CN114716978B - Hierarchical pore structure carrier composite phase change energy storage material and preparation method thereof - Google Patents

Hierarchical pore structure carrier composite phase change energy storage material and preparation method thereof Download PDF

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CN114716978B
CN114716978B CN202210355481.2A CN202210355481A CN114716978B CN 114716978 B CN114716978 B CN 114716978B CN 202210355481 A CN202210355481 A CN 202210355481A CN 114716978 B CN114716978 B CN 114716978B
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pore structure
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storage material
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CN114716978A (en
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高欢
张浩旻
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Chengdu Univeristy of Technology
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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
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    • 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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
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    • Y02E60/14—Thermal energy storage
    • 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
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Abstract

The invention discloses a hierarchical pore structure carrier composite phase change energy storage material and a preparation method thereof. The composite phase change energy storage material takes silicate mineral powder as a main raw material, a binder, a surfactant, a foaming agent and a heat conduction modifier are added, a hierarchical pore silicate mineral carrier is obtained through normal-temperature foaming and heat treatment, and then the phase change material is loaded in an impregnation process to obtain the novel composite phase change energy storage material. The invention firstly prepares the foam mineral material carrier with the hierarchical pore structure, and then prepares the hierarchical pore structure carrier composite phase change energy storage material. The multi-level pore structure composite phase-change material has the advantages of large heat storage capacity, wide phase-change temperature range, excellent packaging performance, good chemical stability, strong leakage prevention capability, no supercooling phenomenon or low supercooling degree, good circulation stability, low-cost and easily obtained raw materials, environment-friendly production process and suitability for industrial production and business.

Description

Hierarchical pore structure carrier composite phase change energy storage material and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a hierarchical pore structure carrier composite phase change energy storage material prepared by using silicate minerals as main raw materials and a preparation method thereof.
Background
In recent years, energy and environment have been areas of intense social concern. In order to solve the problem of energy shortage, development of efficient, energy-saving and environment-friendly energy storage technology has become an important point of research in the fields of materials and engineering. The efficient energy storage technology can well relieve global energy pressure and improve the utilization efficiency of energy. Energy storage technology has been developed for many years, and in different application fields, various energy storage and release technologies have been designed and developed, and the energy storage technology relates to conversion and storage of energy in different forms such as heat energy, electric energy, chemical energy, solar energy, mechanical energy, wind energy, water energy and the like. Currently, energy forms which can be directly utilized by human beings are mainly heat energy, and phase change energy storage materials (PCM) are used for realizing energy storage and release through isothermal absorption or release of a large amount of heat in the phase change process of the phase change materials. The phase change material has the advantages of isothermal phase change, recoverability, chemical stability and the like, and is widely applied to the fields of solar energy recovery, energy-saving building materials, aerospace, military, textiles and the like.
The physicochemical properties of different phase change materials determine their effectiveness in thermal energy storage. At present, the phase change material is mainly divided into an organic phase change material and an inorganic phase change material, wherein the organic phase change material has the obvious advantages of large volume heat capacity, small supercooling effect or no supercooling effect, no toxicity, corrosion resistance, good chemical and thermal stability, wide phase change temperature range and the like, and becomes an important research object of the phase change energy storage material, but has the defects of poor heat conduction performance, small density, easy occurrence of leakage and the like, and can inhibit the heat storage and release efficiency, so that the development of the shaping phase change energy storage composite material with excellent comprehensive properties such as energy storage effect, excellent heat conduction performance, leakage prevention and the like becomes an important research trend.
At present, the preparation modes of the shaping phase-change energy storage composite material comprise a porous inorganic carrier compounding method, a microcapsule method, a sol-gel method, a pressing sintering method, a melt blending method and the like. The microcapsule method utilizes the coating effect of organic materials on phase change materials, the manufacturing cost is relatively high, and the heat storage density, the thermal property, the mechanical property and the heat conduction property are relatively low; the phase change energy storage material obtained by the sol-gel method, the pressing sintering method and the melt blending method has relatively low heat storage effect due to the limitation of adsorption performance; the porous inorganic carrier compounding method uses inorganic matters with a large specific surface area and a micropore structure as supporting materials, and forms a stable composite phase change heat storage material through capillary action of micropores on the phase change material. At present, diatomite, expanded vermiculite, expanded perlite and the like can be used for the porous inorganic carrier material, but the pore structure of the matrix material is usually a single-stage pore structure, the porosity is low, the pore size is not controllable, so that the loading rate and the overall heat storage density of the phase change material are low, and the heat conducting property is difficult to improve. The material with the porous structure belongs to a special mineral functional material, is a non-renewable resource, has limited reserves and needs to consider the substitute product.
There are no reports of multi-stage pore structure carrier composite phase change energy storage materials. The invention adopts inorganic silicate mineral with excellent heat conductivity and low cost as raw material, and aims to obtain the carrier material with high porosity, designable pore structure and multistage pore structure by compounding the inorganic silicate mineral with the cementing material and adopting normal-temperature foaming and calcining treatment. The multistage pore structure carrier composite phase change energy storage material prepared by compositing the carrier material with the millimeter, micron and nanometer multistage pore structures with the phase change material can have excellent energy storage capacity, heat conductivity coefficient, stability and leakage prevention capability, and has wide practical application value.
Disclosure of Invention
According to the invention, the heat conduction modified silicate multistage pore material with a multistage pore structure (simultaneously with nano, micron and millimeter pores) and a large specific surface area structure is prepared, and the prepared material has excellent heat conduction performance, packaging performance and leakage prevention capability. On the basis, the phase change material/silicate mineral hierarchical porous carrier composite phase change energy storage material is prepared, and the heat storage performance, the thermal stability and the heat conduction performance of the composite phase change material are greatly improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the silicate mineral is 20-80 wt%, preferably 30-70 wt%
The binder is 10-80 wt%, preferably 20-80 wt%
The surfactant is 0.1-1 wt%, preferably 0.2-0.8 wt%
The foaming agent is 1.0-10wt%, preferably 3-6wt%
The heat conduction modifier is 1.0-30wt%, preferably 6-15wt%
The method has the advantages that the method is convenient to use, and the device is suitable for the users
The prepared multi-stage pore structure packaging carrier with excellent heat conduction performance, high specific surface area and high porosity is compounded with the phase change material to obtain the novel silicate mineral multi-stage pore structure composite phase change material, so that the phase change material has excellent packaging performance and heat storage performance.
Wherein the silicate mineral is silicate mineral powder, and the particle size of the silicate mineral is less than or equal to 200 mu m, such as kaolinite powder.
The binder is an inorganic binder, preferably water glass, for example, water glass with Baume concentration of 20-60 DEG Be, and the foaming agent is an inorganic foaming agent, preferably hydrogen peroxide, and more preferably hydrogen peroxide with concentration of 20-40%.
Wherein the surfactant is one or more of anionic surfactant, cationic surfactant and nonionic surfactant, preferably anionic surfactant or cationic surfactant, more preferably cationic surfactant.
The anionic surfactant is sulfonate surfactant, preferably sodium alkyl sulfonate or sodium alkyl benzene sulfonate with different chain lengths, such as sodium dodecyl sulfonate, the cationic surfactant is quaternary ammonium salt surfactant, preferably alkyl trimethyl ammonium bromide with different chain lengths, such as cetyl trimethyl ammonium bromide, and the nonionic surfactant is one or more of alkylphenol ethoxylates, higher fatty alcohol ethoxylates, sucrose esters and ethylene oxide adducts of polypropylene glycol.
The heat conduction modifier is one or more of carbonaceous or metal materials with higher heat conduction coefficient, such as graphite, carbon fiber, aluminum powder, copper powder, silver powder and the like.
Wherein the phase change material is characterized in that the phase change material is an organic phase change material or an inorganic phase change material or an organic and inorganic composite phase change material, and the organic phase change material is paraffin, stearic acid, lauric acid, polyalcohol and the like; inorganic phase change materials such as CaCl 2 ·6H 2 O、Na 2 SO 4 ·10H 2 O、MgCl 2 ·6H 2 O、Al(NO 3 )·6H 2 O, etc.; the phase change material may be one of them, or any combination of several.
The invention also relates to a preparation method of the hierarchical pore structure carrier composite phase change energy storage material, wherein the preparation method comprises the following steps:
step 1, preparing raw materials, and uniformly mixing the raw materials to obtain a mixed material;
step 2, placing the mixed material in a mould, leveling, standing and foaming;
step 3, drying and solidifying the product obtained in the step 2, and then calcining;
step 4, putting the product obtained in the step 3 into a completely melted phase change material for impregnation treatment;
and 5, processing the product obtained in the step 4 near the phase change temperature point of the phase change material, removing the redundant phase change material which is not stably packaged in the multi-level pore carrier, and obtaining the multi-level pore structure carrier composite phase change energy storage material product after the processing is completed.
The preparation method is characterized in that:
in the step 1, the raw materials comprise silicate mineral powder, a surfactant, a binder, a heat conduction modifier and a foaming agent; the specific process is as follows: weighing the raw materials according to a proportion, and uniformly mixing, preferably uniformly mixing a surfactant and a binder; then silicate mineral powder and a heat conduction modifier are added and mixed uniformly; adding a foaming agent, and uniformly mixing;
in the step 2, the mold is a mold easy to demolding, such as a silica gel mold, the foaming is performed at normal temperature, preferably at room temperature, for example, the foaming is performed at 5-35 ℃, preferably at 20-25 ℃, and the foaming time is 12-36 h, preferably 18-30 h;
in step 3, the drying treatment is performed at 40-80 ℃ for 10-36 hours, preferably at 45-65 ℃ for 18-30 hours, the calcination temperature is 200-800 ℃, preferably 300-600 ℃, such as 400 ℃, and the calcination time is 0.5-4 hours, preferably 0.5-2 hours, such as 0.5 hours;
in step 4, the impregnation treatment is to impregnate the carrier material with the hierarchical pore structure obtained by the calcination treatment into the completely melted phase change material, wherein the impregnation temperature is higher than the melting temperature of the selected phase change material, for example, the melting temperature of polyethylene glycol 4000 is preferably 60-80 ℃, the impregnation temperature is preferably 80 ℃, and the impregnation method is a direct impregnation method or a vacuum impregnation method, preferably a vacuum impregnation method.
In step 5, the impregnated composite phase change material is subjected to a treatment process of removing unstably packaged phase change material, and is characterized in that the product obtained in step 4 is placed on an adsorption device, such as filter paper, and is treated under the condition of being higher than the phase change temperature of the phase change material, such as in the environment of 30-40 ℃ higher than the phase change temperature range until no leakage occurs.
Compared with the prior art, the invention has the following advantages:
according to the invention, the slurry obtained by uniformly mixing silicate mineral powder, a binder, a surfactant, a heat conduction modifier and a foaming agent is foamed at normal temperature, dried and solidified, and then calcined to obtain the encapsulation carrier material with high porosity and a multi-level pore structure. On the basis, the composite phase change energy storage material prepared by utilizing different impregnation means has higher load rate, generally up to 70% -90%, and has excellent heat storage performance (up to 80% -95% of latent heat of the phase change material) and excellent heat conduction performance.
Drawings
FIG. 1 is a schematic diagram of a hierarchical pore structure carrier and a composite phase change energy storage material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the hierarchical pore silicate foam carrier prepared in example 1;
FIG. 3 is a scanning electron microscope image of the hierarchical pore structure carrier composite phase change energy storage material prepared in example 1;
FIG. 4 is a graph showing pore size distribution of mercury intrusion curves before and after calcination treatment of the hierarchical pore structure encapsulation material of example 1;
FIG. 5 is a graph showing the loading of samples of examples 1-4 with phase change material;
FIG. 6 is a thermal analysis curve of the hierarchical pore structure carrier composite phase change energy storage material prepared in examples 1-4;
fig. 7 shows the thermal conductivity of the hierarchical porous structure carrier and the composite phase change energy storage material prepared in examples 1 and 4.
Detailed Description
The following are examples of the invention used with kaolin powder available from kaolin company, su zhou; the gellant water glass was purchased from yourui refractory, inc; the foaming agent hydrogen peroxide (30 wt%) is purchased from a chemical reagent limited formula of Chengdu Jinshan; the surfactant CTAB was purchased from Colon chemical Co., ltd. In Chengdu, and the graphite and polyethylene glycol were purchased from Shanghai Michlin Biochemical technology Co., ltd.
Example 1
1. Preparation of kaolinite hierarchical pore structure carrier packaging material
(1) Proportioning of: the mass ratio of the kaolinite powder to the binder to the surfactant to the foaming agent is 6:20:0.135:0.808. first, an appropriate amount of binder sodium silicate (Baume: 50; na 2 O/SiO 2 =2.25), pouring into a container, adding a surfactant (cetyl trimethyl ammonium bromide CTAB) and uniformly stirring, pouring into weighed kaolinite powder, and stirring for 5 minutes under the condition of 300 revolutions per minute by using a mechanical stirrer;
(2) Foaming at normal temperature: adding weighed foaming agent (hydrogen peroxide) into the uniformly stirred mixture, immediately stirring, wherein the stirring process needs to be as rapid and complete as possible to avoid foaming in advance, and then pouring 5 x 2.5cm 3 The mould is a semi-closed mould, preferably a mould with a cover, holes are uniformly distributed on the surface of the cover, the surface area of the holes accounts for 40-60% of the total area of the cover, and the foaming is normal-temperature foaming; standing and foaming the prepared half clinker for 12 hours under natural dark conditions;
(2) Drying and curing: after foaming is completed, transferring the foam into a 40 ℃ oven for drying for 24 hours, and then transferring the foam into a 50 ℃ drying oven for drying for 12 hours to complete normal-temperature curing;
(3) Calcining: and demolding the cured material, taking out, placing the cured material into a muffle furnace at 400 ℃ for calcining for 30 minutes, and taking out the cured material after calcining to obtain the kaolinite foam with the hierarchical pore structure.
2. Preparation of multi-level pore structure composite phase change energy storage material
(1) Melting: charging an excess of polyethylene glycol 4000 into a container and melting at a temperature of 70 ℃;
(2) Vacuum impregnation: completely immersing the prepared kaolinite foam into a liquid phase filled with excessive molten polyethylene glycol 4000, putting the mixture into a vacuum drying oven, continuously vacuumizing for 30 minutes at 70 ℃, continuously standing for 1 hour at-0.09 Mpa and 70 ℃, and taking out;
(3) Leakage: and placing the taken sample on filter paper, and performing leakage test for 2 hours in an oven at 85 ℃, and continuously replacing the filter paper in the process until polyethylene glycol 4000 is not separated out, so that the prepared multi-level porous structure kaolinite foam phase-change material is finally obtained.
The performance indexes of the obtained samples are as follows: the average pore size of the macropores of the kaolinite foam was 0.765mm, the loading rate of polyethylene glycol 4000 obtained by vacuum impregnation was 76.17%, the latent heat of fusion thereof was 157.23J/g, and the latent heat of solidification thereof was 138.11J/g.
Example two
1. Preparation of kaolinite hierarchical pore structure packaging material
(1) Proportioning: the mass ratio of the kaolinite powder to the binder to the surfactant to the foaming agent is 6:20:0.139:1.677. first, an appropriate amount of binder sodium silicate (Baume: 50; na 2 O/SiO 2 =2.25), pouring into a container, adding a surfactant (cetyl trimethyl ammonium bromide CTAB) and uniformly stirring, pouring into weighed kaolinite powder, and stirring for 5 minutes under the condition of 300 revolutions per minute by using a mechanical stirrer;
(2) Foaming at normal temperature: adding weighed foaming agent (hydrogen peroxide) into the uniformly stirred mixture, immediately stirring, wherein the stirring process needs to be as rapid and complete as possible to avoid foaming in advance, and then pouring 5 x 2.5cm 3 The mould is a semi-closed mould, preferably a mould with a cover, holes are uniformly distributed on the surface of the cover, the surface area of the holes accounts for 40-60% of the total area of the cover, and the foaming is normal-temperature foaming; standing and foaming the prepared half clinker for 12 hours under natural dark conditions;
(3) Drying and curing: after foaming is completed, transferring the foam into a 40 ℃ oven for drying for 24 hours, and then transferring the foam into a 50 ℃ drying oven for drying for 12 hours to complete normal-temperature curing;
(4) Calcining: and demolding the cured material, taking out, placing the cured material into a muffle furnace at 400 ℃ for calcining for 30 minutes, and taking out the cured material after calcining to obtain the kaolinite foam with the hierarchical pore structure.
2. Preparation of multi-level pore structure composite phase change energy storage material
(1) Melting: charging an excess of polyethylene glycol 4000 into a container and melting at a temperature of 70 ℃;
(2) Vacuum impregnation: completely immersing the prepared kaolinite foam into a liquid phase filled with excessive molten polyethylene glycol 4000, putting the mixture into a vacuum drying oven, continuously vacuumizing for 30 minutes at 70 ℃, continuously standing for 1 hour at-0.09 Mpa and 70 ℃, and taking out;
(3) Leakage: and placing the taken sample on filter paper, and performing leakage test for 2 hours in an oven at 85 ℃, and continuously replacing the filter paper in the process until polyethylene glycol 4000 is not separated out, so that the prepared multi-level porous structure kaolinite foam phase-change material is finally obtained.
The performance indexes of the obtained samples are as follows: the average pore diameter of the macropores of the kaolinite foam is 0.932mm, the loading rate of polyethylene glycol 4000 obtained by vacuum impregnation is 80.93%, the latent heat of fusion is 168.80J/g, and the latent heat of solidification is 146.02J/g.
Example III
1. Preparation of kaolinite hierarchical pore structure packaging material
(1) Proportioning: the mass ratio of the kaolinite powder to the binder to the surfactant to the foaming agent is 6:20:0.135:0.808. first, an appropriate amount of binder sodium silicate (Baume: 50; na 2 O/SiO 2 =2.25), pouring into a container, adding a surfactant (cetyl trimethyl ammonium bromide CTAB) and uniformly stirring, pouring into weighed kaolinite powder, and stirring for 5 minutes under the condition of 300 revolutions per minute by using a mechanical stirrer;
(2) Foaming at normal temperature: adding weighed foaming agent (hydrogen peroxide) into the uniformly stirred mixture, immediately stirring, wherein the stirring process needs to be as rapid and complete as possible to avoid foaming in advance, and then pouring 5 x 2.5cm 3 The mould is a semi-closed mould, preferably a mould with a cover, holes are uniformly distributed on the surface of the cover, the surface area of the holes accounts for 40-60% of the total area of the cover, and the foaming is normal-temperature foaming; standing and foaming the prepared half clinker for 12 hours under natural dark conditions;
(3) Drying and curing: after foaming is completed, transferring the foam into a 40 ℃ oven for drying for 24 hours, and then transferring the foam into a 50 ℃ drying oven for drying for 12 hours to complete normal-temperature curing;
(4) Calcining: and demolding the cured material, taking out, placing the cured material into a muffle furnace at 400 ℃ for calcining for 30 minutes, and taking out the cured material after calcining to obtain the kaolinite foam with the hierarchical pore structure.
2. Preparation of hierarchical pore structure phase change material
(1) Melting: charging an excess of polyethylene glycol 4000 into a container and melting at a temperature of 70 ℃;
(2) Direct impregnation: completely immersing the prepared kaolinite foam into a liquid phase filled with excessive molten polyethylene glycol 4000, putting the kaolinite foam into a blast drying oven, immersing for 2 hours at the environmental condition of 70 ℃, and then taking out;
(3) Leakage: and placing the taken sample on filter paper, and performing leakage test for 2 hours in an oven at 85 ℃, and continuously replacing the filter paper in the process until polyethylene glycol 4000 is not separated out, so that the prepared multi-level porous structure kaolinite foam phase-change material is finally obtained.
The performance indexes of the obtained samples are as follows: the average pore size of the macropores of the kaolinite foam was 0.578mm, the loading rate of polyethylene glycol 4000 obtained by vacuum impregnation was 67.12%, the latent heat of fusion was 123.87J/g, and the latent heat of solidification was 111.25J/g.
Example IV
1. Preparation of graphite/kaolinite hierarchical pore structure packaging material
(1) Proportioning: according to the mass ratio of graphite, kaolinite powder, binder, surfactant and foaming agent of 1.8:3.2:20:0.135:0.808. first, an appropriate amount of binder sodium silicate (Baume: 50; na 2 O/SiO 2 =2.25), pouring into a container, adding a surfactant (cetyl trimethyl ammonium bromide CTAB) and uniformly stirring, pouring into weighed kaolinite powder, and stirring for 5 minutes under the condition of 300 revolutions per minute by using a mechanical stirrer;
(2) Foaming at normal temperature: adding weighed foaming agent (hydrogen peroxide) into the uniformly stirred mixture, immediately stirring, wherein the stirring process needs to be as rapid and complete as possible to avoid foaming in advance, and then pouring 5 x 2.5cm 3 The mould is a semi-closed mould, preferably a mould with a cover, holes are uniformly distributed on the surface of the cover, the surface area of the holes accounts for 40-60% of the total area of the cover, and the foaming is normal-temperature foaming; will be multiplied byStanding and foaming the prepared semi-clinker for 12 hours under the natural dark condition;
(3) Drying and curing: after foaming is completed, transferring the foam into a 40 ℃ oven for drying for 24 hours, and then transferring the foam into a 50 ℃ drying oven for drying for 12 hours to complete normal-temperature curing;
(4) Calcining: and demolding the cured material, taking out, placing the cured material into a muffle furnace at 400 ℃ for calcining for 30 minutes, and taking out the cured material after calcining to obtain the kaolinite foam with the hierarchical pore structure.
2. Preparation of graphite heat conduction modified hierarchical pore structure phase change material
(1) Melting: charging an excess of polyethylene glycol 4000 into a container and melting at a temperature of 70 ℃;
(2) Direct impregnation: completely immersing the prepared kaolinite foam into a liquid phase filled with excessive molten polyethylene glycol 4000, putting the kaolinite foam into a blast drying oven, immersing for 2 hours at the environmental condition of 70 ℃, and then taking out;
(3) Leakage: and placing the taken sample on filter paper, and performing leakage test for 2 hours in an oven at 85 ℃, and continuously replacing the filter paper in the process until polyethylene glycol 4000 is not separated out, so that the prepared multi-level porous structure kaolinite foam phase-change material is finally obtained.
The performance indexes of the obtained samples are as follows: the average pore size of macropores of the graphite/kaolinite foam is 0.576mm, the loading rate of polyethylene glycol 4000 obtained by vacuum impregnation is 81.72%, the latent heat of fusion is 163.07J/g, and the latent heat of solidification is 146.89J/g.
Experimental example
Experimental example 1 sample morphology and Structure analysis
And (3) morphological structure analysis: analyzing the microscopic morphology structure of the hierarchical pore structure packaging material and the hierarchical pore structure carrier composite phase change energy storage material in the embodiment 1 of the invention by using a scanning electron microscope;
multistage pore structure test: the pore size distribution, the average pore size, the total pore area and the porosity of the multi-level pore structure packaging material before and after heat treatment in the embodiment 1 of the invention are tested and analyzed by using a mercury intrusion test method;
fig. 2 shows a scanning electron microstructure of the hierarchical pore structure package material before and after the heat treatment in example 1;
FIG. 3 shows a scanning electron microstructure of a composite phase change material in example 1;
fig. 4 shows pore size distribution of micropores before and after heat treatment of the sample of example 1.
The morphology and structure analysis results of example 1 were made into fig. 2, fig. 3, and fig. 4;
as can be seen from fig. 2, after calcination treatment, the original smooth pore wall has a significantly changed morphology, the roughened specific surface area of the pore wall is increased, and micropores are generated inside the pore wall;
as can be seen from fig. 3, after vacuum impregnation, the phase change material is uniformly loaded in the pore wall of the sample and the microporous structure in the pore wall;
as can be seen from fig. 4, the hierarchical pore structure encapsulating material of example 1 has larger pores in the sample before and after the calcination treatment. Before calcination, the micropores are distributed in the range of 20-220 μm, the large number of micropores are distributed in the range of 33-62 μm, and the main peak is concentrated at 43.8 μm. After the calcination treatment, the pore size distribution of the micrometer scale was changed, and although the pore size distribution of 10 μm or more was not significantly changed, the main pore size was transferred from 51.8 μm to 182.1 μm. The main peak of the calcined sample is concentrated at 146.2 μm, which indicates that the micropore structure is changed before the calcination, and the pore diameter is increased. And the peak appears in the range of 58.57-5783nm, namely a large number of micropores are generated after calcination treatment, and the diameters of most of the micropores are about 748.35 nm. Mercury intrusion test run other data, average pore size changed from 15481.41nm to 2235.31nm before calcination treatment, total pore area from 0.464m 2 /g is increased to 4.696m 2 /g; porosity increased from 78.4214% to 83.6139%, which is due in part to the creation of micropores.
Experimental example 2 sample Performance analysis
Load factor test: according to the formula:calculating the load rate of the phase change material after compounding, wherein eta is the load rate,M 1 is the quality of the hierarchical porous carrier before compounding, M 2 The quality of the composite material is removed after the composite material is not stably packaged in the phase change material;
enthalpy value test: the latent heat of fusion and the latent heat of solidification of the multi-stage pore structure carrier composite phase change energy storage material in the embodiment of the invention are tested and analyzed by utilizing a differential scanning calorimetry;
and (3) heat conduction coefficient test: the thermal conductivity of the hierarchical pore structure packaging material and the hierarchical pore structure carrier composite phase change energy storage material of example 1 was measured by using a laser thermal conductivity meter.
FIG. 5 shows the loading rate of the hierarchical pore structure carrier composite phase change energy storage material prepared in examples 1-4;
FIG. 6 shows the phase change enthalpy values of the hierarchical pore structure carrier composite phase change energy storage materials prepared in examples 1-4;
FIG. 7 shows the thermal conductivity of example 1 and the thermal conductivity of example 4 at 20deg.C, wherein K1 represents the hierarchical pore structure encapsulation material of example 1, and K1-PCM represents the hierarchical pore structure carrier composite phase change energy storage material of example 1; k4 represents the graphite multi-modified hierarchical pore structure packaging material in example 4, and K4-PCM represents the graphite modified hierarchical pore structure carrier composite phase change energy storage material in example 4.
As can be seen from fig. 5 and 4, the phase change enthalpy value is positively correlated with the load factor, and the phase change material obtained by vacuum impregnation is larger than that obtained by direct impregnation, namely, the load factor of vacuum impregnation is 9.05% higher than that obtained by comparison of the test results of example 1 and example 3, and the melting and solidifying enthalpies are 33.36J/g and 26.86J/g higher respectively;
the results are shown in Table 1:
TABLE 1 latent heat of fusion and latent heat of solidification test results
Sample of Load factor (%) Enthalpy of fusion (J/g) Enthalpy of solidification (J/g)
Example 1 76.17 157.23 138.11
Example 2 80.93 168.80 146.02
Example 3 67.12 123.87 111.25
Example 4 81.72 163.07 146.89
As can be seen from FIG. 7, the sample of example 1, which was not loaded with the phase change material, had a good thermal conductivity (1.89W/mK), but the thermal conductivity was reduced (0.36W/mK) when the phase change material was loaded. In contrast, by adding a heat conduction modifier with high heat conduction performance, as in example 4, graphite is added as the heat conduction modifier, so that the heat conduction coefficient of the sample K4 without the phase change material can be remarkably improved, the heat conduction coefficient of the sample K4 with the phase change material not loaded can be calculated by more accurate simulation through an equivalent medium theoretical model, the heat conduction coefficient is improved by 3.3 times compared with K1, the heat conduction coefficient of K4-PCM is improved by 3.54W/m.K, and the heat conduction coefficient is improved by 9.83 times compared with K1-PCM. The heat conduction modifier is added, so that the heat conduction property of the heat conduction modifier can be obviously improved.
In summary, the silicate mineral foam carrier with the multi-level pore structure is obtained by adopting silicate mineral powder (such as kaolinite powder) and adopting different mixing ratios, normal-temperature foaming, drying, solidifying and heat treatment, and the multi-level pore structure carrier composite phase change energy storage material is prepared by loading the phase change material.
The invention has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and scope of the present invention, which all fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (9)

1. The multi-level pore structure carrier composite phase change energy storage material is characterized by being prepared from the following raw materials in percentage by weight:
the utility model discloses a small-sized solar cell.
The utility model discloses a self-priming syringe.
The utility model discloses a self-priming syringe, which is characterized in that the syringe is connected with a syringe through a connecting rod.
The utility model discloses a small-sized solar cell.
The utility model discloses a heat-conducting material, which is used for reducing the heat loss of the heat-conducting material.
The phase change material is formed by mixing the components of the material with the components of the material;
the sum of the weight percentages of the raw materials is 100 percent;
the hierarchical pore structure carrier composite phase change energy storage material is prepared by the following method, and specifically comprises the following steps:
step 1, preparing raw materials, and uniformly mixing the raw materials to obtain a mixed material;
step 2, placing the mixed material into a foaming device, and leveling until the mixed material is fully foamed to obtain a material with a single-stage pore structure;
step 3, drying the product obtained in the step 2, and then calcining to obtain a carrier material with a hierarchical pore structure; the drying treatment is that the drying is carried out for 10 to 36 hours at the temperature of 40 to 80 ℃, the calcining temperature is 200 to 800 ℃, and the calcining time is 0.5 to 4 hours;
step 4, carrying out impregnation treatment on the hierarchical pore structure carrier material obtained in the step 3 by using a phase change material in a molten state;
and 5, processing the product obtained in the step 4 near the phase change temperature point of the phase change material, removing the redundant phase change material which is not stably packaged in the multi-level pore carrier, and obtaining the multi-level pore structure carrier composite phase change energy storage material product after the processing is completed.
2. The hierarchical porous structure carrier composite phase change energy storage material of claim 1, wherein the silicate mineral is a layered silicate mineral with a particle size of 200 μm or less.
3. The hierarchical porous structure carrier composite phase change energy storage material of claim 1, wherein the binder is a sodium silicate solution and the foaming agent is hydrogen peroxide.
4. The hierarchical pore structure carrier composite phase change energy storage material of claim 1, wherein the surfactant is one or more of an anionic surfactant, a cationic surfactant and a nonionic surfactant.
5. The multi-level pore structure carrier composite phase change energy storage material according to claim 4, wherein the anionic surfactant is a sulfonate surfactant, the cationic surfactant is a quaternary ammonium salt surfactant, and the nonionic surfactant is one or more of alkylphenol ethoxylates, high-carbon fatty alcohol ethoxylates, sucrose esters and ethylene oxide adducts of polypropylene glycol.
6. The hierarchical pore structure carrier composite phase change energy storage material of claim 1, wherein the thermally conductive modifier is one or more of a carbonaceous or metallic material.
7. The hierarchical pore structure carrier composite phase change energy storage material according to claim 1, wherein the phase change material is one of an organic phase change material or an inorganic phase change material or an organic and inorganic composite phase change material, or any combination of several of them.
8. The hierarchical pore structure carrier composite phase change energy storage material according to claim 1, wherein in step 1, the raw materials comprise silicate mineral powder, surfactant, binder, thermal conductivity enhancer and foaming agent;
the specific process of the step 1 is as follows: weighing the raw materials according to the weight ratio, uniformly mixing the raw materials of kaolinite and surfactant, then adding a binder, uniformly mixing, then adding a foaming agent, and uniformly mixing; the ratio of the catalyst can regulate and control the aperture size of a final product;
in the step 2, the foaming device is a die which is easy to demould, the foaming is normal-temperature foaming, and the foaming time is 12-36 h;
in the step 4, the impregnation treatment is to impregnate the multistage pore structure carrier material obtained by the calcination treatment into the completely melted phase change material, the impregnation temperature is higher than the melting temperature of the selected phase change material, and the impregnation method is a direct impregnation method or a vacuum impregnation method;
in step 5, the immersed composite phase change material is subjected to a treatment process of removing unstably packaged phase change material: and (3) placing the product obtained in the step (4) on an adsorption device, and under the condition of being higher than the phase change temperature of the phase change material, until no leakage occurs.
9. The use of a hierarchical pore structure carrier composite phase change energy storage material according to one of claims 1 to 7, characterized in that the use of a carrier material with a hierarchical pore structure obtained by foaming and calcining silicate mineral powder at normal temperature is used for packaging, heat conduction and stability improvement of the phase change material.
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