehyde prepolymer MMF modified by methanol as a shell material, adding a heat conducting filler additive, and performing emulsion polymerization reaction under the action of a dispersing agent to obtain a target product, namely the organic-microcapsule phase change material; wherein: the heat conducting filler is carbon nano tube CNT; the dispersing agent is styrene-maleic anhydride copolymer SMA;
The preparation method comprises the following specific steps:
(1) Preparing MMF shell material: adding melamine into urotropine and formaldehyde solution, stirring at high speed to dissolve substances sufficiently, heating to 80 ℃ in water bath, continuously stirring and reacting for 1 hour, adding triethanolamine to adjust pH value to 9 after the solution is clarified, and stirring uniformly to obtain a product melamine-formaldehyde prepolymer MF; adding methanol into the MF solution, and modifying the solution to obtain MMF;
(2) Preparing an SMA solution: adding deionized water into a 250 mL three-neck flask with a high-speed stirrer, slowly adding 10g of SMA powder under stirring, continuously stirring until a suspension without visible particles is formed, then rapidly adding 10 wt% 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 ℃ to obtain 5wt% of SMA solution;
(3) Preparing microcapsule emulsion: adding 115 g phase change material into 150ml of the SMA solution, and mechanically stirring in a high-speed dispersing machine for 10 minutes, wherein the liquid is in a milky emulsion; adding 20g of the MMF shell material prepared in the step (1) and 5g of the heat-conducting filler, accelerating stirring, setting the instrument heating rate to be 2 ℃/min, heating to 80 ℃, and keeping stirring for 1.5 hours at the temperature to obtain an emulsion product, namely microcapsule emulsion;
(4) Preparing an end product organic-microcapsule phase change material: washing the emulsion product obtained in the step (3) with deionized water, filtering, drying the obtained substance in a baking oven at 40 ℃ for 12 hours, and grinding the dried substance into powder to obtain the final product of the organic-microcapsule phase change material.
2. An organic-microcapsule phase change material according to claim 1, characterized in that: the organic-microcapsule phase change material is in a powder shape, the grain diameter is 1-10 mu m, the phase change enthalpy is 100-200 kJ/kg, and the phase change temperature is 30-60 ℃.
3. The organic-microcapsule phase change material according to claim 1, wherein: and (3) adding melamine to react in the step (1), clarifying the solution, detecting whether a cloud point appears, dripping a drop of reactant into deionized water, wherein white precipitation appears to be the cloud point, and adding triethanolamine to adjust the pH value after the cloud point does not exist.
4. Use of the organo-microcapsule phase change material of claim 1 in a battery thermal management system, characterized in that: 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 100-200 mu m; filling the powder into a battery thermal management mould to completely wrap the battery; and monitoring the temperature change of the battery in the charging and discharging processes by using a thermocouple temperature measuring device, and obtaining the real-time temperature, the average temperature and the temperature difference of the battery in different working environments.
5. Use of the organic-microcapsule phase change material according to claim 4 in a battery thermal management system, characterized in that: the packaging material in the battery thermal management system is any one of aluminum alloy, copper or iron, and the radiating fin is foam nickel or foam copper.
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