CN116119959A - Micro-surface enhanced phase change energy storage aggregate and preparation method and application thereof - Google Patents
Micro-surface enhanced phase change energy storage aggregate and preparation method and application thereof Download PDFInfo
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- CN116119959A CN116119959A CN202310083056.7A CN202310083056A CN116119959A CN 116119959 A CN116119959 A CN 116119959A CN 202310083056 A CN202310083056 A CN 202310083056A CN 116119959 A CN116119959 A CN 116119959A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The aggregate is characterized in that the phase change material is loaded in the pores of a regenerated porous supporting material, and the surface of the aggregate is coated with a micro-surface reinforcing layer. The preparation method comprises the following steps: cleaning and dredging the pore structure of the regenerated porous support material, and then soaking the phase change material into the pores; preparing a compound with a hydroxyl or tea phenol structure on the surface; finally depositing a micro-surface reinforcing layer to obtain aggregate, curing the cement mortar by using the aggregate, wherein the compressive strength is 40.2-58.4 MPa, the flexural strength is 6.5-8.4 MPa, the heat conductivity coefficient is 0.85-1.2W/m.K, the heat storage capacity is 8-60J/g, and the retention rate of the heat storage capacity in the service process is higher than 95% over time, and the aggregate is used in the field of construction.
Description
Technical Field
The invention relates to a waste-utilizing phase-change aggregate for building materials, and a preparation method and application thereof, and belongs to the field of civil engineering.
Background
The building industry is an energy consumption intensive industry, carbon dioxide emission generated in the annual building operation process accounts for more than 35% of the total global carbon emission, and more than half of the energy consumption in the building use process is used for indoor temperature regulation, so that living heat comfort is kept, and therefore, high-efficiency heat management is crucial for realizing energy conservation and emission reduction of the building. At present, the improvement of heat preservation and insulation capacity is a method for reducing heat management energy consumption commonly used in buildings, and the specific measure is to arrange an independent heat preservation and insulation layer in an enclosure structure. However, the heat insulation layer still has some problems in the practical application process. On one hand, because the thermal conductivity coefficients of the wall filling materials are greatly different, a cold bridge effect is easy to generate when the indoor and outdoor temperature difference is large, and the durability, the safety and the attractiveness of the wall are all very adversely affected; on the other hand, common heat-insulating filling materials such as polystyrene boards, phenolic materials, rock wool and the like have certain harm to the environment, and the use of a large amount of wall heat-insulating materials can increase the construction cost and cause environmental pollution. The building thermal comfort regulation is divided into two major types, namely active regulation and passive regulation, and the traditional thermal comfort regulation mainly comprises active regulation, including air conditioning, heating and other electrical equipment, and has the characteristics of high energy consumption, low efficiency, high carbon dioxide emission, high environmental hazard and the like. In contrast, passive thermal conditioning systems that are more energy efficient have received more and more attention in recent years. Cement mortar is a filling material commonly used in building enclosure structures, has a larger contact area with indoor and outdoor environments in the building, is a main carrier medium for heat exchange in the building, has important influence on indoor temperature fluctuation, living thermal comfort and thermal management efficiency due to the thermal physical property, but has limited heat storage capacity and cannot realize efficient passive heat energy adjustment and distribution.
The phase change material is a functional material with high heat storage capacity, and is characterized by being capable of absorbing or releasing a large amount of heat energy in the form of latent heat in the phase change process. Meanwhile, due to reversibility of the phase change process, the phase change material can respond to rising or falling of the ambient temperature in time, and the effect of adjusting the temperature in real time is achieved. The phase change material is added into the cement mortar, so that the cement mortar can be endowed with excellent heat storage capacity, and the phase change material is an ideal heat energy adjusting and managing building material. However, the introduction of the phase-change material often causes the obvious reduction of the mechanical strength, the heat transfer capability, the heat storage capacity and the retention rate of the heat storage capacity with time in the service process of the phase-change energy storage cement mortar. In the existing research, the mechanical strength of the phase-change energy-storage cement mortar is weakened to different degrees, in order to ensure high heat storage and release efficiency and structural performance, nano materials with higher heat conductivity coefficient are generally required to be added into the phase-change energy-storage cement mortar to improve the mechanical strength and the heat conductivity coefficient of a cement matrix, such as graphene, carbon nano tubes, carbon nano fibers and the like, so that the preparation cost of the phase-change energy-storage cement mortar is greatly increased, and meanwhile, in order to improve the heat storage capacity of the phase-change energy-storage cement mortar and the retention rate of the heat storage capacity in the service process for time, macro encapsulation is often required, the formed phase-change material has larger volume and cannot be well combined with the cement matrix, and the phase-change energy-storage cement mortar is beneficial to large-scale application and popularization. The disadvantages of high cost, low mechanical strength, insufficient heat conduction capability, poor shaping capability, small heat storage capacity, low retention rate of heat storage capacity in the service process and the like of the phase-change energy storage cement mortar seriously prevent the application of the phase-change energy storage cement mortar as a building structure and functional material.
Disclosure of Invention
The invention aims to solve the technical problems of high cost, low mechanical strength, insufficient heat conduction capability, poor shaping capability, small heat storage capacity and low retention rate of heat storage capacity with time in the service process of the traditional phase-change energy storage cement mortar, and provides a micro-surface reinforced phase-change energy storage aggregate, and a preparation method and application thereof. The recycled porous materials recovered from agricultural waste, industrial byproducts and municipal domestic waste are used as supporting materials for packaging the waste-utilized phase change materials, the problem of high cost of the phase change energy storage cement mortar is solved, a micro-surface reinforcing layer is immediately introduced to promote compatibility between the phase change energy storage aggregate and the cement base, and cement hydration products are induced to directionally deposit and grow at the micro-interfaces of the phase change energy storage aggregate, so that the porosity in the phase change energy storage cement mortar and the interfacial thermal resistance between the phase change energy storage aggregate and the cement base are reduced, and further the remarkable improvement of the mechanical strength, the heat conducting performance, the heat storage capacity, the setting capacity and the time retention rate of the heat storage capacity in the service process of the phase change energy storage cement mortar is realized, and the problems of low mechanical strength, insufficient heat conducting capacity, poor setting capacity, small heat storage capacity and low time retention rate of the heat storage capacity in the service process in the background technology are solved. Meanwhile, the porous supporting framework using the recycled material as the phase-change aggregate has the characteristics of low carbon and environmental protection for the phase-change energy storage cement mortar.
The micro-surface reinforced phase change energy storage aggregate consists of a regenerated porous supporting material, a phase change material and a micro-surface reinforced layer; the phase change material is loaded in the pores of the regenerated porous supporting material, and the micro-surface reinforcing layer is coated on the surface of the regenerated porous supporting material;
wherein the regenerated porous supporting material is a porous material recovered from solid waste, and comprises biochar, porous biomass material, porous waste plastic, porous waste rubber, fly ash, heavy putty, sludge ash, garbage incineration ash, agricultural solid waste incineration ash or waste wood;
the micro-surface enhancement layer is nano SiO 2 Layer or nano CaCO 3 A layer.
Further, the phase change material is a solid-liquid phase change material; the solid-liquid phase change material is an organic phase change material, an inorganic phase change material or a eutectic phase change material composed of the organic phase change material and the inorganic phase change material.
Furthermore, the inorganic phase-change material is a hydrated salt, and the organic phase-change material is paraffin and derivatives thereof, polyethylene glycol or fatty acid.
The preparation method of the micro-surface reinforced phase change energy storage aggregate comprises the following steps:
1. firstly adding the regenerated porous support material into a sodium hydroxide solution for ultrasonic cleaning for 1-3.5 h, then adding the regenerated porous support material into a hydrochloric acid solution for ultrasonic cleaning for 1-3.5 h, and then drying to obtain the aim of dredging the pore structure;
2. melting the phase change material, adding the regenerated porous support material into the melted phase change material, and dipping the melted phase change material into the pores of the regenerated porous support material by a vacuum adsorption method to obtain the waste-utilizing phase change material;
3. preparing a layer of compound with hydroxyl or a layer of compound with a tea phenol structure on the surface of the waste-utilizing phase-change material by a dipping or emulsifying method;
4. depositing and coating nano SiO on the surface of waste-utilizing phase-change material 2 Layer or nano CaCO 3 And taking the layer as a micro-surface reinforcing layer, washing and drying to obtain the micro-surface reinforced phase change energy storage aggregate.
Further, the concentration of the sodium hydroxide solution in the first step is 6 to 12mol/L.
Further, the concentration of the hydrochloric acid solution in the first step is 0.58-0.13 mol/L.
Still further, the compound having a hydroxyl group in the third step is sodium polyacrylate, polyacrylamide, lauryl alcohol chloride, polyethylene glycol or chitosan.
Still further, the chemical having a theanine structure in the third step is dopamine or DOPA.
Further, depositing coated nano SiO on the surface of the waste-utilizing phase-change material in the fourth step 2 The method of the layer is as follows:
placing the waste-utilizing phase-change material treated in the third step into a container, then adding deionized water, absolute ethyl alcohol and tetraethoxysilane into the container, fully stirring for 1.5-3.5 h at a stirring rate of 400-1200 rmp, gradually dropwise adding ammonia water in the stirring process, and regulating the pH value of the reaction solution to 8-10, so that the surface of the waste-utilizing phase-change material is directionally deposited, and a micro-surface reinforcing layer is formed. The method realizes nano SiO through hydroxyl induction or mussel bionic grafting 2 And (3) uniformly, compactly and highly-cohesively coating the micro-surface reinforcing layer.
Further, depositing coated nano CaCO on the surface of the waste-utilizing phase-change material in the fourth step 3 The method of the layer is as follows: placing the waste-utilizing phase change material treated by the third stepIn a container, deionized water and anhydrous CaCl are added into the container 2 Fully stirring for 1-3 h at the stirring rate of 300-600 rmp, and then continuously dripping Na with the concentration of 0.1-0.3 mol/L 2 CO 3 Solutions of CaCl 2 And Na (Na) 2 CO 3 The ratio of the amounts of the substances is (0.8-1.2): stop Na at 1 2 CO 3 And (3) dropwise adding the solution to enable the surface of the waste-utilizing phase change material to be directionally deposited to form a micro-surface enhancement layer. The method realizes nano CaCO through hydroxyl induction or mussel bionic grafting 3 And (3) uniformly, compactly and highly-cohesively coating the micro-surface reinforcing layer.
The application of the micro-surface enhanced phase-change energy storage aggregate can be used for preparing phase-change energy storage cement mortar by utilizing the micro-surface enhanced phase-change energy storage aggregate. The phase-change energy-storage cement mortar is prepared by mixing 9.4-15.3% of micro-surface enhanced phase-change energy-storage aggregate, 26.6-32.5% of hydraulic cementing material, 39.5-45.4% of sand and 6.8-24.5% of water according to mass percentage. The phase-change energy-storage cement mortar has the advantages of low cost, high mechanical strength, good heat-conducting property, large heat storage capacity, excellent shaping capability and high retention rate of heat storage capacity in the service process.
Furthermore, the difference between the thermal expansion coefficient of the micro-surface reinforced phase-change energy storage aggregate and the thermal expansion coefficient of the cement matrix is not more than 20%, so that the cooperation between the phase-change energy storage aggregate and the cement matrix after full hardening is satisfied.
Further, the hydraulic cementing material is P.I type silicate cement, P.II type silicate cement, P.O type ordinary silicate cement, sulphoaluminate cement or a mixture formed by the hydraulic cementing material and an active mineral admixture, wherein the active mineral admixture is fly ash, granulated blast furnace slag or silica fume.
Furthermore, the sand is standard sand, river sand, machine-made sand, sea sand or desert sand with the fineness modulus of 2.3-3.
The method for preparing the phase-change energy-storage cement mortar by utilizing the micro-surface reinforced phase-change energy-storage aggregate comprises the following steps of: adding the micro-surface reinforced phase-change energy-storage aggregate, the hydraulic cementing material and the sand into a mortar stirrer for stirring, and adding water for continuous stirring after uniform mixing to obtain the phase-change energy-storage cement mortar.
And filling the phase-change energy-storage cement mortar into a mould, fully vibrating, and curing until the strength reaches the use requirement to obtain the high-strength phase-change energy-storage cement.
The invention provides the phase-change energy-storage cement mortar based on the waste-utilization-type phase-change energy-storage aggregate, which has the advantages of low cost, high mechanical strength, good heat-conducting property, large heat storage capacity, excellent shaping capability and high retention rate of heat storage capacity with time in the service process, and the micro-surface/interface strengthening technology thereof. The phase-change energy-storage cement mortar consists of micro-surface-reinforced phase-change energy-storage aggregate, hydraulic cementing material, sand and water. The micro-surface enhanced phase change aggregate consists of a supporting material, a phase change material and a micro-surface enhancement layer, wherein the supporting material is a regenerated porous material recovered from agricultural waste, industrial byproducts and municipal domestic waste, the phase change material is a solid-liquid phase change material, and the micro-surface enhancement layer is nano SiO 2 And nano CaCO 3 . The working principle of the micro-surface enhancement layer is that nano SiO is adopted 2 And nano CaCO 3 The deposition of cement hydration products is induced, so that the micro-interface compactness between the phase-change energy storage aggregate and the matrix is improved, the microstructure of the phase-change energy storage cement mortar is effectively improved, the purposes of improving the setting capacity of the phase-change energy storage aggregate, reducing the interface thermal resistance and improving the compressive strength are achieved, and the effects of synergistically strengthening the heat storage capacity, the heat transfer capacity and the mechanical property of the phase-change energy storage cement mortar are achieved. The phase-change energy-storage cement mortar based on the waste-utilization-type phase-change energy-storage aggregate has the advantages of low cost, high mechanical strength, good heat-conducting property, large heat-storage capacity, excellent setting capacity and high retention rate of heat-storage capacity in the service process, and the micro-surface/interface strengthening technology thereof, provides a novel low-carbon environment-friendly heat-storage building material, solves the problems of poor mechanical strength, low heat storage efficiency and large heat-storage capacity loss after long-term service of the phase-change energy-storage cement-based material, realizes the synergistic enhancement of the structural performance and the thermophysical performance of the phase-change energy-storage cement-based material, and has application value in the aspect of building energy conservation.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a phase-change energy-storage cement mortar based on micro-surface reinforced phase-change energy-storage aggregate, which has the advantages of low cost, high mechanical strength, good heat-conducting property, large heat-storage capacity, excellent shaping capacity and high retention rate of heat-storage capacity with time in the service process, and a preparation method thereof, wherein the use of the micro-surface reinforced phase-change energy-storage aggregate can reduce the weakening of the heat-storage efficiency of the phase-change material by the cement mortar while avoiding the adverse effect of the phase-change material on the mechanical property of the cement mortar, so that the phase-change energy-storage cement mortar overcomes the defects of weak mechanical property, low heat-storage efficiency and poor shaping stability of the conventional phase-change energy-storage cement mortar, and has the following specific beneficial effects:
1. the micro-surface enhancement of the phase-change energy-storage aggregate is realized by using a novel induced synthesis path, and the method can uniformly and compactly form nano SiO on the surface of the phase-change energy-storage aggregate, unlike the traditional physical coating or dipping method 2 And nano CaCO 3 The micro-surface reinforcing layer has stronger bonding effect between the phase-change energy-storage aggregate and the micro-surface reinforcing layer due to hydroxyl induction or mussel bionic grafting effect, the micro-surface-reinforced phase-change energy-storage aggregate is introduced into the cement mortar, and the self-strength thermophysical property of the phase-change aggregate is enhanced by inducing the micro-surface reinforcing layer to directionally deposit on the surface of the phase-change energy-storage aggregate, so that the compatibility of the phase-change energy-storage aggregate and a cementing material in the cement mortar is improved, and the cracking resistance in the mixing process with cement and the heat storage capacity after long-term service are improved.
2. Nano SiO in micro surface enhancement layer 2 Can react with calcium hydroxide in cement hydration product to generate C-S-H gel, while nano CaCO in micro surface enhancement layer 3 Can form monocarbon aluminate and semi-carbon aluminate with ettringite in cement hydration products. The micro-surface enhancement layer realizes the directional induced deposition growth of hydration products between the phase-change energy-storage aggregate and the cement matrix, reforms the micro-interface between the phase-change energy-storage aggregate and the cement matrix, so that the micro-interface is more compact, reduces the interface thermal resistance between the phase-change energy-storage aggregate and the cement matrix, and improves the cementing material between the phase-change energy-storage aggregate and the cement mortarThe interface connection strength is improved, the number of harmful pores is greatly reduced, the microstructure of the phase-change energy-storage cement mortar is effectively improved, the mechanical strength, the heat transfer capability and the heat storage capacity of the phase-change energy-storage cement mortar are improved, and the field problem that the traditional phase-change energy-storage cement mortar is difficult to be used as a building structure material and has low heat management efficiency is solved.
3. The micro-surface/interface strengthening technology is adopted to improve the microstructure of the phase-change energy-storage cement mortar, so that the durability of the phase-change energy-storage cement mortar containing the waste-utilizing phase-change material with the micro-surface strengthening is obviously improved, and the later maintenance cost is also greatly saved.
4. The phase-change energy-storage cement mortar provided by the invention can realize the cooperative reinforcement of mechanical strength, heat transfer capability and heat storage capacity, improves the service performance and heat storage performance of the structure, has simple preparation process and low cost, and has a practical foundation for large-scale application, production and popularization.
5. The micro-surface enhanced phase change aggregate uses the regenerated material as a supporting framework, so that the natural resource consumption and the carbon dioxide emission are reduced; the phase-change energy-storage cement mortar based on micro-surface enhancement has the advantages of low cost, good heat conduction performance, large heat storage capacity, excellent shaping capacity, high retention rate of heat storage capacity in the service process over time, and can realize real-time indoor temperature adjustment, building thermal comfort, energy conservation, emission reduction and the like.
6. The phase-change energy-storage cement has the advantages of low cost, high mechanical strength, good heat-conducting property, large heat storage capacity, excellent shaping capability and high retention rate of heat storage capacity in the service process over time, has the compression strength of 40.2-58.4 MPa, the flexural strength of 6.5-8.4 MPa, the heat conductivity coefficient of 0.85-1.2W/m.K, the heat storage capacity of 8-60J/g and the retention rate of heat storage capacity in the service process over time of more than 95 percent, and can be used in the field of buildings.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a waste-type phase change material according to example 1; in the figure, 1 is a two-way flask, 2 is a first connecting pipe, 3 is a first vacuum valve, 4 is a vacuum gauge, 5 is a vacuum pump, 6 is a second connecting pipe, 7 is a second vacuum valve, and 8 is a beaker;
FIG. 2 is a scanning electron microscope image of the micro-surface enhanced phase change energy storage aggregate prepared in example 2;
FIG. 3 is a scanning electron micrograph of a micro-surfacing/interface-enhanced phase change energy storage cement mortar sample from example 2.
Detailed Description
The following examples are used to demonstrate the benefits of the present invention.
Example 1: the preparation method of the micro-surface reinforced phase change energy storage aggregate comprises the following steps:
1. adding the regenerated porous supporting material fly ash into 10mol/L sodium hydroxide solution for ultrasonic cleaning for 2 hours, adding the regenerated porous supporting material fly ash into 0.2mol/L hydrochloric acid solution for ultrasonic cleaning for 2 hours, filtering the fly ash, repeatedly washing the fly ash with deionized water, and drying to obtain the porous supporting material fly ash, so as to ensure that pores on the surface of the fly ash are completely exposed, and achieve the aim of dredging a pore structure;
2. preparing a waste-utilizing phase change material:
(1) With binary eutectic hydrated salt EHS (Na 2 CO 3 ·10H 2 O-Na 2 HPO 4 ·12H 2 O) as a phase change material, placing the EHS in a beaker 8, and then placing the beaker in a water bath kettle for heating, wherein the temperature of the water bath kettle is set to 55 ℃;
(2) The diagram of the device for preparing the waste-type phase change material is shown in fig. 1, and the device consists of a two-way flask 1, a first connecting pipe 2, a first vacuum valve 3, a vacuum gauge 4, a vacuum pump 5, a second connecting pipe 6 and a second vacuum valve 7; one end of the two-way flask 1 is connected with a vacuum pump 5 through a first connecting pipe 2, a first vacuum valve 3 is arranged on the first connecting pipe 2, and a vacuum gauge 4 is arranged on the vacuum pump 5; the other end of the two-way flask 1 is connected with a second connecting pipe 6; a second vacuum valve 7 is arranged on the second connecting pipe 6; placing the fly ash treated in the first step into a two-way flask 1, and connecting a second connecting pipe 6 into a melting EHS; closing the second vacuum valve 7, opening the first vacuum valve 3, immediately starting the vacuum pump 5, carrying out vacuum treatment on the fly ash in the flask, closing the vacuum pump when the vacuum degree in the flask is lower than-0.08 MPa, and continuously maintaining for 1h to finish the vacuum treatment of the fly ash;
(3) Opening a second vacuum valve 7, and under the action of atmospheric pressure, allowing the molten EHS to enter a flask filled with the fly ash until the molten EHS completely submerges the fly ash in the flask, closing the second vacuum valve 7, and keeping the state for 2 hours, so that the EHS is immersed in pores of the fly ash to obtain the waste-utilizing type phase-change energy-storage aggregate; the whole process melts EHS sufficiently to ensure that no air enters the flask;
(4) After the step (3) is completed, carrying out suction filtration on the mixed liquid in the flask to obtain the waste-utilizing type phase change material;
3. adding 5g of waste-utilizing phase-change material and 20g of hydroxyl inducer polyethylene glycol (PEG) into a beaker, stirring at 60 ℃ for 30min at a rotating speed of 800r/min, and preparing a layer of compound with hydroxyl on the surface of the waste-utilizing phase-change energy storage aggregate;
4. adding 500mL of ethyl orthosilicate ethanol solution with the mass percentage of 12.5% and 50mL of deionized water into a beaker, continuously stirring for 2 hours at the rotating speed of 400r/min, and dropwise adding excessive ammonia water in the stirring process to completely hydrolyze the ethyl orthosilicate to generate SiO 2 Covering the surface of the fly ash, filtering, washing and drying to obtain the micro-surface reinforced phase change energy storage aggregate. The method realizes nano SiO through hydroxyl induction 2 And (3) performing in-situ orientation on the micro-surface deposition growth of the waste-utilizing phase change material to finish the coating process of the micro-surface reinforcing layer.
The reference cement mortar, the non-micro-surface/interface reinforced phase-change energy-storage mortar containing the waste-type phase-change material and the micro-surface/interface reinforced phase-change energy-storage cement mortar containing the micro-surface reinforced phase-change energy-storage aggregate prepared in the step two and the micro-surface reinforced phase-change energy-storage aggregate prepared in the step four of the embodiment 1 are prepared by the specific methods as follows:
weighing 12.7% of micro-surface reinforced phase-change energy-storage aggregate, 30.2% of hydraulic cementing material P.O-type Portland cement, 44.6% of standard sand and 12.5% of water according to mass percentage, stirring the micro-surface reinforced phase-change energy-storage aggregate, the standard sand and the P.O-type Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain micro-surface/interface reinforced phase-change energy-storage cement mortar;
weighing 12.7% of waste-utilizing phase-change material, 30.2% of hydraulic cementing material P.O type Portland cement, 44.6% of standard sand and 12.5% of water according to mass percentage, stirring the waste-utilizing phase-change material, the standard sand and the P.O type Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain the non-micro-surface/interface reinforced phase-change energy storage mortar;
according to the mass percentage, weighing 30.2% of hydraulic cementing material P.O type Portland cement, 57.3% of standard sand and 12.5% of water, stirring the standard sand and the P.O Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain the reference cement mortar.
And (3) filling the three cement mortars into a mould, vibrating, and curing for 28 days under standard conditions to obtain a reference cement mortar test piece, an unprecedented micro-surface/interface reinforced phase-change energy-storage mortar test piece containing the beneficial waste phase-change energy-storage aggregate and a micro-surface/interface reinforced phase-change energy-storage cement mortar test piece containing the micro-surface reinforced phase-change energy-storage aggregate.
The compressive strength, flexural strength, thermal conductivity, heat storage capacity and thermal cycle test were respectively carried out on the reference cement mortar test piece prepared in example 1, the micro-surface/interface-reinforced phase-change energy storage mortar test piece not carried out, and the micro-surface/interface-reinforced phase-change energy storage cement mortar test piece containing the micro-surface-reinforced phase-change energy storage aggregate, and the specific test results are shown in table 1.
Table 1 thermophysical properties of the phase-change energy-storage cement mortar of example 1
In example 1, the decrease in mechanical strength and heat transfer performance was smaller than those of the reference sample, and the phase-change energy storage cement mortar was far superior to those without micro-surface/interface strengthening in terms of mechanical strength, heat conductivity coefficient, and heat storage capacity.
In addition, the change of the heat storage capacity during long-term service can be expressed by the time-lapse retention (beta) of the heat storage capacity during service, and the time-lapse retention of the heat storage capacity during service can be calculated by the formula (1):
β＝ΔH 2 /ΔH 1 (1)
wherein beta is the retention rate of heat storage capacity with time and delta H in the service process of the phase-change energy storage cement mortar 1 Is the heat storage capacity delta H before the phase change energy storage cement mortar is in service 2 The heat storage capacity of the phase-change energy storage cement mortar after hundreds of times of thermal cycles.
According to calculation, the time-lapse retention rate of the heat storage capacity of the micro-surface/interface reinforced phase-change energy storage mortar test piece containing the waste-type phase-change material and the micro-surface/interface reinforced phase-change energy storage cement mortar test piece containing the micro-surface reinforced phase-change energy storage aggregate is shown in table 1, and the time-lapse retention rate of the heat storage capacity of the micro-surface/interface reinforced phase-change energy storage cement mortar test piece containing the micro-surface reinforced phase-change energy storage aggregate is up to 99.1%, while the time-lapse retention rate of the heat storage capacity of the time-lapse retention rate of the micro-surface/interface reinforced phase-change energy storage mortar test piece containing the waste-type phase-change material is 0%. The introduction of the micro-surface reinforcing layer is shown, the long-term service performance of the phase-change energy-storage cement mortar is remarkably improved, and the excellent heat storage functionality of the phase-change energy-storage cement mortar in the long-term service process is ensured.
Example 2: the preparation method of the micro-surface reinforced phase change energy storage aggregate comprises the following steps:
1. adding the regenerated porous support material of the fly ash floating beads into a 12mol/L sodium hydroxide solution for ultrasonic cleaning for 2 hours, adding the regenerated porous support material of the fly ash floating beads into a 0.1mol/L hydrochloric acid solution for ultrasonic cleaning for 2 hours, filtering the fly ash floating beads out, repeatedly washing the fly ash floating beads with deionized water, and then drying the fly ash floating beads to obtain the porous support material of the fly ash floating beads, so that the surface pores of the fly ash floating beads are completely exposed, and the purpose of dredging the pore structure is achieved;
2. preparing a waste-utilizing phase change material:
(1) The mass ratio of the decanoic acid to the polyethylene glycol 1500 is 1:1, taking the binary eutectic as a phase change material, placing the eutectic in a beaker, and then placing the beaker in a water bath for heating, wherein the temperature of the water bath is set to 55 ℃;
(2) The device diagram for preparing the waste-utilizing phase-change material is shown in figure 1, the fly ash floating beads treated in the step one are placed in a two-way flask, and a second connecting pipe is connected to the molten eutectic; closing the second vacuum valve, opening the first vacuum valve, immediately starting the vacuum pump, carrying out vacuum treatment on the fly ash floating beads in the flask, closing the vacuum pump when the vacuum degree in the flask is lower than-0.08 MPa, and continuously maintaining for 1h to finish the vacuum treatment on the fly ash floating beads;
(3) Opening a second vacuum valve, and under the action of atmospheric pressure, allowing the molten eutectic to enter a flask filled with the fly ash floating beads until the molten eutectic completely submerges the fly ash floating beads in the flask, closing the second vacuum valve, and keeping for 2 hours, so that the eutectic is immersed in the pores of the fly ash floating beads to obtain the waste-utilizing phase-change energy-storage aggregate; the molten eutectic is sufficient in the whole process, so that no air enters the flask;
(4) After the step (3) is completed, carrying out suction filtration on the mixed liquid in the flask to obtain the waste-utilizing type phase change material;
3. adding 5g of waste-utilizing phase-change material and 0.2g of dopamine into a beaker filled with 50ml of deionized water, and stirring the mixture in the beaker at a speed of 800r/min for 30min at 40 ℃;
4. adding 500mL of 12.5% ethanol solution into a beaker, continuously stirring at 400r/min for 2h, and dropwise adding excessive ammonia water during stirring to completely hydrolyze the ethyl orthosilicate to generate SiO 2 Covering the surface of the fly ash floating beads, filtering, washing and drying to obtain the micro-surface reinforced phase change energy storage aggregate. The method realizes nano SiO through mussel bionic grafting effect 2 And (3) performing in-situ orientation on the micro-surface deposition growth of the waste-utilizing phase change material to finish the coating process of the micro-surface reinforcing layer.
Scanning of the micro-surface enhanced phase change energy storage aggregate obtained in this example 2The electron microscope photograph is shown in figure 2, figure 2 shows that the mussel bionic grafting nano SiO 2 Deposition growth on the surface of the fly ash floating beads, as can be seen from FIG. 2, nano SiO 2 The uniform and compact deposition growth of the waste-utilizing phase-change material is realized through the bionic grafting effect of mussels.
The reference cement mortar, the non-micro-surface/interface reinforced phase-change energy-storage mortar containing the waste-type phase-change material and the micro-surface/interface reinforced phase-change energy-storage cement mortar containing the micro-surface reinforced phase-change energy-storage aggregate prepared in the step two and the micro-surface reinforced phase-change energy-storage aggregate prepared in the step four of the embodiment 2 are prepared by the specific methods as follows:
weighing 12.5% of micro-surface enhanced phase-change energy-storage aggregate, 31.7% of hydraulic cementing material P.O type ordinary Portland cement, 44.3% of standard sand and 11.5% of water according to mass percentage, stirring the micro-surface enhanced phase-change energy-storage aggregate, the standard sand and the P.O type ordinary Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain micro-surface/interface enhanced phase-change energy-storage cement mortar of the micro-surface enhanced phase-change energy-storage aggregate;
weighing 12.5% of waste-utilizing phase-change energy-storage material, 31.7% of hydraulic cementing material P.O type ordinary Portland cement, 44.3% of standard sand and 11.5% of water according to mass percentage, stirring the waste-utilizing phase-change energy-storage material, the standard sand and the P.O ordinary Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain the non-micro-surface/interface reinforced phase-change energy-storage mortar containing the waste-utilizing phase-change energy-storage material;
according to the mass percentage, weighing 31.7% of hydraulic cementing material P.O type Portland cement, 56.8% of standard sand and 11.5% of water, stirring the standard sand and the P.O Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain the reference cement mortar.
And (3) filling the three cement mortars into a mould, vibrating, and curing for 28 days under standard conditions to obtain a reference cement mortar test piece, a non-micro-surface/interface reinforced phase-change energy storage mortar test piece containing the beneficial waste type phase-change energy storage material and a micro-surface/interface reinforced phase-change energy storage cement mortar test piece containing the micro-surface reinforced phase-change energy storage aggregate.
The compressive strength, flexural strength, thermal conductivity, heat storage capacity and thermal cycle of the reference cement mortar test piece prepared in example 2, the non-micro-surface/interface-reinforced phase-change energy storage mortar test piece containing the advantageous waste-type phase-change energy storage material, and the micro-surface/interface-reinforced phase-change energy storage cement mortar test piece containing the micro-surface-reinforced phase-change energy storage aggregate were respectively tested, and the specific test results are shown in table 2.
TABLE 2 Thermophysical Properties of the phase-change energy-storage Cement mortar in example 2
In this embodiment, a scanning electron microscope photograph of a micro-surface/interface-enhanced phase-change energy-storage cement mortar sample containing the micro-surface-enhanced phase-change energy-storage aggregate is shown in fig. 3, fig. 3 shows compatibility of the micro-surface-enhanced phase-change energy-storage aggregate with a cement matrix and deposition of hydration products at the interface, and as can be seen from fig. 3, the interface between the micro-surface-enhanced phase-change energy-storage aggregate and the cement matrix is very compact, and a large amount of cement hydration products are deposited and grown at the interface in a large amount. It can be also confirmed from table 2 that the phase-change energy-storage mortar subjected to micro-surface/interface strengthening is significantly higher in compressive strength, flexural strength and thermal conductivity than the phase-change energy-storage cement mortar not subjected to micro-surface/interface strengthening. Meanwhile, the forming of the micro-surface reinforcing layer also improves the setting capability of the phase-change energy storage aggregate and the cracking resistance in the mixing process with the cement mortar, after 300 times of thermal cycle test, the heat storage capacity of the micro-surface/interface reinforced phase-change energy storage cement mortar sample containing the micro-surface reinforced phase-change energy storage aggregate is almost not lost, the retention rate of the heat storage capacity in the service process is as high as 97.9 percent over time, compared with 28.1 percent of the phase-change energy storage cement mortar without the micro-surface/interface reinforcement, the heat storage stability in the long-term service is obviously improved, and the heat storage capacity of the phase-change energy storage cement mortar without the micro-surface/interface reinforcement is obviously reduced.
Example 3: the preparation method of the micro-surface reinforced phase change energy storage aggregate comprises the following steps:
1. firstly adding the regenerated porous supporting material waste incineration ash into a 12mol/L sodium hydroxide solution for ultrasonic cleaning for 3 hours, then adding the regenerated porous supporting material waste incineration ash into a 0.1mol/L hydrochloric acid solution for ultrasonic cleaning for 3 hours, filtering the treated waste incineration ash, repeatedly washing the treated waste incineration ash with deionized water, and then drying the treated waste incineration ash to obtain the regenerated porous supporting material waste incineration ash, so that the surface pores of the waste incineration ash are completely exposed, and the purpose of dredging the pore structure is achieved;
2. preparing a waste-utilizing type phase-change energy storage material:
(1) Taking industrial paraffin as a phase change material, placing the paraffin into a beaker, and then placing the beaker into a water bath kettle for heating, wherein the temperature set by the water bath kettle is 70 ℃;
(2) The device diagram for preparing the waste-utilizing type phase-change material is shown in figure 1, the waste incineration ash treated in the step one is placed in a two-way flask, and a second connecting pipe is connected to molten paraffin; closing the second vacuum valve, opening the first vacuum valve, starting a vacuum pump immediately, carrying out vacuum treatment on the garbage incineration ash in the flask, closing the vacuum pump when the vacuum degree in the flask is lower than-0.08 MPa, and continuously maintaining for 1h to finish the vacuum treatment on the garbage incineration ash;
(3) Opening a second vacuum valve, and under the action of atmospheric pressure, allowing molten paraffin to enter a flask filled with waste incineration ash until the molten paraffin completely submerges the waste incineration ash in the flask, closing the second vacuum valve, and keeping for 2 hours, so that the paraffin is immersed in the pores of the waste incineration ash to obtain the waste-utilizing type phase-change energy-storage aggregate; the molten paraffin is sufficient in the whole process, so that no air enters the flask;
(4) After the step (3) is completed, carrying out suction filtration on the mixed liquid in the flask to obtain the waste-utilizing type phase change material;
3. adding 5g of waste-utilizing phase-change energy-storage aggregate and 0.3g of sodium polyacrylate aqueous solution into a beaker containing 200ml of deionized water, and stirring at 80 ℃ for 20min at a rotating speed of 700 r/min;
4. then 11.1g of anhydrous CaCl was added to the beaker 2 Stirring was continued at 400r/min for 2h, followed byContinuously dripping 0.15mol/L Na into the suspension 2 CO 3 Solutions of CaCl 2 And Na (Na) 2 CO 3 The molar ratio of (2) is 1: stop Na at 1 2 CO 3 And (3) dropwise adding the solution, filtering, washing and drying to obtain the micro-surface enhanced phase change energy storage aggregate. The method realizes nano CaCO through hydroxyl induction 3 And (3) coating the micro-surface enhancement layer.
The reference cement mortar, the non-micro surface/interface reinforced phase-change energy storage mortar containing the waste-type phase-change material and the micro surface/interface reinforced phase-change energy storage cement mortar containing the micro surface-reinforced phase-change energy storage aggregate prepared in the embodiment 3 are prepared by utilizing the waste-type phase-change material and the micro surface-reinforced phase-change energy storage aggregate, and the specific methods are as follows:
weighing 9.8% of micro-surface reinforced phase-change energy-storage aggregate, 32.5% of hydraulic cementing material P.O type Portland cement, 45.3% of standard sand and 12.4% of water according to the mass percentage, stirring the micro-surface reinforced phase-change energy-storage aggregate, the standard sand and the P.O Portland cement together for 3min, adding water after stirring uniformly, and continuously stirring for 5min to obtain micro-surface/interface reinforced phase-change energy-storage cement mortar containing the micro-surface reinforced phase-change energy-storage aggregate;
according to the mass percentage, 9.8% of waste-utilizing phase-change material, 32.5% of hydraulic cementing material P.O type Portland cement, 45.3% of standard sand and 12.4% of water are weighed, the waste-utilizing phase-change material, the standard sand and the P.O Portland cement are stirred for 3min together, water is added after the uniform stirring, and the stirring is continued for 5min, so that the non-micro-surface/interface reinforced phase-change energy storage mortar containing the waste-utilizing phase-change material is obtained;
according to the mass percentage, 32.5% of hydraulic cementing material P.O type Portland cement, 55.1% of standard sand and 12.4% of water are weighed, the standard sand and the P.O Portland cement are stirred for 3min together, and water is added to continuously stir for 5min after the standard sand and the P.O Portland cement are stirred uniformly, so that the reference cement mortar is obtained.
And (3) filling the three cement mortars into a mould, vibrating, and curing for 28 days under standard conditions to obtain a reference cement mortar test piece, an unprecedented micro-surface/interface reinforced phase-change energy storage mortar test piece containing the beneficial waste phase-change material and a micro-surface/interface reinforced phase-change energy storage cement mortar test piece containing the micro-surface reinforced phase-change energy storage aggregate.
The compressive strength, flexural strength, thermal conductivity, heat storage capacity and thermal cycle of the reference cement mortar test piece prepared in example 3, the non-micro-surface/interface-reinforced phase-change energy storage mortar test piece containing the advantageous waste-type phase-change energy storage aggregate, and the micro-surface/interface-reinforced phase-change energy storage cement mortar test piece containing the micro-surface-reinforced phase-change energy storage aggregate were respectively tested, and the specific test results are shown in table 3.
TABLE 3 Thermophysical Properties of the phase-change energy-storage Cement mortar in example 3
As can be seen from table 3, the compressive strength, flexural strength, thermal conductivity and heat storage capacity of the micro-surface/interface reinforced phase-change energy storage cement mortar sample containing the micro-surface reinforced phase-change energy storage aggregate are higher than those of the non-micro-surface/interface reinforced phase-change energy storage mortar sample containing the waste-type phase-change material, and the compressive strength, flexural strength and thermal conductivity are only slightly lower than those of the reference cement mortar, which indicates that the micro-surface reinforced phase-change energy storage aggregate can remarkably improve the heat storage capacity of the phase-change energy storage cement mortar. On the other hand, after 300 times of thermal cycles, the thermal storage capacity time retention rate of the micro-surface/interface reinforced phase-change energy storage cement mortar sample containing the micro-surface reinforced phase-change energy storage aggregate in the service process is as high as 95.5%, which is obviously higher than the thermal storage capacity time retention rate of the micro-surface/interface reinforced phase-change energy storage mortar sample containing the beneficial waste phase-change material in the service process, which is not used for the micro-surface/interface reinforced phase-change energy storage mortar sample, in the service process. The micro-surface/interface reinforced phase-change energy storage cement mortar containing the micro-surface reinforced phase-change energy storage aggregate can ensure that the loss of heat storage capacity is small after long-term service, and can also ensure excellent mechanical strength, heat transfer performance and heat storage capacity.
The embodiment proves that when the waste-utilizing type phase-change material for the building material and the micro-surface/interface strengthening technology thereof are applied to cement mortar, the obtained phase-change energy-storage cement mortar has the advantages of high strength, excellent heat conduction performance, low price, simple preparation, high-value utilization of wastes, low energy storage capacity loss after long-term service and the like, and the phase-change energy-storage cement mortar with different mechanical strength, heat conduction capacity and heat storage capacity can be obtained by adjusting the proportion of phase-change energy-storage aggregate, water, cementing material and sand.
Claims (10)
1. The micro-surface reinforced phase change energy storage aggregate is characterized by being composed of a regenerated porous supporting material, a phase change material and a micro-surface reinforcing layer; the phase change material is loaded in the pores of the regenerated porous supporting material, and the micro-surface reinforcing layer is coated on the surface of the regenerated porous supporting material;
wherein the regenerated porous supporting material is a porous material recovered from solid waste, and comprises biochar, porous biomass material, porous waste plastic, porous waste rubber, fly ash, heavy putty, sludge ash, garbage incineration ash, agricultural solid waste incineration ash or waste wood;
the micro-surface enhancement layer is nano SiO 2 Layer or nano CaCO 3 A layer.
2. The micro-surface enhanced phase change energy storage aggregate according to claim 1, wherein the phase change material is a solid-liquid phase change material; the solid-liquid phase change material is an organic phase change material, an inorganic phase change material or a eutectic phase change material composed of the organic phase change material and the inorganic phase change material.
3. The micro-surface enhanced phase change energy storage aggregate according to claim 2, wherein the inorganic phase change material is a hydrated salt, and the organic phase change material is paraffin and its derivatives, polyethylene glycol or fatty acid.
4. A method for preparing the micro-surface enhanced phase change energy storage aggregate as claimed in claim 1, which is characterized by comprising the following steps:
1. firstly adding the regenerated porous support material into a sodium hydroxide solution for ultrasonic cleaning for 1-3.5 h, then adding the regenerated porous support material into a hydrochloric acid solution for ultrasonic cleaning for 1-3.5 h, and then drying to obtain the aim of dredging the pore structure;
2. melting the phase change material, adding the regenerated porous support material into the melted phase change material, and dipping the melted phase change material into the pores of the regenerated porous support material by a vacuum adsorption method to obtain the waste-utilizing phase change material;
3. preparing a layer of compound with hydroxyl or a layer of compound with a tea phenol structure on the surface of the waste-utilizing phase-change material by a dipping or emulsifying method;
4. depositing and coating nano SiO on the surface of waste-utilizing phase-change material 2 Layer or nano CaCO 3 And taking the layer as a micro-surface reinforcing layer, washing and drying to obtain the micro-surface reinforced phase change energy storage aggregate.
5. The method for preparing a micro-surface enhanced phase change energy storage aggregate according to claim 4, wherein the compound with hydroxyl in the third step is sodium polyacrylate, polyacrylamide, lauryl alcohol chloride, polyethylene glycol or chitosan.
6. The method for preparing a micro-surface enhanced phase change energy storage aggregate according to claim 4 or 5, wherein the chemical having a theanine structure in the step three is dopamine or DOPA.
7. The method for preparing the micro-surface enhanced phase-change energy storage aggregate according to claim 4 or 5, wherein the method for preparing the micro-surface enhanced phase-change energy storage aggregate is characterized in that in the fourth step, nano SiO is coated on the surface of the waste-utilizing phase-change material in a deposition manner 2 The method of the layer is as follows: placing the waste-utilizing phase-change material treated in the third step into a container, then adding deionized water, absolute ethyl alcohol and tetraethoxysilane into the container, fully stirring for 1.5-3.5 h at a stirring rate of 400-1200 rmp, gradually dropwise adding ammonia water in the stirring process, and regulating the pH value of the reaction solution to 8-10, so that the surface of the waste-utilizing phase-change material is directionally deposited, and a micro-surface reinforcing layer is formed.
8. The method for preparing the micro-surface enhanced phase change energy storage aggregate according to claim 4 or 5, wherein the method for preparing the micro-surface enhanced phase change energy storage aggregate is characterized in that in the fourth step, nano CaCO is deposited and coated on the surface of the waste-utilizing phase change material 3 The method of the layer is as follows: placing the waste-utilizing phase-change material treated in the third step into a container, and then adding deionized water and anhydrous CaCl into the container 2 Fully stirring for 1-3 h at the stirring rate of 300-600 rmp, and then continuously dripping Na with the concentration of 0.1-0.3 mol/L 2 CO 3 Solutions of CaCl 2 And Na (Na) 2 CO 3 The ratio of the amounts of the substances is (0.8-1.2): stop Na at 1 2 CO 3 And (3) dropwise adding the solution to enable the surface of the waste-utilizing phase change material to be directionally deposited to form a micro-surface enhancement layer.
9. The application of the micro-surface reinforced phase-change energy storage aggregate as claimed in claim 1, which is characterized in that the micro-surface reinforced phase-change energy storage aggregate is used for preparing phase-change energy storage cement mortar.
10. The application of the micro-surface enhanced phase-change energy storage aggregate according to claim 9, wherein the phase-change energy storage cement mortar is prepared by mixing 9.4-15.3% of micro-surface enhanced phase-change energy storage aggregate, 26.6-32.5% of hydraulic cementing material, 39.5-45.4% of sand and 6.8-24.5% of water according to mass percent.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671136A (en) * | 2008-09-09 | 2010-03-17 | 同济大学 | Method for preparing phase change thermal storage-based novel energy-storing and heat-insulating mortar |
| CN103508702A (en) * | 2012-06-17 | 2014-01-15 | 唐伯明 | Cold-mix phase change type asphalt mixture for thermal energy storage |
| KR101618352B1 (en) * | 2014-11-07 | 2016-05-04 | 라성에너지(주) | Heat resistant thermal storage materials using paraffin phase change materials and preparation method thereof |
| CN105621918A (en) * | 2016-01-11 | 2016-06-01 | 东南大学 | Building phase-change heat storage composite material used as light aggregate |
| KR20200018307A (en) * | 2018-08-10 | 2020-02-19 | 톤산 어데시브, 아이엔씨. | Phase change energy storage microcapsule preparation and use thereof |
| CN111004011A (en) * | 2019-12-16 | 2020-04-14 | 中国科学院青海盐湖研究所 | Magnesium cement phase-change building material and preparation method thereof |
| CN113173740A (en) * | 2020-05-09 | 2021-07-27 | 中国科学院青海盐湖研究所 | Phase-change thermal insulation mortar and preparation method thereof |
-
2023
- 2023-02-08 CN CN202310083056.7A patent/CN116119959B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671136A (en) * | 2008-09-09 | 2010-03-17 | 同济大学 | Method for preparing phase change thermal storage-based novel energy-storing and heat-insulating mortar |
| CN103508702A (en) * | 2012-06-17 | 2014-01-15 | 唐伯明 | Cold-mix phase change type asphalt mixture for thermal energy storage |
| KR101618352B1 (en) * | 2014-11-07 | 2016-05-04 | 라성에너지(주) | Heat resistant thermal storage materials using paraffin phase change materials and preparation method thereof |
| CN105621918A (en) * | 2016-01-11 | 2016-06-01 | 东南大学 | Building phase-change heat storage composite material used as light aggregate |
| KR20200018307A (en) * | 2018-08-10 | 2020-02-19 | 톤산 어데시브, 아이엔씨. | Phase change energy storage microcapsule preparation and use thereof |
| CN111004011A (en) * | 2019-12-16 | 2020-04-14 | 中国科学院青海盐湖研究所 | Magnesium cement phase-change building material and preparation method thereof |
| CN113173740A (en) * | 2020-05-09 | 2021-07-27 | 中国科学院青海盐湖研究所 | Phase-change thermal insulation mortar and preparation method thereof |
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