CN116119955A - Preparation method of phase-change energy-storage microspheres for building - Google Patents
Preparation method of phase-change energy-storage microspheres for building Download PDFInfo
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- CN116119955A CN116119955A CN202310083054.8A CN202310083054A CN116119955A CN 116119955 A CN116119955 A CN 116119955A CN 202310083054 A CN202310083054 A CN 202310083054A CN 116119955 A CN116119955 A CN 116119955A
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- phase
- change energy
- storage
- microsphere
- change
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- 238000004146 energy storage Methods 0.000 title claims abstract description 158
- 239000004005 microsphere Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000012782 phase change material Substances 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002195 synergetic effect Effects 0.000 claims abstract description 12
- 239000011257 shell material Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000945 filler Substances 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002563 ionic surfactant Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000002910 solid waste Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000004568 cement Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000003181 co-melting Methods 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004056 waste incineration Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000003469 silicate cement Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229940018038 sodium carbonate decahydrate Drugs 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 3
- 230000008859 change Effects 0.000 abstract description 40
- 239000004566 building material Substances 0.000 abstract description 19
- 238000005338 heat storage Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000007493 shaping process Methods 0.000 abstract description 4
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 51
- 238000011068 loading method Methods 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011162 core material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229940001593 sodium carbonate Drugs 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
-
- 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
- C04B20/12—Multiple coating or impregnating
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0071—Phase-change materials, e.g. latent heat storage materials used in concrete compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
A preparation method of phase change energy storage microspheres for buildings relates to a preparation method of hydraulic high-performance shaping phase change materials for building energy storage, and belongs to the field of civil engineering. The method aims to solve the problems of low strength, poor heat conduction performance, poor compatibility with building materials, poor mechanical performance of the phase-change energy-storage building materials, defects of microstructures, low heat transfer efficiency and limited heat storage capacity of the phase-change energy-storage microspheres, and comprises the following steps: 1. preparing a high thermal conductivity network precursor; 2. preparing a hydraulic cementing material shell; 3. and preparing the phase-change energy storage microsphere. The phase-change energy-storage microsphere has the advantages of low cost, high latent heat, high heat conductivity coefficient and high strength, wherein the high-strength phase-change energy-storage microsphere shell provides a basis for the excellent mechanical properties, the application range is widened due to the use of the phase-change material inner cores with different phase-change temperatures, the activity of the phase-change energy-storage microsphere in the hydration reaction of the cementing material is excited by the novel surface synergistic design, and the heat conductivity of the phase-change energy-storage microsphere is improved.
Description
Technical Field
The invention relates to a preparation method of a hydraulic high-performance shaping phase-change material for building energy storage, belonging to the field of civil engineering.
Background
The building material has stable strength, simple and convenient preparation and low cost, and is therefore commonly used as a building heat preservation and insulation material and a matrix material of various heat storage units. The phase change material can realize the absorption, storage and release of heat energy in the phase change process, and has a good heat regulation function. According to the phase change process, the phase change materials can be classified into solid-solid phase change materials, solid-liquid phase change materials, solid-gas phase change materials, liquid-gas phase change materials and the like, wherein the solid-liquid phase change materials are rich in sources, low in cost and most widely applied. However, the defect of poor shape stability of the solid-liquid phase change material in the phase change process greatly limits the maximum utilization of the heat storage function of the solid-liquid phase change material, and the phase change energy storage microsphere with the core-shell structure can be prepared by coating the phase change material with the shaping material. The phase-change energy-storage building material formed by combining the phase-change energy-storage microspheres and the building material can greatly improve the heat storage capacity of the building material, realize the efficient heat regulation function, and has application potential in the fields of building thermal comfort, agriculture, food industry, electronic equipment heat management and the like.
The phase change material can absorb or release a large amount of heat in the phase transition process, is an excellent energy storage material, is prepared into phase change energy storage microspheres through a certain packaging method, and is an important mode for applying the phase change material by doping the phase change energy storage microspheres into different base materials (such as cement-based materials, plastics and the like) according to the use scene. However, the existing phase-change energy storage microspheres often have the problem of low strength, so that the phase-change material is easy to break and leak in the preparation and use processes, the heat storage capacity is reduced, and the heat-force performance of the material is comprehensively deteriorated due to the leakage of the phase-change material in an application matrix; moreover, the inherent low heat conductivity coefficient of the phase-change material restricts the energy storage efficiency of the phase-change energy storage microsphere, so that the phase-change material in the phase-change energy storage microsphere is difficult to completely melt or solidify, thereby reducing the utilization efficiency of the phase-change material; in addition, the compatibility with the application matrix material also causes obvious defects of the microstructure of the matrix material, which not only can lead to obvious reduction of the strength of the phase-change energy storage building material and seriously weaken the bearing capacity of the phase-change energy storage building material, but also can improve the interface thermal resistance and influence the internal heat energy transmission efficiency of the phase-change energy storage building material. One of the main current research ideas is to improve the strength and the heat conductivity of the matrix material, for example, nano-admixture, carbon fiber, metal fiber and the like with high strength and high heat conductivity coefficient are additionally added into the matrix material. However, the method has an unsatisfactory effect on strengthening mechanical properties, greatly increases the production cost of the phase-change energy storage building material, and cannot effectively solve the problems of the strength, the thermal conductivity and the compatibility of the matrix of the phase-change energy storage microsphere; in addition, the heat conducting property of the phase-change energy storage material is improved by adding the high-heat-conducting filler on the surface of the phase-change energy storage microsphere or in the phase-change material. Unfortunately, the problem of poor dispersibility of the heat conducting filler is difficult to solve by directly adding the high heat conducting filler into the phase change material, and the technology is difficult to directly apply to the preparation of the phase change energy storage microsphere, while the problem of inherent low heat conducting efficiency of the internal phase change material cannot be solved by introducing the high heat conducting filler into the surface of the phase change energy storage microsphere. The poor thermal performance of the phase-change energy storage microspheres greatly limits the application of the phase-change energy storage building material.
Disclosure of Invention
The invention aims to solve the technical problems of low strength, poor heat conduction performance, poor compatibility with building materials, poor mechanical properties of the phase-change energy-storage building materials, defects of microstructures, low heat transfer efficiency and limited heat storage capacity of the phase-change energy-storage microspheres, and provides a preparation method of the phase-change energy-storage microspheres for buildings.
The preparation method of the phase change energy storage oriented to the building comprises the following steps:
1. preparing a high heat conduction network precursor:
weighing 5-20 parts of network supporting structure, 79.99-94.999 parts of soluble salt and 0.001-0.01 part of high heat conduction filler according to the parts by weight, wherein the total parts of the network supporting structure, the soluble salt and the high heat conduction filler are 100 parts,
uniformly mixing the soluble salt and the network support structure, adding 1000 parts by mass of water, continuously stirring to completely dissolve the soluble salt and the network support structure, completely dispersing the high-heat-conductivity filler into the mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high-heat-conductivity network precursor;
in the first step, the network support structure is lignocellulose, sodium polyacrylate or sodium alginate;
the soluble salt in the first step is sodium chloride, sodium sulfate or calcium chloride;
in the first step, the high-heat-conductivity filler is carbon powder, graphene or graphene oxide;
2. preparing a hydraulic cementing material shell:
weighing 20-80 parts of hydraulic cementing material and 20-80 parts of high heat conduction network precursor according to the parts by weight, wherein the total parts of the hydraulic cementing material and the high heat conduction network precursor are 100 parts, mixing and stirring the hydraulic cementing material and the high heat conduction network precursor uniformly, and adding water to form slurry, wherein the addition amount of the water is 20-50% of the total mass of the hydraulic cementing material and the high heat conduction network precursor (the prepared slurry has good fluidity and viscosity, and ensures that the high heat conduction network precursor is stably and uniformly dispersed in the slurry)
Dropwise adding slurry into the oil continuous phase and continuously stirring, gradually heating the oil continuous phase to 50-80 ℃ at a heating rate of 5-10 ℃ per minute after the slurry forms microspheres in the continuous phase, and filtering, washing and drying after reacting for 0.5-12 h to obtain a hydraulic cementing material shell;
step two, adding the slurry into the oil continuous phase dropwise and stirring at the rotating speed of 800 rmp;
the hydraulic cementing material in the second step is silicate cement, sulphoaluminate cement, magnesium phosphate cement, gypsum or waste alkali excitation material;
the waste alkali excitation material consists of solid waste and an alkali exciting agent, wherein the solid waste is one or more of tailings, slag, municipal waste incineration ash and industrial waste incineration ash, and the alkali exciting agent is NaOH solution and Na solution 2 CO 3 Solution, na 2 SiO 3 Solution, KOH solution, K 2 CO 3 Solutions or K 2 SiO 3 Solution of waste alkali exciting material according to SiO 2 With Al 2 O 3 The mass ratio of (2) is 0.8-2.2, na 2 O or K 2 O and Al 2 O 3 The mass ratio of (C) is 0.5-1.5, H 2 O and Na 2 O or K 2 The mass ratio of O is 15-19 to determine the dosage of alkali-exciting agent;
the compressive strength of the high-strength hydraulic cementing material shell in the second step is not lower than 20MPa;
in the second step, the oil continuous phase is carbon tetrachloride, polyethylene glycol or paraffin; the polyethylene glycol is PEG600 or PEG800;
3. preparing phase-change energy-storage microspheres:
immersing the hydraulic cementing material shell in the phase-change material for 1-5 h under the vacuum condition at the temperature of 50-80 ℃, and obtaining the phase-change energy storage microspheres through filtration, washing and drying;
in the third step, the phase change material is prepared by co-melting two or more of paraffin, fatty acid, lauric acid, capric acid, polyethylene glycol disodium hydrogen phosphate dodecahydrate, sodium carbonate decahydrate and calcium chloride hexahydrate;
4. surface synergy is carried out on the phase-change energy storage microsphere:
placing the phase-change energy-storage microspheres prepared in the step three into an ionic surfactant solution, adding a surface synergistic shell material, stirring for 1-5 h, filtering, washing and drying to obtain the phase-change energy-storage microspheres;
the mass ratio of the ionic surfactant to the phase-change energy-storage microspheres is 0.01-0.1;
the mass ratio of the surface synergistic shell material to the phase-change energy storage microsphere is 0.005-0.1;
and step four, the surface synergistic shell material is nano silicon dioxide or nano calcium carbonate.
The ionic surfactant in the fourth step is 1% of hexadecyl ammonium bromide aqueous solution, dodecyl benzene sulfonic acid aqueous solution, fatty alcohol acyl sodium sulfate aqueous solution, ethoxylated fatty acid methyl ester sodium sulfonate aqueous solution and secondary alkyl sodium sulfonate aqueous solution by mass percent.
The ionic surfactant in the fourth step is alcohol ether sulfate or alcohol ether phosphate.
The high-heat-conductivity network precursor is used as a template to control the shape of the high-heat-conductivity network precursor, the prepared high-heat-conductivity network precursor enables the high-heat-conductivity filler to be uniformly dispersed to a network supporting structure, the high-heat-conductivity filler is compounded with the phase change material through the network supporting structure, the problem that the high-heat-conductivity filler is difficult to disperse in the phase change material is perfectly solved, meanwhile, a high-efficiency heat conduction path is constructed, and the problems that the traditional phase change energy storage microsphere only solves surface heat conduction and inconsistent melting of internal phase change material core materials are difficult to solve are solved;
the hydraulic cementing material shell ensures that the prepared phase-change energy-storage microsphere has excellent mechanical properties, thereby widening the application scene of the phase-change energy-storage microsphere.
In the preparation of the hydraulic binder housing, the soluble salts in the highly thermally conductive network precursor contained inside the housing are first dissolved out. After the moisture is removed by drying, the residual polymer network and the high heat conduction filler form a porous high heat conduction network.
No matter what kind of hydraulic cementing material is adopted for preparing the high-strength shell, the formed continuous slurry is ensured to have better fluidity so as to ensure that the continuous slurry can be dispersed to form microspheres, and certain viscosity of the continuous slurry is ensured so that the continuous slurry can be completely wrapped on the high-heat-conductivity network precursor and is prevented from being broken in the subsequent stirring process.
The specific surface synergy forming process of the phase change energy storage microsphere comprises the steps of firstly, coating a layer of ionic surfactant on the surface of a hydraulic cementing material shell, and using electrostatic induction to lead the surface synergy material (nano SiO 2 Nano CaCO 3 Etc.) grafted onto the surface of the hydraulic binder housing.
According to the invention, the hollow microsphere carrier is prepared by taking the hydraulic cementing material as a matrix, a high-heat-conductivity supporting structure is used for constructing a heat-conducting passage in the carrier, the phase-change energy storage microsphere is prepared by adopting a vacuum impregnation method, and the phase-change energy storage microsphere is modified by using an interface synergistic agent. The adopted high heat conduction support structure serves as a hollow microsphere template when the carrier is prepared, and after dissolution and freeze-drying treatment, a reticular porous heat conduction network is formed inside the hollow microsphere template, so that the setting capacity and the energy storage efficiency of the phase-change energy storage microsphere are greatly improved. The phase change energy storage microsphere after surface modification can be stably dispersed in a hydrophilic matrix, is convenient to apply to hydraulic building materials, and forms tight adhesion with the hydraulic building materials in the hydration process of the hydraulic building materials, thereby remarkably improving the microstructure, reducing the interface thermal resistance and improving the mechanical property. The material is derived from various cementing materials, can be widely applied to solid waste alkali excitation materials to prepare high-strength high-heat-conductivity carriers, and solves the problems of poor mechanical property and low internal heat conduction efficiency of the phase change energy storage material while reducing the cost. When the phase-change energy storage building material is applied to hydraulic building materials, the mechanical property and the energy storage efficiency of the phase-change energy storage building material can be effectively improved.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a hydraulic high-performance shaped phase-change material for building energy storage, which solves the problems of low strength, poor compatibility with an application matrix, poor mechanical property, defect in microstructure, low heat transfer efficiency, limited heat storage capacity and the like of the phase-change energy storage microsphere mentioned in the background art based on the high strength of the hydraulic cementing material and good heat conductivity of a surface synergistic layer, thereby improving the reliability of the phase-change energy storage material and widening the application range of the phase-change energy storage microsphere. Meanwhile, the phase-change energy storage microspheres prepared by using the solid waste and the alkali excitant can achieve the purposes of energy conservation and emission reduction.
The phase-change energy-storage microsphere has the advantages of low cost, high latent heat, high heat conductivity coefficient and high strength, wherein the high-strength phase-change energy-storage microsphere shell provides a basis for the excellent mechanical properties, the application range is widened due to the use of the phase-change material inner cores with different phase-change temperatures, the activity of the phase-change energy-storage microsphere in the hydration reaction of the cementing material is excited by the novel surface synergistic design, and the heat conductivity of the phase-change energy-storage microsphere is improved.
The invention improves the energy storage effect of the phase-change energy storage microsphere. On one hand, the phase-change energy storage microsphere has higher strength, and can avoid leakage of the phase-change material caused by external damage factors in the use process; on the other hand, the interface connection between the phase change energy storage microsphere subjected to surface synergy treatment and the application matrix is effectively enhanced, and the microstructure of the application matrix reduces the interface thermal resistance, so that the heat transfer efficiency is greatly improved; more importantly, the high-heat-conductivity network precursor adopted by the invention plays roles of a template, a heat-conductivity network and a shaping network, the shape of the phase-change energy storage microsphere is controllable and adjustable by manufacturing the high-heat-conductivity network precursor with different sizes as the template, and after soluble salt is dissolved out, the high-heat-conductivity network formed by the network support structure and the high-heat-conductivity filler is reserved, so that a stable and efficient heat transfer path and a heat transport channel are constructed, incomplete melting of an inner core of the phase-change material in the phase-change energy storage microsphere is reduced, the utilization rate of the phase-change material is improved, the heat storage efficiency of the microsphere is obviously enhanced, and the network is combined with the inner core of the phase-change material through various intermolecular forces such as Van der Waals force, hydrogen bond and the like, so that the leakage of the inner core of the phase-change material is further avoided. Based on the principle and the effect, the preparation method provided by the invention realizes high strength and high heat conduction performance, and the solid waste is used as the raw material for preparing the phase-change energy storage microsphere shell, so that the natural resource consumption and the carbon dioxide emission can be effectively reduced, and the preparation method is favorable for environmental protection, energy conservation and emission reduction.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the phase change energy storage for the building comprises the following steps:
1. preparing a high heat conduction network precursor:
weighing 5-20 parts of network supporting structure, 79.99-94.999 parts of soluble salt and 0.001-0.01 part of high heat conduction filler according to the parts by weight, wherein the total parts of the network supporting structure, the soluble salt and the high heat conduction filler are 100 parts,
uniformly mixing the soluble salt and the network support structure, adding 1000 parts by mass of water, continuously stirring to completely dissolve the soluble salt and the network support structure, completely dispersing the high-heat-conductivity filler into the mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high-heat-conductivity network precursor;
in the first step, the network support structure is lignocellulose, sodium polyacrylate or sodium alginate;
the soluble salt in the first step is sodium chloride, sodium sulfate or calcium chloride;
in the first step, the high-heat-conductivity filler is carbon powder, graphene or graphene oxide;
2. preparing a hydraulic cementing material shell:
weighing 20-80 parts of hydraulic cementing material and 20-80 parts of high heat conduction network precursor according to the parts by weight, wherein the total part of the hydraulic cementing material and the high heat conduction network precursor is 100 parts, mixing and stirring the two materials uniformly, adding water to form slurry, wherein the addition amount of the water is 20-50% of the total mass of the hydraulic cementing material and the high heat conduction network precursor, dropwise adding the slurry into an oil continuous phase, continuously stirring, gradually heating the oil continuous phase to 50-80 ℃ at the heating rate of 5-10 ℃ per minute after the slurry forms microspheres in the continuous phase, and filtering, washing and drying after the reaction is carried out for 0.5-12 hours to obtain a hydraulic cementing material shell;
the hydraulic cementing material in the second step is silicate cement, sulphoaluminate cement, magnesium phosphate cement, gypsum or waste alkali excitation material;
the waste alkali-activated material consists of solid waste and an alkali-activated agent, wherein the alkali-activated agent is NaOH solution and Na 2 CO 3 Solution, na 2 SiO 3 Solution, KOH solution, K 2 CO 3 Solutions or K 2 SiO 3 Solution of waste alkali exciting material according to SiO 2 With Al 2 O 3 The mass ratio of (2) is 0.8-2.2, na 2 O or K 2 O and Al 2 O 3 The mass ratio of (C) is 0.5-1.5, H 2 O and Na 2 O or K 2 The mass ratio of O is 15-19 to determine the dosage of alkali-exciting agent;
in the second step, the oil continuous phase is carbon tetrachloride, polyethylene glycol or paraffin;
3. preparing phase-change energy-storage microspheres:
immersing the hydraulic cementing material shell in the phase-change material for 1-5 h under the vacuum condition at the temperature of 50-80 ℃, and obtaining the phase-change energy storage microspheres through filtration, washing and drying;
in the third step, the phase change material is prepared by co-melting two or more of paraffin, fatty acid, lauric acid, capric acid, polyethylene glycol disodium hydrogen phosphate dodecahydrate, sodium carbonate decahydrate and calcium chloride hexahydrate;
the phase change material has any ratio of the components.
4. Surface synergy is carried out on the phase-change energy storage microsphere:
placing the phase-change energy-storage microspheres prepared in the step three into an ionic surfactant solution, adding a surface synergistic shell material, stirring for 1-5 h, filtering, washing and drying to obtain the phase-change energy-storage microspheres;
the mass ratio of the ionic surfactant to the phase-change energy-storage microspheres is 0.01-0.1;
the mass ratio of the surface synergistic shell material to the phase-change energy storage microsphere is 0.005-0.1;
the surface synergistic shell layer material in the fourth step is nano silicon dioxide or nano calcium carbonate;
the ionic surfactant in the fourth step is 1% of hexadecyl ammonium bromide aqueous solution, dodecyl benzene sulfonic acid aqueous solution, fatty alcohol acyl sodium sulfate aqueous solution, ethoxylated fatty acid methyl ester sodium sulfonate aqueous solution and secondary alkyl sodium sulfonate aqueous solution by mass percent.
The second embodiment is as follows: this embodiment differs from the first embodiment in that in step two, the slurry is added dropwise to the oil continuous phase and stirred at a speed of 800 rmp. The other is the same as in the first embodiment.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that the solid waste in the second step is one or more of tailings, slag, municipal waste incineration ash, and industrial waste incineration ash. The other embodiments are the same as those of the first or second embodiment.
In the present embodiment, when the solid waste is a composition, the components are in any ratio.
The specific embodiment IV is as follows: the difference between the present embodiment and one to three embodiments is that the compressive strength of the high-strength hydraulic cementing material shell in the second step is not lower than 20MPa. The other is the same as in one of the first to third embodiments.
Fifth embodiment: the difference between the present embodiment and the first to fourth embodiments is that the polyethylene glycol in the second step is PEG600 or PEG800. The others are the same as in one to one fourth embodiments.
Specific embodiment six: this embodiment differs from one to fifth embodiments in that the ionic surfactant described in step four is an alcohol ether sulfate or an alcohol ether phosphate. The other is the same as in one of the first to fifth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
the preparation method of the phase change energy storage oriented to the building comprises the following steps:
1. preparing a high heat conduction network precursor:
weighing 10 parts of lignocellulose, 89.99 parts of sodium chloride and 0.01 part of carbon powder according to parts by weight, uniformly mixing the sodium chloride and the lignocellulose, adding 1000 parts of water, continuously stirring to completely dissolve the sodium chloride and the lignocellulose, completely dispersing the carbon powder into a mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high heat conduction network precursor;
2. preparing a hydraulic cementing material shell:
mixing and stirring uniformly 20 parts by mass of a mixture of solid waste iron tailing powder and slag, 35% by mass of solid content and 20 parts by mass of sodium silicate solution of a 1 mould, adding 60 parts by mass of a high heat conduction network precursor (and preparing a control group by using sodium chloride salt balls), fully stirring, mixing and stirring uniformly the two, adding water accounting for 20% of the total mass of all materials, mixing uniformly to form slurry, dropwise adding the slurry into melted PEG800, continuously stirring, gradually heating an oil continuous phase to 50 ℃ at a heating rate of 5 ℃ per minute after the slurry forms microspheres in the continuous phase, stirring at a rotating speed of 800rmp for 4 hours, filtering, washing with hot water, and drying to obtain a hydraulic cementing material shell;
3. preparing phase-change energy-storage microspheres:
immersing a hydraulic cementing material shell in a capric acid-paraffin co-melted phase change material (prepared by co-melting capric acid paraffin) for 2 hours at the temperature of 50 ℃ under the vacuum condition, and filtering, washing and drying to obtain phase change energy storage microspheres;
4. surface synergy is carried out on the phase-change energy storage microsphere:
45g of phase-change energy-storage microspheres and 1g of hexadecyl ammonium bromide are added into 500ml of water and stirred for 30min, then 50ml of 10% calcium chloride solution with mass fraction is added and stirred for 2h, and then 50ml of 10% sodium carbonate solution with mass fraction is added and stirred for 2h, so that the phase-change energy-storage microspheres are obtained.
The thermal properties of the phase-change energy-storage microspheres prepared in the experiment are shown in table 1.
As can be seen from table 1, the phase change material loading rate of the phase change energy storage microsphere without the high heat conduction network is 45.37%, the phase change material loading rate of the phase change energy storage microsphere with the high heat conduction filler added on the surface of the shaped shell is 47.37%, and compared with the phase change material loading rate of the phase change energy storage microsphere with the high heat conduction network is 51.26%, the phase change material loading rate is remarkably improved.
The latent heat value of the phase-change energy-storage microsphere without the high heat-conducting network is 95.1J/g, the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting filler added on the surface of the shaped shell is 99.3J/g, compared with the phase-change material loading rate of the phase-change energy-storage microsphere with the high heat-conducting network is 107.5J/g, and the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting network design is obviously improved.
The heat conductivity coefficient of the phase-change energy-storage microspheres without the high heat-conducting network is improved by 74%, the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting filler added on the surface of the shaped shell is improved by 117%, and compared with the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting network is improved by 173%, the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting network design is obviously improved.
TABLE 1 thermal properties of phase change energy storage microspheres
Note that: Δh in the above table represents latent heat.
Experiment II:
the preparation method of the phase change energy storage oriented to the building comprises the following steps:
1. preparing a high heat conduction network precursor:
weighing 10 parts of lignocellulose, 89.99 parts of sodium chloride and 0.01 part of carbon powder according to parts by weight, uniformly mixing the sodium chloride and the lignocellulose, adding 1000 parts of water, continuously stirring to completely dissolve the sodium chloride and the lignocellulose, completely dispersing the carbon powder into a mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high heat conduction network precursor;
2. preparing a hydraulic cementing material shell:
fully stirring 20 parts by mass of sulphoaluminate cement and 80 parts by mass of a high heat conduction network precursor (and preparing a control group by using sodium chloride salt balls), adding 50 parts by mass of water to form slurry, dropwise adding the slurry into melted PEG600, continuously stirring, gradually heating an oil continuous phase to 50 ℃ at a heating rate of 5 ℃ per minute after the slurry forms microspheres in the continuous phase, stirring for 4 hours at a rotating speed of 800rmp, filtering, washing with hot water, and drying to obtain a hydraulic cementing material shell;
3. preparing phase-change energy-storage microspheres:
immersing a hydraulic cementing material shell in a capric acid-paraffin co-melted phase change material (prepared by co-melting capric acid paraffin) for 2 hours at the temperature of 50 ℃ under the vacuum condition, and filtering, washing and drying to obtain phase change energy storage microspheres;
4. surface synergy is carried out on the phase-change energy storage microsphere:
45g of phase-change energy-storage microspheres and 1g of hexadecyl ammonium bromide are added into 500ml of water and stirred for 30min, then 50ml of 10% calcium chloride solution with mass fraction is added and stirred for 2h, and then 50ml of 10% sodium carbonate solution with mass fraction is added and stirred for 2h, so that the phase-change energy-storage microspheres are obtained.
The thermal properties of the phase-change energy-storage microspheres prepared in the experiment are shown in Table 2.
The thermal properties of the phase-change energy-storage microspheres are shown in Table 2. As can be seen from table 2, the phase change material loading rate of the phase change energy storage microsphere without the high thermal conductivity network is 43.57%, the phase change material loading rate of the phase change energy storage microsphere with the high thermal conductivity filler added to the surface of the shaped shell is 44.37%, and compared with the phase change material loading rate of the phase change energy storage microsphere with the high thermal conductivity network is 49.25%, the phase change material loading rate is remarkably improved.
The latent heat value of the phase-change energy-storage microsphere without the high heat-conducting network is 91.5J/g, the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting filler added on the surface of the shaped shell is 93.2J/g, compared with the phase-change material loading rate of the phase-change energy-storage microsphere with the high heat-conducting network is 103.4J/g, and the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting network design is obviously improved.
The heat conductivity coefficient of the phase-change energy-storage microspheres without the high heat-conducting network is 79%, the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting filler added on the surface of the shaped shell is 97%, and compared with the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting network is 147%, the heat conductivity coefficient of the phase-change energy-storage microspheres with the high heat-conducting network design is obviously improved.
TABLE 2 thermal properties of phase change energy storage microspheres
Note that: Δh in the above table represents latent heat.
Experiment III:
the preparation method of the phase change energy storage oriented to the building comprises the following steps:
1. preparing a high heat conduction network precursor:
weighing 10 parts of lignocellulose, 89.99 parts of sodium chloride and 0.01 part of carbon powder according to the parts by weight,
uniformly mixing sodium chloride and lignocellulose, adding 1000 parts by mass of water, continuously stirring to completely dissolve the sodium chloride and the lignocellulose, completely dispersing carbon powder into the mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high-heat-conductivity network precursor;
2. preparing a hydraulic cementing material shell:
mixing and stirring uniformly 20 parts by mass of a mixture of solid waste iron tailing powder and slag and 20 parts by mass of a sodium silicate solution with a solid content of 35% and a 1.5 mould, adding 60 parts of a high heat conduction network precursor (and preparing a control group by using sodium chloride salt balls), fully stirring, mixing and stirring uniformly the two, adding water accounting for 20% of the total mass of all materials to form slurry,
adding the slurry into PEG800 dropwise and continuously stirring, after the slurry forms microspheres in the continuous phase, gradually heating the oil continuous phase to 50 ℃ at 7 ℃ per minute, stirring for 4 hours at a rotating speed of 800rmp, filtering, washing with hot water, and drying to obtain a hydraulic cementing material shell;
3. preparing phase-change energy-storage microspheres:
immersing a hydraulic cementing material shell in a capric acid-paraffin co-melted phase change material (prepared by co-melting capric acid paraffin) for 2 hours at the temperature of 50 ℃ under the vacuum condition, and filtering, washing and drying to obtain phase change energy storage microspheres;
4. surface synergy is carried out on the phase-change energy storage microsphere:
45g of phase-change energy-storage microspheres and 1g of hexadecyl ammonium bromide are added into 500ml of water and stirred for 30min, then 50ml of 10% calcium chloride solution with mass fraction is added and stirred for 2h, and then 50ml of 10% sodium carbonate solution with mass fraction is added and stirred for 2h, so that the phase-change energy-storage microspheres are obtained.
The thermal properties of the phase-change energy-storage microspheres prepared in the experiment are shown in Table 3.
The thermal properties of the phase change energy storage microspheres are shown in Table 3. As can be seen from table 3, the phase change material loading rate of the phase change energy storage microsphere without the high thermal conductivity network is 53.31%, the phase change material loading rate of the phase change energy storage microsphere with the high thermal conductivity filler added to the surface of the shaped shell is 55.37%, and compared with the phase change material loading rate of the phase change energy storage microsphere with the high thermal conductivity network is 60.25%, the phase change material loading rate is remarkably improved.
The latent heat value of the phase-change energy-storage microsphere without the high heat-conducting network is 112.0J/g, the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting filler added on the surface of the shaped shell is 116.3J/g, and compared with the phase-change material loading rate of the phase-change energy-storage microsphere with the high heat-conducting network is 126.6J/g, the latent heat value of the phase-change energy-storage microsphere with the high heat-conducting network design is obviously improved.
The heat conductivity coefficient of the phase-change energy-storage microsphere without the high heat-conducting network is improved by 81%, the heat conductivity coefficient of the phase-change energy-storage microsphere with the high heat-conducting filler added on the surface of the shaped shell is improved by 107%, and compared with the heat conductivity coefficient of the phase-change energy-storage microsphere with the high heat-conducting network is improved by 157%, the heat conductivity coefficient of the phase-change energy-storage microsphere with the high heat-conducting network design is obviously improved.
TABLE 3 thermal properties of phase change energy storage microspheres
Note that: Δh in the above table represents latent heat.
Compared with other types of phase-change energy-storage microspheres, the phase-change energy-storage microsphere has the advantages that the high-heat-conductivity network is built in the phase-change energy-storage microsphere, the heat transfer efficiency of the phase-change energy-storage microsphere is higher, the heat storage capacity is stronger, the high-heat-conductivity network and the heat-conducting filler on the surface form a transmission channel, and the phase-change material is promoted to enter the high-strength shell, so that the load rate of the phase-change material of the phase-change energy-storage microsphere containing the high-heat-conductivity network is improved and the heat storage capacity is obviously enhanced under the same impregnation time; compared with other preparation methods, the preparation method has the advantages of simple flow, scientific and clear principle, low carbon and environmental protection.
Claims (6)
1. The preparation method of the phase-change energy storage microsphere for the building is characterized by comprising the following steps of:
1. preparing a high heat conduction network precursor:
weighing 5-20 parts of network supporting structure, 79.99-94.999 parts of soluble salt and 0.001-0.01 part of high heat conduction filler according to the parts by weight, wherein the total parts of the network supporting structure, the soluble salt and the high heat conduction filler are 100 parts,
uniformly mixing the soluble salt and the network support structure, adding 1000 parts by mass of water, continuously stirring to completely dissolve the soluble salt and the network support structure, completely dispersing the high-heat-conductivity filler into the mixed solution, heating to 80 ℃, continuously stirring until the water in the mixed solution is completely evaporated, and forming a granular high-heat-conductivity network precursor;
in the first step, the network support structure is lignocellulose, sodium polyacrylate or sodium alginate;
the soluble salt in the first step is sodium chloride, sodium sulfate or calcium chloride;
in the first step, the high-heat-conductivity filler is carbon powder, graphene or graphene oxide;
2. preparing a hydraulic cementing material shell:
weighing 20-80 parts of hydraulic cementing material and 20-80 parts of high heat conduction network precursor according to the parts by weight, wherein the total part of the hydraulic cementing material and the high heat conduction network precursor is 100 parts, mixing and stirring the two materials uniformly, adding water to form slurry, wherein the addition amount of the water is 20-50% of the total mass of the hydraulic cementing material and the high heat conduction network precursor, dropwise adding the slurry into an oil continuous phase, continuously stirring, gradually heating the oil continuous phase to 50-80 ℃ at the heating rate of 5-10 ℃ per minute after the slurry forms microspheres in the continuous phase, and filtering, washing and drying after the reaction is carried out for 0.5-12 hours to obtain a hydraulic cementing material shell;
the hydraulic cementing material in the second step is silicate cement, sulphoaluminate cement, magnesium phosphate cement, gypsum or waste alkali excitation material;
the waste alkali-activated material consists of solid waste and an alkali-activated agent, wherein the alkali-activated agent is NaOH solution and Na 2 CO 3 Solution, na 2 SiO 3 Solution, KOH solution, K 2 CO 3 Solutions or K 2 SiO 3 Solution of waste alkali exciting material according to SiO 2 With Al 2 O 3 The mass ratio of (2) is 0.8-2.2, na 2 O or K 2 O and Al 2 O 3 The mass ratio of (C) is 0.5-1.5, H 2 O and Na 2 O or K 2 The mass ratio of O is 15-19 to determine the dosage of alkali-exciting agent;
in the second step, the oil continuous phase is carbon tetrachloride, polyethylene glycol or paraffin;
3. preparing phase-change energy-storage microspheres:
immersing the hydraulic cementing material shell in the phase-change material for 1-5 h under the vacuum condition at the temperature of 50-80 ℃, and obtaining the phase-change energy storage microspheres through filtration, washing and drying;
in the third step, the phase change material is prepared by co-melting two or more of paraffin, fatty acid, lauric acid, capric acid, polyethylene glycol disodium hydrogen phosphate dodecahydrate, sodium carbonate decahydrate and calcium chloride hexahydrate;
4. surface synergy is carried out on the phase-change energy storage microsphere:
placing the phase-change energy-storage microspheres prepared in the step three into an ionic surfactant solution, adding a surface synergistic shell material, stirring for 1-5 h, filtering, washing and drying to obtain the phase-change energy-storage microspheres;
the mass ratio of the ionic surfactant to the phase-change energy-storage microspheres is 0.01-0.1;
the mass ratio of the surface synergistic shell material to the phase-change energy storage microsphere is 0.005-0.1;
the surface synergistic shell layer material in the fourth step is nano silicon dioxide or nano calcium carbonate;
the ionic surfactant in the fourth step is 1% of hexadecyl ammonium bromide aqueous solution, dodecyl benzene sulfonic acid aqueous solution, fatty alcohol acyl sodium sulfate aqueous solution, ethoxylated fatty acid methyl ester sodium sulfonate aqueous solution and secondary alkyl sodium sulfonate aqueous solution by mass percent.
2. The method for preparing the phase-change energy-storage microspheres for construction according to claim 1, wherein in the second step, the slurry is added dropwise into the oil continuous phase and stirred at a rotation speed of 800 rmp.
3. The method for preparing the phase-change energy-storage microspheres for construction according to claim 1, wherein in the second step, the solid waste is one or more of tailings, slag, municipal waste incineration ash and industrial waste incineration ash.
4. The method for preparing the phase-change energy storage microspheres for construction according to claim 1, wherein the compressive strength of the high-strength hydraulic cementing material shell in the second step is not lower than 20MPa.
5. The method for preparing the phase-change energy-storage microsphere for building according to claim 1, wherein the polyethylene glycol in the second step is PEG600 or PEG800.
6. The method for preparing a phase-change energy-storage microsphere for building according to claim 1, wherein the ionic surfactant in the fourth step is alcohol ether sulfate or alcohol ether phosphate.
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