CN1450141A - Phase-changing energy-storage composite material for building and preparation process thereof - Google Patents

Phase-changing energy-storage composite material for building and preparation process thereof Download PDF

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CN1450141A
CN1450141A CN 03116286 CN03116286A CN1450141A CN 1450141 A CN1450141 A CN 1450141A CN 03116286 CN03116286 CN 03116286 CN 03116286 A CN03116286 A CN 03116286A CN 1450141 A CN1450141 A CN 1450141A
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phase
change
energy
storage
porous material
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CN1303181C (en
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张东
吴科如
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Tongji University
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Tongji University
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Abstract

The presnt invention relates to a phase-changed energy storage composite material for building. Said invention uses the air-setting or hydraulic binding materials of gypsum and cement, etc. as base body, in which the porous material aggregates of expansive clay, etc. are dispersed, and in the porous material aggregates the organic phase-change materials of paraffin wax or butyl stearate, etc. are stored. Said invention adopts the vacuum impregnation method to prepare phase-change energy-storing aggregate firstly, then utilizes the conventional method for making building material to prepare the invented phase-change energy-storing composite material.

Description

Phase-change energy-storage composite material for building and preparation method thereof
Technical field
The invention belongs to building material technical field, specifically is a kind of phase-change energy-storage composite material and preparation method thereof.
Background technology
Utilize material energy-absorbing and the characteristics of releasing energy in phase transition process, realize that the storage of energy and utilization are one of directions of enlivening in recent years in various fields such as the energy, material, aerospace, weaving, electric power, medical instrument, building.Phase-change accumulation energy has advantages such as energy storage density height, energy storage easy control of temperature and range of choice are wide, practicability and commercialization stage have been entered in some fields at present, as having adopted based on LiF-CaF in the solar thermal machine power generating system on the Freedom space station of US Airways Space Agency (NASA) 2The heat reservoir of excellent attitude salt phase-changing energy storage material is to satisfy the without interruption of no photophase electric power; At garment industry, commercialization phase-change energy-storage fibre-Outlast fiber has appearred, the heat that human body distributes can be collected and store to dress-goods by this fibrous woven manufacturing, improves the warming ability of clothes, has more application aspect sportwear and the extreme environment clothes.
The phase-changing energy storage material kind is a lot, can be divided into organic phase change material and inorganic phase-changing material by substance classes, can be divided into solid-liquid phase change material, solid-solid phase change material, solid and gas phase change material and liquid-gas phase transition material etc. by the phase transition process form.Attempt adopting phase-changing energy storage material to reduce building energy consumption at building field long history has been arranged.From the thirties in last century, just the someone explores and adopt phase change material in the heating buildings system on America and Europe and other places, comprises organic phase change material and inorganic phase-changing material.First relevant patent [US 2 342 211 (1944)]-phase-change accumulation energy refrigeration and warmer appearred.1948, doctor Telkes of masschusetts, u.s.a engineering college built first experiment room-Dover House that utilizes phase-changing energy storage material to store and utilize sun power.The energy dilemma of the seventies has further promoted the research and development of energy utilization technology.The research and development of phase-changing energy storage material are changed into by state organization by the loose behavior that has color among the people, even international organization's united and coordinating, demonstrate its great potential and value in the energy uses.Nineteen eighty-two, USDOE at first started the R﹠D work of this respect.In recent years, International Energy Agency (International Energy Agency, IEA) also carried out research and application plan (Annex10 and 17) that phase-changing energy storage material uses aspect building energy saving field, some developed countries participate in by Europe, the United States, day etc., have obtained some achievements in succession.As adopting encapsulation technology various organic phase changing matters to be encapsulated in the polymkeric substance such as high-density polyethylene, polyacetal and polyureas, the preparation shape is the fixed phase change material relatively; Or adopt macromolecular materials such as crosslined polyacetal and cellulose graft copolymer to prepare phase change material.Make a general survey of the applicable cases of present phase-changing energy storage material in building energy conservation, mainly have the problem of following three aspects:
(1) endurance issues of energy-storage function: compare with other Application Areas, the environmental factors complexity of building, abominable, to the life requirement of material of construction than higher, therefore many phase-changing energy storage materials that can fine use in other field, usually expose short, easy shortcoming such as aging of life-span in the environment for use in building, can not life-time service, lack practical value, this also is that the above-mentioned U.S. first phase-change accumulation energy experiment room-Dover House only continues promptly to fail less than 1 year, and occurs the major cause of practical phase-change accumulation energy fabrication so far not yet.
(2) economy problems: building volume is all very big, requires the usage quantity of phase change material very big.Therefore, if the cost of phase-changing energy storage material is too high, then can not be in architectural acquisition application truly.Cost is too high to be present phase-changing energy storage material another major reason before building field application deterioration not.
(3) material compatibility problem: mineral-type phase change material for example, owing to have corrodibility, using under construction usually needs to adopt the form of pipeline or container that it is stored, and has increased complicacy, failure rate and the Pollution risk of building structure.
Summary of the invention
The objective of the invention is to propose a kind of energy-storage function phase-change energy-storage composite material for building durable, with low cost, applied widely and preparation method thereof.
The phase-change energy-storage composite material for building that the present invention proposes, it is as follows that it constitutes component, is matrix with the higher air-setting of solidity ratio or the gelling material of the hydraulicity, wherein disperses porous material to gather materials, and the volume ratio that porous material gathers materials with matrix is 0.4-1.5; Store organic phase change material in porous material gathers materials, storage capacity is the 30-70% weight ratio.The multiple building member that the phase-change energy-storage composite material of being made up of above-mentioned starting material prepares can possess above 10MJ/m 3About energy storage density, transformation temperature can be regulated between 15~60 ℃, satisfies the requirement of buildings heating and refrigeration.
Above-mentioned phase-change energy-storage composite material can adopt lime, cement, gypsum etc. as the gelling material of matrix; Porous material gathers materials and can adopt swelling clay, expansion leaf rock, pearlstone, expanding powder coal ash etc.; Organic phase change material can adopt paraffin, butyl stearate etc.
The preparation method of phase-change energy-storage composite material of the present invention is as follows:
Adopt the vacuum infiltration method, porous material is gathered materials absorb and the storage organic phase change material, detailed process is: at first adopt the method that vacuumizes, extract the air in the porous material, vacuum is pressed must be higher than 80kPa, pumpdown time with organic phase change material soaked with liquid porous material, is removed vacuum generally greater than 30 minutes then under vacuum environment, continue to soak more than 30 minutes, take out porous material, add sealing ply, make phase-change accumulation energy and gather materials.
In this step; the porous material that adopts gathers materials for have the porous light-weight aggregate of widespread usage in building field; as swelling clay haydite, expansion leaf rock ceramic granule, expanding powder flyash haydite or pearlstone etc.; the porosity of selected porous material is (mercury penetration method) between 30~90%, and the hole connectedness is (image analytical method) between 50~95%.These material sources are extensive, low price, and acid or alkali environment is neutral in the hole, and organic phase change material is had no side effect; be suitable for large vol and the long-time organic phase change material that stores; and protect organic phase change material to avoid the external environment effect, and prolong the life-span of its energy-storage function, improve its weather resistance.The enthalpy of phase change of selected organic phase change material requires more than 100J/g, and transformation temperature is selected between 15~60 ℃, low price, a large amount of easily the acquisition.
In order to prevent organic phase change material oozing out in use, stored the surface that the porous material of organic phase change material gathers materials in absorption and made sealing ply with materials such as polymer cement or polymer emulsions, the porosity of sealing ply requires less than 5% (mercury penetration method), and the hole connectedness is less than 2% (image analytical method).At last, the phase-change accumulation energy of formation gathers materials and can divide coarse aggregate and fine aggregate by size, can be used for the making of different size building slab.
On the basis that phase-change accumulation energy gathers materials, prepare phase-change energy-storage composite material, can carry out at the scene, construction site, also can in building slab factory for prefabrication, finish, and the general preparation method that can continue to use material of construction gathers materials phase-change accumulation energy and body material mixed phase-change energy-storage composite material.For example, adopt the preparation method of light aggregate concrete, can gather materials by phase-change accumulation energy, material preparation phase-change accumulation energy concrete material such as cement, water and chemical admixture, can construct concrete wall with this material, be used to regulate the indoor thermal environment of buildings and reduce building energy consumption with phase-change accumulation energy function.Can also adopt methods for gypsum board production, utilize the phase-change accumulation energy of tiny type to gather materials and gypsum mixed, make plasterboard with phase-change accumulation energy function, can carry out building energy-saving renovation to existing building easily with this material.
Compare with existing phase-changing energy storage material, New-type phase change energy-storage composite material that the present invention proposes and preparation method thereof, be to have utilized at storage medium, sealing ply material and the body material of the widely used porous material of building field as organic phase change material, material cost is cheaper; Simultaneously, owing to can adopt the conventional preparation technology of material of construction, make the suitability for industrialized production conversion of this material be easy to realize that preparation technology's cost is also very low.In addition, adopt closely knit material that organic phase change material is sealed, improved the weather resistance of phase change material in various architectural environments, reduced the pollution that phase change material may bring architectural environment to greatest extent.Therefore, phase-change energy-storage composite material provided by the invention and preparation method thereof is fit to the application requiring of building field more.
Embodiment
Embodiment 1
Adopting porosity is the porous medium of 75.6% swelling clay haydite as the storage organic phase change material, and the maximum particle diameter of haydite is 20 millimeters, and shape approximation is spherical.Selecting fusing point for use is 45 ℃, and enthalpy of phase change is that the paraffin of 130J/g is organic phase change material.Vacuum immersion process parameter is: the pumpdown time is 30 minutes, and vacuum is pressed and to be 80kPa, goes that soak time is 30 minutes after the vacuum, and soaking temperature is 100 ℃.The storage capacity of organic phase change material in porous material is about 65%wt..The sealing ply material adopts polymer emulsion modified cement material, and its proportioning is: cement: polymer emulsion: water=100: 20: 17.5, and polymer emulsion adopts commercial SBR emulsion, and solid matter content is 50%.Add phase-change accumulation energy behind the sealing ply gather materials in the content of organic phase change material be about 60%wt.
Utilize this phase-change accumulation energy gather materials and concrete formulating method prepare the phase-change accumulation energy concrete material, mix proportion is: cement: water: phase-change accumulation energy gathers materials: sand=100: 50: 190: 170.In the phase-change accumulation energy concrete material, the content of organic phase change material is approximately 22%wt..Building concrete wall with this material can heat energy storage, is used for warming, and its thermal energy storage temperature is 45 ℃, and thermal energy storage density is about 50MJ/m 3
Embodiment 2
Adopting porosity is the porous medium of 73.3% swelling clay pottery sand as the storage organic phase change material, and the maximum particle diameter of pottery sand is 3 millimeters, is shaped as elliposoidal.Selecting fusing point for use is 45 ℃, and enthalpy of phase change is that the paraffin of 130J/g is organic phase change material.Vacuum immersion process parameter is: the pumpdown time is 40 minutes, and vacuum is pressed and is 85kPa, and soak time is 45 minutes after the vacuum, and soaking temperature is 100 ℃.The storage capacity of organic phase change material in porous material is 60%wt..The sealing ply material adopts the polymer emulsion compound through multiviscosisty, and emulsion adopts commercial SBR emulsion, and solid matter content is 75% after the multiviscosisty.Add phase-change accumulation energy behind the sealing ply gather materials in the content of organic phase change material be 58%wt..
Utilize this phase-change accumulation energy to gather materials and the preparation method of gypsum dividing plate prepares phase-change accumulation energy gypsum dividing plate matrix material, the proportioning of gypsum dividing plate is: the plaster of Paris: water: phase-change accumulation energy gathers materials: fortifying fibre: retardant=100: 60: 40: 1: 0.1.In phase-change accumulation energy gypsum dividing plate matrix material, the content of organic phase change material is approximately 15%.Building plasterboard partition wall with this material can heat energy storage, is used for warming, and its thermal energy storage temperature is 45 ℃, and thermal energy storage density is about 20MJ/m 3
Embodiment 3
Adopting porosity is the porous medium of 75.6% swelling clay haydite as the storage organic phase change material, and the maximum particle diameter of haydite is 20 millimeters, and shape approximation is spherical.Selecting fusing point for use is 22 ℃, and enthalpy of phase change is that the butyl stearate of 128.5J/g is an organic phase change material.Vacuum immersion process parameter is: the pumpdown time is 30 minutes, and vacuum is pressed and to be 88.5kPa, goes that soak time is 40 minutes after the vacuum, and soaking temperature is 30 ℃.The storage capacity of organic phase change material in porous material is 67.5%wt..The sealing ply material adopts polymer emulsion modified cement material, and its proportioning is: cement: polymer emulsion: water=100: 20: 17.5, and polymer emulsion adopts commercial SBR emulsion, and solid matter content is 50%.Add phase-change accumulation energy behind the sealing ply gather materials in the content of organic phase change material be 63%wt..
Utilize this phase-change accumulation energy gather materials and concrete formulating method prepare the phase-change accumulation energy concrete material, mix proportion is: cement: water: phase-change accumulation energy gathers materials: sand=100: 50: 190: 170.In the phase-change accumulation energy concrete material, the content of organic phase change material is approximately 23%wt..Build concrete wall with this material and can store cold, be used for refrigeration in summer, its cold storing temp is 22 ℃, and storage density is about 52MJ/m 3

Claims (7)

1, a kind of phase-change energy-storage composite material for building is characterized in that with the higher air-setting of solidity ratio or the gelling material of the hydraulicity be matrix, wherein disperses porous material to gather materials, and the volume ratio that porous material gathers materials with matrix is 0.4-1.5; Store organic phase change material in porous material gathers materials, storage capacity is the 30-70% weight ratio.
2, phase-change energy-storage composite material according to claim 1 is characterized in that adopting gypsum, cement or lime as the gelling material of matrix; Porous material gathers materials and adopts swelling clay, expansion leaf rock, pearlstone, expanding powder coal ash; Organic phase change material adopts paraffin, butyl stearate.
3, a kind of preparation method of phase-change energy-storage composite material for building as claimed in claim 1, it is characterized in that adopting the vacuum infiltration method, porous material is gathered materials absorb and the storage organic phase change material, detailed process is: at first adopt the method that vacuumizes, extract the air in the porous material, vacuum is pressed must be higher than 80kPa, pumpdown time was greater than 30 minutes, under vacuum environment, use organic phase change material soaked with liquid porous material, remove vacuum then, continue to soak more than 30 minutes, take out porous material, add sealing ply, make phase-change accumulation energy and gather materials; By usual method phase-change accumulation energy is gathered materials at last and the mixed phase-change energy-storage composite material that gets of body material.
4, preparation method according to claim 3, the enthalpy of phase change that it is characterized in that used organic phase change material is more than 100J/g, and transformation temperature is 15~60 ℃.
5, preparation method according to claim 3 is characterized in that sealing ply adopts polymer cement or polymer emulsion, and its porosity is less than 5%, and the hole connectedness is less than 2%.
6, according to the described preparation method of claim 3-5, it is characterized in that adopting the preparation method of light aggregate concrete, with described phase-change accumulation energy gather materials, cement, water and chemical admixture be prepared into the phase-change accumulation energy concrete material.
7, according to the described preparation method of claim 3-5, it is characterized in that adopting methods for gypsum board production, the phase-change accumulation energy of tiny type is gathered materials make phase-change energy-storage gypsum plate.
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CN100387544C (en) * 2006-08-02 2008-05-14 北京中远汇丽精细化工有限公司 Phase change anticracking grout and preparation method of used phase change material particulate
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