CN115044185A - Carbon-based aerogel loaded modified polyethylene glycol composite phase change material for battery thermal management and preparation method and application thereof - Google Patents
Carbon-based aerogel loaded modified polyethylene glycol composite phase change material for battery thermal management and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 53
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 53
- 239000004964 aerogel Substances 0.000 title claims abstract description 47
- 239000012782 phase change material Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000007726 management method Methods 0.000 title description 11
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 16
- 238000005470 impregnation Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000017 hydrogel Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
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- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
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- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
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- 239000010439 graphite Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
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- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 10
- 238000005338 heat storage Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
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- 239000011232 storage material Substances 0.000 abstract description 3
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- 239000000523 sample Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
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- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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Abstract
The invention relates to the field of battery thermal management and phase change energy storage materials, and particularly discloses a carbon-based aerogel load modified polyethylene glycol composite phase change material, and a preparation method and application thereof. By a freeze-drying method, a three-dimensional network is established by utilizing a carbohydrate-assisted carbon-based material to prepare the carbon-based aerogel; adding nano particles as a heat conduction reinforcing agent to modify polyethylene glycol, and preparing the composite phase change material by adopting a vacuum impregnation method. Compared with other similar technologies, the composite phase change material constructed by the method has good stability due to the hollow structure of the three-dimensional network, and the effective impregnation rate and the effective latent heat storage performance can reach more than 87%; the carbon-based material has high heat conduction characteristic and the nano particles are used as a heat conduction reinforcing agent, and a certain synergistic effect exists between the carbon-based material and the nano particles, so that the phase-change material has the characteristics of high heat conduction and high latent heat, is not easy to leak, and has a good application prospect in the aspect of battery heat management.
Description
Technical Field
The invention relates to the field of battery thermal management and phase change energy storage materials, in particular to a carbon-based aerogel load modified polyethylene glycol composite phase change material for battery thermal management and a preparation method and application thereof.
Background
The most widely used lithium battery in the electric vehicle has the advantages of high energy density, long cycle life, low self-discharge rate, no pollution and the like, and is the most promising and competitive secondary battery at present. However, the operating temperature of a lithium ion battery directly affects its safety and life. When the temperature is too high, the generation of thermal runaway phenomena is easily caused, and smoking, fire, even explosion and the like are caused, so that the thermal runaway phenomenon is one of the main potential safety hazards when energy storage and power batteries are used. The power generation capacity, the service life and the anti-damage and severe environment capacity of the lithium ion battery directly influence the service life and the cruising ability of the automobile. Meanwhile, the performance of the battery module is very sensitive to temperature, the optimal working temperature is 20-40 ℃, and the maximum temperature difference in the battery module is lower than 5 ℃. The decomposition of the solid electrolyte phase interface film can be accelerated by overhigh temperature, so that the hidden danger of thermal runaway is caused; and the low temperature can increase the viscosity of the electrolyte, influence the charge and discharge performance of the battery, and accelerate the lithium deposition reaction rate to form a lithium plating layer or lithium dendrite. In addition, the module temperature gradient is too large, which may cause a difference in discharge performance between the unit cells. The temperature of some regions is often lower or higher than this temperature, such as the northeast or the central and south regions, so the power battery of the automobile must be subjected to efficient thermal management, so that the temperature distribution of the electric battery pack tends to be uniform, and the operating temperature is stabilized within a reasonable temperature range. Meanwhile, the battery density is continuously developed towards the direction of high energy density along with the social demand, and higher requirements are also provided for a battery management system based on the phase change energy storage material.
Compared with the active management technology, the phase-change material does not need to be driven by external energy, can absorb waste heat of the battery and realize preheating of the battery in a low-temperature environment, and has a good development prospect. The phase change material should be selected taking into account several aspects: firstly, the phase transition temperature range of the material is in or near the ideal working range of the lithium ion battery; secondly, the material has high latent heat, small volume change in the phase change process and high cycle stability, and the phenomena of obvious supercooling and phase separation can not occur; in addition, the heat conduction coefficient is high while high latent heat is kept, and heat transfer is accelerated.
Disclosure of Invention
The invention provides a carbon-based aerogel prepared by using saccharides and carbon-based materials as raw materials through freeze drying, and finally preparing a carbon-based aerogel loaded modified polyethylene glycol composite phase change material by immersing a phase change material in the carbon-based aerogel through vacuum impregnation.
A method for preparing a carbon-based aerogel supported modified polyethylene glycol composite phase-change material comprises the following steps:
(1) mixing the saccharide with water to form a hydrogel;
(2) adding a carbon-based material into the hydrogel, and then preparing the carbon-based aerogel by a freeze-drying method;
(3) dispersing the nano particles in an organic solvent uniformly, adding the dispersed nano particles into molten polyethylene glycol, and mixing uniformly to obtain modified polyethylene glycol;
(4) and (3) mixing the modified polyethylene glycol in the step (3) with the aerogel prepared in the step (2), and then carrying out vacuum impregnation to prepare the carbon-based aerogel load modified polyethylene glycol composite phase change material.
Further, the saccharide in the step (1) is at least one of xanthan gum, chitosan, sodium alginate, hydroxymethyl cellulose and the like;
further, the mass fraction of the saccharides in the step (1) can be 3% -8%, and aerogels with different porosities can be prepared;
further, the step (1) of mixing the saccharide and the water by mechanical stirring to form the hydrogel, wherein the mechanical stirring speed is 1200r/min-1600 r/min;
further, the carbon-based material in the step (2) may be at least one of nano graphene, graphene oxide, expanded graphite, carbon nanotube, and the like;
further, the mass fraction of the carbon-based material in the step (2) is 3% -15%;
further, the freeze-drying temperature of the step (2) is-10-20 ℃, and the freeze-drying time is 24-72 h;
further, the content of the nanoparticles in the modified polyethylene glycol in the step (3) is 1 wt% to 10 wt%, preferably 1 wt% to 5 wt%, more preferably 1 wt%, 2 wt%, 3 wt%. The polyethylene glycol may have a molecular weight of 700-6000.
Further, the nano particles in the step (3) can be at least one of nano aluminum nitride, nano aluminum oxide, nano zinc oxide and the like;
further, the vacuum impregnation in the step (4) is completed in a vacuum oven, and the vacuum degree of the vacuum oven is-0.1 Mpa;
further, the vacuum impregnation time in the step (4) is 1-2h, and the temperature is 65-85 ℃;
the finally prepared carbon-based aerogel load modified polyethylene glycol composite phase change material is a black block;
the composite phase change material of the carbon-based aerogel loaded modified polyethylene glycol for battery thermal management is prepared by the method.
The carbon-based aerogel load modified polyethylene glycol composite phase change material for battery thermal management is applied to battery thermal management.
The carbon-based aerogel is prepared by taking saccharides and carbon-based materials as raw materials through freeze drying, and then the modified polyethylene glycol is immersed in the carbon-based aerogel to finally prepare the carbon-based aerogel-loaded modified polyethylene glycol composite phase change material. The carbon-based aerogel presents a three-dimensional porous structure, the leakage problem of the phase-change material in the phase-change process can be effectively inhibited, the nano particles are added as a heat conduction reinforcing agent, and the heat conductivity of the composite phase-change material is further improved due to the synergistic effect of the nano particles and the carbon-based material; in the prepared composite phase change material, the load rate of the phase change material is high, the composite phase change material has excellent shape stability, meanwhile, under the condition of keeping high latent heat, the heat transfer rate is accelerated due to the improvement of the heat conductivity coefficient, in addition, the preparation method of the material is simple, the raw materials are cheap and easy to obtain, the operation requirement is low, and the system can be used for battery heat management equipment.
Drawings
Fig. 1 is a differential scanning calorimetry curve of the graphene-based aerogel load 1 wt% aluminum nitride modified polyethylene glycol composite phase change material prepared in example 1;
fig. 2 is a sample diagram of aluminum nitride modified polyethylene glycol composite phase change materials with graphene-based aerogels prepared in example 1, example 4 and example 5 respectively loaded with mass fractions of 1%, 2% and 3%;
FIG. 3 is a graph showing the thermal conductivity of the final products obtained in example 1 and comparative examples 1 to 3.
Detailed Description
The following is a detailed description of the embodiments of the present invention, which is made on the premise of the technical solution of the present invention, and the embodiments and the specific operation procedures are given, but not limited to the present invention. The impregnation described in the examples is as is conventional to those skilled in the art, i.e. the aerogel is immersed in the solution. Thermal conductivity was measured by the transient plane source method using (Hot Disk TPS2500, Sweden) differential scanning calorimetry (TA. Q20, USA) at 5 ℃/min in N 2 Is carried out in an atmosphere. The molecular weight of the polyethylene glycol used in the examples was 2000; the molecular weights referred to in the present invention are average molecular weights.
Example 1
(1) Fully dissolving 1.0g of chitosan with the molecular weight of 3000 into 200mL of 0.3mol/L acetic acid aqueous solution to obtain 0.5% of saccharide solution, and mechanically stirring the saccharide solution to uniformly mix the saccharide solution and the saccharide solution to form hydrogel;
(2) then dispersing the nano graphene into the solution (1), stirring for 30min at room temperature, and stirring for 2h to ensure that the nano graphene is uniformly dispersed, thereby obtaining a nano graphene dispersion liquid with the mass fraction of 3%;
(3) subpackaging the solution with about 25g per part, freezing in a refrigerator for 24 h;
(4) placing the frozen sample in a freeze dryer, setting the freeze drying temperature to be-10-20 ℃, setting the freeze drying time to be 48h, and obtaining the nano graphene aerogel after the freeze drying is finished;
(5) dissolving nano aluminum nitride in ethanol solution, performing ultrasonic treatment for 40min, adding the mixture into molten polyethylene glycol after the nano aluminum nitride is uniformly dispersed, heating the mixture in a water bath at 85 ℃, and mechanically stirring the mixture to uniformly mix the mixture, wherein the mass fraction of the nano aluminum nitride in the obtained modified polyethylene glycol is 1%;
(6) soaking the aerogel in the solution in the step (5), placing the aerogel in a vacuum drying oven, and soaking for 1.5h at 75 ℃;
(7) and taking out the soaked sample, and cooling the sample to obtain the graphene aerogel loaded aluminum nitride modified polyethylene glycol composite phase change material.
The graphene aerogel loaded aluminum nitride modified polyethylene glycol composite phase change material obtained by the invention is black and hard, wherein the loading capacity of polyethylene glycol can reach 89.9%, and a differential scanning calorimetry curve is shown in figure 1; the latent heat of phase change can reach 176J/g, the coefficient of heat conductivity can reach 0.69W/m.K, and the heat conductivity is obviously improved; meanwhile, the effective impregnation rate and the effective latent heat storage performance can reach 88.6 percent.
Example 2
(1) Fully dissolving 1.0g of sodium alginate with the molecular weight of 222 into 200mL of deionized water solution to obtain 0.5% of saccharide solution;
(2) then dispersing the nano graphene into the solution (1), stirring for 30min at room temperature, and stirring for 2h to ensure that the nano graphene is uniformly dispersed, so as to obtain a nano graphene dispersion liquid with the mass fraction of 3%;
(3) subpackaging the solution with about 25g per part, freezing in a refrigerator for 24 h;
(4) placing the frozen sample in a freeze dryer, setting the freeze drying temperature to be-10-20 ℃, setting the freeze drying time to be 48h, and obtaining the nano graphene aerogel after the freeze drying is finished;
(5) adding nano zinc oxide into molten polyethylene glycol, heating in water bath at 85 ℃, and mechanically stirring to uniformly mix the zinc oxide and the molten polyethylene glycol, wherein the mass fraction of nano aluminum nitride in the obtained modified polyethylene glycol is 1%.
(6) Soaking the aerogel in the solution in the step (5), placing the aerogel in a vacuum drying oven, and soaking for 1.5 hours at 75 ℃;
(7) and taking out the soaked sample, and cooling the sample to obtain the successfully prepared graphene aerogel loaded zinc oxide modified polyethylene glycol composite phase change material.
The graphene aerogel loaded zinc oxide modified polyethylene glycol composite phase change material obtained by the invention is black and hard, wherein the loading capacity of polyethylene glycol can reach 87.6%; the latent heat of phase change can be as high as 170J/g, the heat conductivity coefficient can be as high as 0.75W/m.K, and the heat conductivity is obviously improved; meanwhile, the effective impregnation rate and the effective latent heat storage performance can reach 86.8 percent.
Example 3
(1) Fully dissolving 1.0g of hydroxymethyl cellulose with the molecular weight of 240 into 200mL of deionized water to obtain 0.5% of saccharide solution;
(2) then dispersing the nano graphene into the solution (1), stirring for 30min at room temperature, and stirring for 2h to ensure that the nano graphene is uniformly dispersed; obtaining nano graphene dispersion liquid with the mass fraction of 3%;
(3) subpackaging the solution with about 25g of each portion, freezing in a refrigerator for 24 h;
(4) placing the frozen sample in a freeze dryer, setting the freeze drying temperature to be-10-20 ℃, setting the freeze drying time to be 48h, and obtaining the nano graphene aerogel after the freeze drying is finished;
(5) adding nano aluminum oxide into molten polyethylene glycol, heating in a water bath at 85 ℃, and mechanically stirring to uniformly mix the nano aluminum oxide and the molten polyethylene glycol, wherein the mass fraction of the nano aluminum nitride in the obtained modified polyethylene glycol is 1%.
(6) Soaking the aerogel in the solution in the step (5), placing the aerogel in a vacuum drying oven, and soaking for 1.5h at 75 ℃;
(7) and taking out the soaked sample, and cooling the sample to obtain the graphene aerogel loaded alumina modified polyethylene glycol composite phase change material.
The graphene aerogel loaded alumina modified polyethylene glycol composite phase change material obtained by the invention is black and hard, wherein the loading capacity of polyethylene glycol can reach 84.2%; the latent heat of phase change is as high as 168J/g, the heat conductivity coefficient can be as high as 0.74W/m.K, and the heat conductivity is obviously improved; meanwhile, the effective impregnation rate and the effective latent heat storage performance of the composite material can reach 89.0 percent.
Example 4
Example 4 is different from example 1 in that the nano aluminum nitride added in the step (5) has a mass fraction of 2%.
The graphene aerogel loaded aluminum nitride modified polyethylene glycol composite phase-change material obtained by the invention is black block-shaped, wherein the loading capacity of polyethylene glycol can be up to 87.3%; the latent heat of phase change can be up to 161.8J/g, the heat conductivity coefficient can be up to 0.60W/m.K, and the heat conductivity is obviously improved; meanwhile, the effective impregnation rate and the effective latent heat storage performance can reach 85.5 percent.
Example 5
Example 5 is different from example 1 in that the nano aluminum nitride added in step (5) has a mass fraction of 3%.
The graphene aerogel loaded aluminum nitride modified polyethylene glycol composite phase-change material obtained by the invention is black block-shaped, wherein the loading capacity of polyethylene glycol can be up to 85.7%; the latent heat of phase change can be up to 160.28J/g, the heat conductivity coefficient can be up to 0.57W/m.K, and the heat conductivity is obviously improved; meanwhile, the effective impregnation rate and the effective latent heat storage performance can reach 84.8 percent.
Comparative example 1
The comparative example is different from example 1 in that the nano graphene aerogel and the nano aluminum nitride are not added, and only the polyethylene glycol phase change material (PEG) is prepared.
Comparative example 2
The comparative example is different from example 1 in that the steps (1) to (4) and (6) are not included, namely the aluminum nitride modified polyethylene glycol composite phase change material (PEG @ AlN Foam) is prepared.
Comparative example 3
The difference between the comparative example and the example 1 is that the graphene aerogel modified polyethylene glycol composite phase change material (PEG @ GNPs Foam) is prepared without adding nano aluminum nitride.
The embodiments of the present invention have been described in detail, but the present invention is only by way of example, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. All equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A method for preparing a carbon-based aerogel load modified polyethylene glycol composite phase change material for battery thermal management is characterized by comprising the following steps:
(1) mixing the saccharide with water to form a hydrogel;
(2) adding a carbon-based material into the hydrogel, and then preparing the carbon-based aerogel by a freeze-drying method;
(3) dispersing the nano particles in an organic solvent uniformly, adding the dispersed nano particles into molten polyethylene glycol, and mixing uniformly to obtain modified polyethylene glycol;
(4) and (3) mixing the modified polyethylene glycol in the step (3) with the aerogel prepared in the step (2), and then carrying out vacuum impregnation to prepare the carbon-based aerogel load modified polyethylene glycol composite phase change material.
2. The method of claim 1, wherein: the saccharide in the step (1) is at least one of xanthan gum, chitosan, sodium alginate and hydroxymethyl cellulose.
3. The method of claim 1, wherein: the mass fraction of the saccharides in the step (1) is 3-8%.
4. The method of claim 1, wherein: the carbon-based material in the step (2) is at least one of nano graphene, graphene oxide, expanded graphite and carbon nano tubes.
5. The method of claim 1, wherein: the mass fraction of the carbon-based material in the step (2) is 3% -15%.
6. The method of claim 1, wherein: and (3) the nano particles are at least one of nano aluminum nitride, nano aluminum oxide and nano zinc oxide.
7. The method of claim 1, wherein: the content of the nano particles in the modified polyethylene glycol in the step (3) is 1 wt% -10 wt%.
8. The method of claim 1, wherein: the vacuum impregnation time in the step (4) is 1-2h, and the temperature is 65-85 ℃.
9. A carbon-based aerogel supported modified polyethylene glycol composite phase change material for battery thermal management, which is prepared by the method of any one of claims 1-8.
10. The use of the carbon-based aerogel-supported modified polyethylene glycol composite phase change material for battery thermal management according to claim 9 in battery thermal management.
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