CN111978923A - Phase change material - Google Patents
Phase change material Download PDFInfo
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- CN111978923A CN111978923A CN201910421422.9A CN201910421422A CN111978923A CN 111978923 A CN111978923 A CN 111978923A CN 201910421422 A CN201910421422 A CN 201910421422A CN 111978923 A CN111978923 A CN 111978923A
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- 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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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Abstract
The present invention relates to a phase change material. The phase change material comprises phase change wax, a cross-linking agent and a filler, wherein the filler comprises a zero-dimensional material and a one-dimensional material and/or a two-dimensional material. The phase-change material adopts the zero-dimensional material and the one-dimensional material and/or the two-dimensional material to form the filler, and a three-dimensional internal network is formed in the filler and has internal structures with different scales, so that the phase-change material and the phase-change wax have the functions of effective load and series connection. The multi-dimensional composite phase change material has rich internal structures and functional units, so that the multi-dimensional composite phase change material has good thermal stability, high phase change enthalpy and high heat conduction speed, and can be widely applied to the field of heat management systems such as heat protection, waste heat recovery and the like.
Description
Technical Field
The invention belongs to the technical field related to phase change materials, and relates to a phase change material.
Background
The phase-change material can absorb energy from the environment and release energy to the environment, so that the contradiction that the energy supply and demand are not matched in time and space is solved well, and the utilization rate of the energy is effectively improved. Meanwhile, the temperature of the phase-change energy storage material is basically kept constant in the phase-change process, and the phase-change energy storage material can be used for regulating and controlling the temperature of the surrounding environment and can be repeatedly used.
The research on phase change materials is relatively mature, but most of solid-liquid phase change materials, especially medium-low temperature phase change materials, have a low thermal conductivity coefficient, which directly causes the largest problem of the phase change materials in the application of a thermal management system to be that the thermal conductivity coefficient is low (about 0.2W/mK), while the phase change materials in the thermal management system usually need to absorb and emit heat faster, otherwise, only part of the phase change materials undergo phase change absorption or heat emission, which leads to the reduction of the effect of the phase change materials in the thermal management system, and also causes a safety problem due to thermal runaway under extreme conditions such as high temperature or large current.
In order to solve the problems in the prior art, the invention provides a phase change material.
Disclosure of Invention
The invention aims to solve the technical problems that phase-change wax is easy to leak when heated, low in thermal conductivity and low in strength and easy to pulverize, and provides a phase-change material. The method is simple, and the phase-change material which has good thermal stability, high heat conduction speed, high energy storage density, high strength, easy molding and difficult pulverization can be prepared.
In order to solve the above technical problems, the present invention provides a phase change material comprising:
the phase change material comprises phase change wax, a cross-linking agent and a filler, wherein the filler comprises a zero-dimensional material and a one-dimensional material and/or a two-dimensional material.
Illustratively, the zero-dimensional material comprises one or a mixture of quantum dots, nano-particles and micro-particles.
Illustratively, the one-dimensional material includes one or more of a nanowire, a nanotube, a nanorod, a nanobelt, a microwire, a microtube, a microrod, a nanobelt, and the like.
Illustratively, the two-dimensional material includes one or a mixture of nanosheets, microsheets.
Illustratively, the filler comprises one or a mixture of several of graphene, graphene oxide, silicon alkene, two-dimensional sulfide, two-dimensional oxide, silicon carbide, BN and black scale.
Illustratively, the crosslinking agent is one or a mixture of more of polyester resin, polyether resin, amino resin, phenolic resin, epoxy resin, furan resin, polyacrylamide, polyimide, vinyl polymer, silane coupling agent, organic silica gel, asphalt and starch.
Illustratively, the phase change material further comprises a stabilizer for stabilizing the phase change material.
Illustratively, the stabilizer is one or more mixed materials of organic rare earth, organic tin, organic antimony, magnesium stearate, aluminum stearate, potassium stearate, calcium stearate, zinc stearate and the like.
Illustratively, the phase-change wax comprises 60-90 wt% of phase-change wax, 5-25 wt% of filler, and 5-15 wt% of cross-linking agent.
Compared with the prior art, the invention has the following advantages:
in conclusion, the phase-change material of the invention adopts the zero-dimensional material and the one-dimensional material and/or the two-dimensional material to form the filler, and the filler forms a three-dimensional internal network and has internal structures with different scales, thereby playing the roles of effective load and series connection on the zero-dimensional material and the phase-change wax. The multi-dimensional composite phase change material has rich internal structures and functional units, so that the multi-dimensional composite phase change material has good thermal stability, high phase change enthalpy and high heat conduction speed, and can be widely applied to the field of heat management systems such as heat protection, waste heat recovery and the like.
Drawings
The invention will be further described with reference to the accompanying drawings, which are only schematic illustrations and illustrations of the invention, and do not limit the scope of the invention.
FIG. 1 is a flow diagram of a method of making a phase change material according to one embodiment of the invention.
Detailed Description
In order to clearly understand the objects, technical solutions and technical effects of the present invention, the present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.
Example one
A method of preparing the phase change material of the present invention is exemplarily illustrated with reference to fig. 1. It is to be understood that the following methods are merely exemplary, and that any phase change material prepared by any method, including the zero-dimensional material of the present invention and the filler of the one-dimensional material and/or the two-dimensional material, can achieve the effects of the present invention.
Referring to fig. 1, step S1 is first performed: a phase-change wax of a first composition is obtained and heated to obtain a first liquid.
Illustratively, the phase change wax of the first component is weighed into a beaker using a balance and heated using an electric heater. Exemplary phase change waxes include one or more of higher aliphatic hydrocarbons having 12-65 carbon atoms, higher aliphatic alcohols having 8-20 carbon atoms, and paraffin-type waxes having a melting point of-15 to 140 ℃. In this example, the phase change wax employs a higher aliphatic hydrocarbon having 12 to 65 free carbon atoms, which is heated to 60 ℃ to melt to form a first liquid.
The phase-change material prepared by the invention comprises 60-90% (weight) of phase-change wax, 5-25% (weight) of filler, 2-5% (weight) of cross-linking agent, 1-5% (weight) of stabilizer and 2-5% (weight) of dispersant. Therefore, in each step, a material of a corresponding composition is obtained according to the total weight of the phase change material to be prepared.
Illustratively, the first component is calculated based on the amount of phase change material to be prepared. In one example, about 10g of phase change material is prepared, and the amount of phase change wax of the first component obtained is 6 g.
It should be understood that this example is only illustrative of the method of the present invention, and one skilled in the art can obtain any weight of phase change material according to the method of the present invention, so that any composition of phase change wax can be obtained, as long as it meets the composition distribution of the phase change material to be prepared.
Illustratively, the step S1 is further performed by adding a cross-linking agent while heating the phase-change wax, and mixing the phase-change wax and the cross-linking agent uniformly to form the first liquid.
Because the edges of the filler macromolecules contain a plurality of oxygen-containing functional groups (such as hydroxyl groups, aldehyde groups and the like), after the cross-linking agent is added, the cross-linking agent enables the oxygen-containing functional groups among the fillers to be bridged, so that the linear or slightly branched macromolecules are converted into a three-dimensional network structure, and the strength, the wear resistance, the solvent resistance and other properties of the finally formed phase-change material are improved.
Illustratively, the crosslinking agent includes one or more of polyester resin, polyether resin, amino resin, phenolic resin, epoxy resin, furan resin, polyacrylamide, polyimide, vinyl polymer, silane coupling agent, organic silica gel, asphalt and starch.
Illustratively, the phase change material prepared according to the present invention further comprises 1 to 5 wt% of a cross-linking agent, and thus, the cross-linking agent of the corresponding component is obtained in this step according to the total weight of the phase change material to be prepared. In this example, the crosslinking agent was a phenol resin, specifically, 0.5g of phenol resin was added dropwise to the phase-change wax melt liquid while stirring uniformly to obtain a first liquid.
Next, with continued reference to fig. 1, step S2 is performed: and obtaining a filler of a second component and a dispersant of a third component, and uniformly mixing the filler and the dispersant to obtain a second liquid.
Also, the amounts of the filler and the dispersant are obtained according to the amount of the phase change material to be prepared.
The filler comprises a zero-dimensional material and a one-dimensional material and/or a two-dimensional material.
Illustratively, the zero-dimensional material comprises one or a mixture of quantum dots, nano-particles and micro-particles.
Illustratively, the one-dimensional material includes one or more of a nanowire, a nanotube, a nanorod, a nanobelt, a microwire, a microtube, a microrod, a nanobelt, and the like.
Illustratively, the two-dimensional material includes one or a mixture of nanosheets, microsheets.
The filler is formed by a zero-dimensional material and a one-dimensional material and/or a two-dimensional material, a three-dimensional internal network is formed in the filler, and the filler has internal structures with different scales, so that the zero-dimensional material and the phase-change wax are effectively loaded and connected in series, and the phase-change wax is filled in the filler, so that the finally formed phase-change material has thermal stability, high thermal conductivity and corrosion resistance, and has certain strength. The formed phase-change material has a more stable internal structure, and has the characteristics of good mechanical property, high heat transfer speed, high phase-change enthalpy, difficult pulverization in use and the like. In addition, the multi-dimensional composite phase change material has good thermal stability and environmental safety; the preparation method of the obtained multi-dimensional composite phase change material is simple, strong in operability and suitable for large-scale preparation.
In order to uniformly fill the phase-change wax with the filler, the filler is mixed with the dispersing agent, the filler is uniformly dispersed into the dispersing agent to form a second liquid, and then the second liquid is further mixed with the phase-change wax in the first liquid, so that the phase-change wax uniformly fills the filler, and the stability and the strength of the finally formed phase-change material are improved.
Illustratively, the dispersant comprises one or more of deionized water, ethanol, propanol, isopropanol, ethylene glycol, glycerol, oleic acid acyl, oily ammonia, pentane, hexane, N-methyl pyrrolidone, N-dimethylformamide, polyethylene glycol p-isooctyl phenyl ether, ethyl acetate, tristearin and fatty acid polyglycol ester.
Illustratively, the step S2 is further performed by adding a cross-linking agent while mixing the filler and the dispersant, and uniformly mixing the filler, the dispersant and the cross-linking agent to form the second liquid.
Also, as described in step S1, since the edges of the filler macromolecules contain a plurality of oxygen-containing functional groups (such as hydroxyl groups, aldehyde groups, etc.), after the cross-linking agent is added, the cross-linking agent bridges the oxygen-containing functional groups between the fillers, so that the linear or slightly branched macromolecules are converted into a three-dimensional network structure, thereby improving the strength, wear resistance, solvent resistance, etc. of the finally formed phase-change material.
In this example, ethanol was used as the dispersant and carbon foam as the filler. Specifically, about 5mL of absolute ethyl alcohol is poured into a beaker and stirred at normal temperature; 2.5g of carbon foam was added to the stirred alcohol mixture, and after completion, stirring was continued for 0.5h sufficiently to obtain a second liquid.
Next, with continued reference to fig. 1, step S3 is performed: and uniformly mixing the first liquid and the second liquid under the heating condition to obtain a third liquid.
In the step, in the process of mixing and uniformly mixing the first liquid and the second liquid, the filler fully adsorbs the phase-change wax, and finally the phase-change material of the phase-change wax filling filler is formed.
Exemplarily, the method further includes, after the step S3: and adding a stabilizer into the third liquid and uniformly mixing. The stabilizer can reduce the surface tension and prevent the photo-thermal decomposition or oxidative decomposition of the finally formed phase-change material.
Also, the amount of the stabilizer is obtained according to the amount of the phase change material to be prepared.
In this step, exemplary methods of mixing include one or more of sonication, stirring, and ball milling.
Illustratively, the stabilizer comprises one or more of organic rare earth, organic tin, organic antimony, magnesium stearate, aluminum stearate, potassium stearate, calcium stearate and zinc stearate.
In the present example, zinc stearate was used as a stabilizer, specifically, 0.5g of zinc stearate was uniformly mixed with the third solution obtained in the foregoing step S3 to obtain a four-liquid.
Illustratively, in the step S3, the method further includes adding a cross-linking agent during the step of uniformly mixing the first liquid and the second liquid under heating.
In this embodiment, specifically, the fully stirred carbon foam alcohol solution is slowly poured into the molten phase-change wax liquid, and after completion, the fully stirred and heated solution is continuously stirred for 10min, so that the mixture is fully and uniformly mixed.
Illustratively, the mixing method includes one or more of ultrasound, stirring, and ball milling.
Next, with continued reference to fig. 1, step S4 is performed: treating the third liquid to obtain a solid powder.
Illustratively, the third liquid is subjected to heating treatment or pressure suction filtration treatment to obtain solid powder, and the solid powder is the phase-change material.
Illustratively, after obtaining the solid powder, the method further comprises performing a molding process on the solid powder to form the phase-change material with a specific shape. Exemplary methods of forming include molding, extrusion, isostatic pressing, rolling, injection, or slip casting.
In this embodiment, the heating temperature is increased to 95 degrees according to the third liquid obtained in step S3, and the stirring is continued until the liquid turns into a dry solid powder. Therefore, the phase-change material to be prepared is obtained, because the dispersing agent is added in the preparation process of the material, the filler and the dispersing agent are uniformly mixed by fully stirring, so that the filler forms enough dispersion volume, and the phase-change wax is fully and uniformly filled and adsorbed in the heat-conducting filling material in the step S3, so that the phase-change material with uniform particle size and stable performance can be finally formed, is easy to form, has high phase-change enthalpy, high heat-conducting speed, good mechanical strength, difficult pulverization due to stress and collision, good thermal stability and environmental safety, is a very ideal phase-change heat storage material, and can be widely applied to the related fields of energy industry, electronic industry, aerospace technology and the like; meanwhile, the phase-change material has the advantages of low manufacturing cost, simple preparation method, high process repeatability, simple process and less time consumption, and is suitable for industrial production.
The multi-dimensional composite phase change material has rich internal structures and functional units, good thermal stability, high phase change enthalpy and high heat conduction speed, and can be widely applied to the field of heat management systems such as heat protection, waste heat recovery and the like. The multi-dimensional composite phase change material can be prepared from economic and reasonable raw materials through a process with high repeatability, a simple process and less time consumption, and is suitable for industrial production.
Examples the preparation method of the phase change material according to the present invention is described in detail, and in the following examples, examples will be given according to the contents of the components in the phase change material, and the detailed description of the specific steps will not be provided. It is to be understood that the following examples are merely illustrative of the phase change material of the present invention and the method of preparing the same, and are not intended to be limiting.
Example two
A method of preparing the phase change material of the present invention comprises: heating 6g of phase-change wax at 60 ℃ for melting; adding 0.5g of phenolic resin into the phase-change wax liquid; 5mL of absolute ethyl alcohol is taken to be stirred at normal temperature; 0.5g of silane coupling agent is dripped into the stirred absolute ethyl alcohol and stirred fully and uniformly; adding 1g of carbon quantum dots, 1g of carbon nanotubes and 0.5g of graphene into the stirred absolute ethyl alcohol mixed solution, and then continuing to stir fully for 0.5 h; slowly pouring the fully stirred solution into the melted phase-change wax, and continuously fully stirring and heating for 10 min; adding 0.5g of stabilizer into the mixed wax, fully stirring, raising the heating temperature to 95 ℃, and continuously stirring until the mixed liquid is converted into dry solid powder; and (3) carrying out extrusion molding on the granular powder by adopting an extrusion molding method under the condition of applying 8 tons of force in a die-molding environment at the temperature of 35 ℃.
EXAMPLE III
A method of preparing the phase change material of the present invention comprises: heating 9g of phase-change wax at 80 ℃ for melting; 0.1g of polyether resin is dripped into the phase-change wax liquid; taking about 50mL of absolute alcohol to stir at normal temperature; dripping about 0.1g of dispersant into the stirred alcohol, and stirring fully and uniformly; adding 0.7g of carbon foam into the stirred alcohol solution, and continuing to stir fully for 0.5h after the completion; slowly pouring the fully stirred foam carbon alcohol solution into the melted phase-change wax, and continuously fully stirring and heating for 0.5h after the completion; adding 0.5g of stabilizer into the mixed wax, fully stirring, raising the heating temperature to 75 ℃ after the stirring is finished, and continuously stirring until the mixed liquid is converted into solid powder; and (3) performing compression molding on the granular powder by adopting a compression molding method under the condition of applying 3 tons of force in a compression molding environment at the temperature of 60 ℃.
Example four
A method of preparing the phase change material of the present invention comprises: pouring 9g of paraffin into a beaker, and heating to melt; pouring about 50mL of absolute alcohol into a beaker, and stirring at normal temperature; dripping about 0.1g of dispersant into the stirred alcohol, and stirring fully and uniformly; adding 0.7g of carbon foam into the stirred alcohol solution, and continuing to stir fully for 0.5h after the completion; slowly pouring the fully stirred expanded graphite alcohol solution into the melted paraffin, and continuously fully stirring and heating for 5min after the completion; 0.1g of polyether resin is dripped into the mixed wax, and then the heating temperature is increased to 75 ℃ to be continuously stirred until the mixed liquid is converted into solid powder; and (3) performing compression molding on the granular powder by adopting a compression molding method under the condition of applying 3 tons of force in a compression molding environment at the temperature of 60 ℃.
It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The present invention has been illustrated by the above embodiments, but it should be understood that the above embodiments are for illustrative and descriptive purposes only and are not intended to limit the invention to the scope of the described embodiments. It is to be understood that the invention is not limited to the details of construction and to the arrangements of the components set forth herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A phase change material comprising a phase change wax, a cross-linking agent and a filler, wherein the filler comprises a zero-dimensional material and a one-dimensional material and/or a two-dimensional material.
2. The phase change material as claimed in claim 1, wherein the zero-dimensional material comprises one or more of quantum dots, nano-particles, micro-particles.
3. The phase change material as claimed in claim 1, wherein the one-dimensional material comprises one or more of nanowires, nanotubes, nanorods, nanobelts, microwires, microtubes, nanorods, and nanobelts.
4. The phase change material of claim 1, wherein the two-dimensional material comprises one or a mixture of nanoplatelets, nanoplatelets.
5. The phase change material according to claim 1, wherein the filler comprises one or more of graphene, graphene oxide, silylene, two-dimensional sulfide, two-dimensional oxide, silicon carbide, BN, black scale.
6. The phase change material as claimed in claim 1, wherein the cross-linking agent is one or more of polyester resin, polyether resin, amino resin, phenolic resin, epoxy resin, furan resin, polyacrylamide, polyimide, vinyl polymer, silane coupling agent, organic silica gel, asphalt and starch.
7. The phase change material as claimed in claim 1, further comprising a stabilizer to stabilize the phase change material.
8. The phase change material as claimed in claim 1, wherein the stabilizer is one or more of organic rare earth, organic tin, organic antimony, magnesium stearate, aluminum stearate, potassium stearate, calcium stearate, zinc stearate, etc.
9. The phase change material of claim 1, comprising 60% to 90% by weight of the phase change wax, 5% to 25% by weight of the filler, and 5% to 15% by weight of the cross-linking agent.
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Cited By (1)
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| CN113637282A (en) * | 2021-07-15 | 2021-11-12 | 广东工业大学 | Photo-thermal conversion phase-change energy-storage gel composite material and preparation method thereof |
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Application publication date: 20201124 |