CN110305635A - A kind of forming heat accumulating and preparation method thereof - Google Patents
A kind of forming heat accumulating and preparation method thereof Download PDFInfo
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- CN110305635A CN110305635A CN201910652781.5A CN201910652781A CN110305635A CN 110305635 A CN110305635 A CN 110305635A CN 201910652781 A CN201910652781 A CN 201910652781A CN 110305635 A CN110305635 A CN 110305635A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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Abstract
The present embodiments relate to heat accumulating fields, and in particular to a kind of forming heat accumulating and preparation method thereof.Highly heat-conductive material is prepared into porous foam or aeroge by preparation method provided by the invention, loads heat accumulating then to get the sizing thermal energy storage material with quick charge and discharge thermal energy power is arrived；It is mixed, is poured with concrete by the thermal energy storage material that will be formed again, hardened, obtained the forming heat accumulating suitable for various shape, size and occasion, significantly improve the service performance of heat accumulating, extend the application range of heat accumulating.Preparation method provided by the invention, it can be used for preparing the forming heat accumulating with high heat storage capacity, quick charge and discharge thermal energy power, sizing heat storage capacity, high ease of use, thermal energy storage can be widely used in, the fields such as heat supply, heating, industrial exhaust heat Waste Heat Recovery utilize.
Description
Technical field
The present invention relates to heat accumulating fields, and in particular to a kind of forming heat accumulating and preparation method thereof.
Background technique
With society and expanding economy, demand rapid growth of the mankind to the energy.Traditional fossil energy is limited,
And often aggravate climate change and environment with the discharge of the pernicious gases such as carbon dioxide and sulfur dioxide in use
Pollution.Efficiency of energy utilization is improved to play an important role alleviation energy problem, promotion environmental protection.
Heat-storage technology has extensively in the fields such as building temperature adjustment, heating, industrial exhaust heat and Waste Heat Reuse, the adjusting of electric system peak valley
General application, can effectively improve efficiency of energy utilization.Heat accumulating is the key that heat-storage technology.Heat accumulating can be by aobvious
Heat or the mode of latent heat store or discharge heat.Developing has high heat storage capacity, quick charge and discharge thermal energy power, high easy-to-use height
Performance heat accumulating is the developing direction of heat-storage technology.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of forming heat accumulatings and preparation method thereof.
Highly heat-conductive material is prepared into porous foam or aeroge by preparation method provided by the invention, then load heat accumulating to get
To the sizing thermal energy storage material with quick charge and discharge thermal energy power；Again by mixing thermal energy storage material with concrete, pour,
Hardening obtains the forming heat accumulating suitable for various shape, size and occasion, significantly improves the usability of heat accumulating
Can, extend the application range of heat accumulating.
Preparation method provided by the invention, can be used for preparing has high heat storage capacity, quick charge and discharge thermal energy power, sizing heat accumulation
It is useless can be widely used in thermal energy storage, heat supply, heating, industrial exhaust heat for the forming heat accumulating of ability, high ease of use
Recuperation of heat such as utilizes at the fields.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of preparation methods for shaping heat accumulating, comprising: will
Highly heat-conductive material is prepared into foam or aeroge；Heat accumulating is loaded, sizing thermal energy storage material is obtained；To be formed compound heat accumulation
Material is mixed with concrete, forming, obtains forming heat accumulating.The foam is loose and porous structure.
Highly heat-conductive material in one possible implementation, is prepared into the side of foam or aeroge by above-mentioned preparation method
Method include hydro-thermal self-assembly method, templating self-assembly method, chemical vapour deposition technique, 3D printing method, sol-gel method, solvent-thermal method,
Liquid phase extrusion molding, foaming squeeze and cut at least one of comminution granulation or presoma conversion method；Tune can be passed through according to actual needs
Preparation process is saved to regulate and control the shape and size of foam or aeroge.
Above-mentioned preparation method in one possible implementation, after heat accumulating is melted, is loaded into highly heat-conductive material
In the foam or aeroge of preparation.
In one possible implementation, the method for loading heat accumulating includes absorption, injection, squeezes above-mentioned preparation method
At least one of enter, be pressed into, instill or penetrate into.
In one possible implementation, forming includes the following steps: the compound heat accumulation material that will be formed to above-mentioned preparation method
Material is poured with the mixture that concrete is mixed to get, and forming heat accumulating is obtained after hardened.It can obtain according to actual needs
To the forming heat accumulating for being suitable for various shape, size and applications.
In one possible implementation, sizing thermal energy storage material volume obtains above-mentioned preparation method after accounting for hardening
Shape the 1-70vol% of heat accumulating total volume.
Above-mentioned preparation method in one possible implementation, will sizing thermal energy storage material when being mixed with concrete,
It is additionally added heat filling.
In one possible implementation, heat filling accounts for concrete and heat filling gross mass to above-mentioned preparation method
1-60wt%；It is optionally 1%-40%；It is still optionally further 1%-20%.
In one possible implementation, highly heat-conductive material includes graphene, graphene oxide, stone to above-mentioned preparation method
Ink, carbon fiber, graphite fibre, expanded graphite, carbon nanotube, carbon nano-fiber, silicon carbide, metal powder, metallic fiber, metal
Nanofiber, metal organic frame, copper nano-wire, fullerene, boron nitride, silicon nitride, aluminium nitride, silicon carbide, boron carbide, carbonization
Magnesium, zirconium carbide, calcium carbide, chromium carbide, tungsten carbide, vanadium carbide, aluminium oxide, zinc oxide, magnesia, biomass conversion carbon material,
Macromolecule presoma converts at least one of carbon material；Optionally, highly heat-conductive material includes carbon nanotube and graphene oxide
Mixture, graphene oxide, the mixture of carbon fiber and graphene oxide, boron nitride, silicon nitride and graphene oxide it is mixed
Close object, the mixture of aluminium nitride and graphene oxide, carbon nano-fiber, biomass conversion carbon material, the conversion of macromolecule presoma
At least one of carbon material.
In one possible implementation, heat accumulating includes the fusible heat accumulation of fusing point≤800 DEG C to above-mentioned preparation method
Material.The heat accumulation mode of heat accumulating both be can also be and be combined either sensible heat, is also possible to latent heat of phase change.
In one possible implementation, heat accumulating includes paraffin, higher aliphatic hydrocarbon, sugar or sugar to above-mentioned preparation method
Alcohols, alcohols, polyhydroxy carbonic acid class, polyolefins, polymeric polyalcohols, acetic acid, camphenilone, 1- bromine docosane, 15 ketone, 8-
Heptadecanone, cyanamide, 2- heptadecanone, 3- heptadecanone, pelargone amphene, acetamide, ethyl-lithium, high-density polyethylene
Alkene, catechol, antifebrin, butanedioic anhydride, urea, hydroquinone, crystalline hydrate salt, sodium sulphate, chlorate, nitrate,
At least one of carbonate, fluoride salt, hydroxide, complex salt, metal or alloy class；Optionally, sugar or glycitols include
Xylitol, D-sorbite, antierythrite, glucose, fructose, isomalt, maltitol, lactitol, D- xylose, L- wood
At least one of sugar, d- mannitol or galactitol；Alcohols includes in pentaerythrite, tromethamine or polyvinyl alcohol
It is at least one；Acetic acid includes chloroacetic acid, heptadecanoic acid, α-monoxone, glycolic, acrylic acid, phenylacetic acid, glutaric acid, benzoic acid, horse
Come sour, malonic acid, cinnamic acid, suberic acid, adipic acid, dicarboxylic acids, salicylic acid, decanedioic acid, lauric acid, vaccenic acid, tetradecanoic acid,
At least one of pentadecanoic acid or hexadecanoic acid stearic acid；Crystalline hydrate salt includes magnesium chloride hexahydrate, ferric chloride (FeCl36H2O), five
Be hydrated sodium thiosulfate, epsom salt, sodium acetate trihydrate, lithium diacetate dihydrate, a hydronium(ion) sodium oxide molybdena, barium hydroxide,
At least one of six water alums, calcium chloride hexahydrate or sal glauberi；Chlorate includes aluminium chloride, potassium chloride, chlorination
At least one of zinc, magnesium chloride, lithium chloride, iron chloride, calcium chloride, sodium chloride or palladium chloride；Nitrate includes sodium nitrate, nitre
Sour nickel, ferric nitrate, magnesium nitrate, zinc nitrate, aluminum nitrate, lithium nitrate, calcium nitrate, zirconium nitrate, copper nitrate, silver nitrate, palladium nitrate, carbon
At least one of sour sodium or potassium carbonate；Carbonate includes aluminium carbonate, magnesium carbonate, lithium carbonate, calcium carbonate, barium carbonate, ferric carbonate
Or at least one of lithium carbonate；Fluoride salt includes at least one of sodium fluoride, potassium fluoride or lithium fluoride；Hydroxide includes
At least one of sodium hydroxide, potassium hydroxide or calcium hydroxide；Complex salt includes 50 sodium nitrate/50 potassium nitrate, 31.9 chlorinations
Zinc/68.1 potassium chloride, 50 lithium hydroxides/50 potassium hydroxide, 38.5 magnesium chlorides/61.5 sodium chloride or 20 potassium nitrate/40 sodium nitrate/
At least one of 40 sodium nitrites, wherein number refers to parts by weight；Metal includes in silver, aluminium, magnesium, zinc, tin, beryllium, bismuth, lead or copper
At least one；Alloy include aluminium/silicon alloy, aluminum/zinc alloy, aluminum/magnesium alloy, aluminium/magnesium/kirsite, tin/zinc/bismuth alloy,
In tin/zinc/copper alloy, magnesium/kirsite, aluminium/copper alloy, magnesium/copper alloy, bismuth/lead/tin/indium, bismuth/chromium/indium or bismuth/lead extremely
Few one kind；Still optionally further, heat accumulating includes paraffin, sal glauberi, magnesium nitrate, sodium nitrate, calcium chloride hexahydrate, magnalium
At least one of kirsite.
In one possible implementation, heat filling includes graphene, graphene oxide, stone to above-mentioned preparation method
Ink, carbon fiber, graphite fibre, expanded graphite, carbon nanotube, carbon nano-fiber, silicon carbide, metal powder, metallic fiber, metal
Nanofiber, metal organic frame, copper nano-wire, fullerene, boron nitride, silicon nitride, aluminium nitride, silicon carbide, boron carbide, carbonization
Magnesium, zirconium carbide, calcium carbide, chromium carbide, tungsten carbide, vanadium carbide, aluminium oxide, zinc oxide, magnesia, copper, silver, aluminium, magnesium, iron, life
Substance converts at least one of carbon material, macromolecule conversion carbon material；Optionally, heat filling include graphene, carbon fiber,
At least one of expanded graphite, carbon nanotube, aluminium nitride, aluminium oxide.
In one possible implementation, concrete includes: water, cement and aggregate to above-mentioned preparation method；Optionally,
Concrete further includes at least one of additive or modifying agent.The constituent and proportion of concrete can be according to being specifically actually subjected to
It asks and is selected.
Above-mentioned preparation method in one possible implementation, by sizing thermal energy storage material and concrete hybrid mode
Including manually stirring or carrying out mechanical stirring using blender.
Above-mentioned preparation method in one possible implementation, firm time 1-10d.
The embodiment of the invention also provides shape heat accumulating made from above-mentioned preparation method.
The embodiment of the invention also provides above-mentioned preparation method or above-mentioned forming heat accumulating industrial exhaust heat, waste heat and from
The storage of right thermal energy and the application for utilizing field.
Beneficial effect
(1) it is provided in an embodiment of the present invention forming heat accumulating preparation method, by will be formed thermal energy storage material and
Concrete mixing, further pours the forming heat accumulating that can be obtained suitable for various shape, size and occasion, significantly improves
The service performance of heat accumulating, extends the application range of heat accumulating, can be widely used in thermal energy storage, heat supply,
Heating, industrial exhaust heat Waste Heat Recovery such as utilize at the fields, and preparation process is simple, easy to use, scale industrial production easy to accomplish
And application.
(2) preparation method of forming heat accumulating provided in an embodiment of the present invention, foam or gas made of highly heat-conductive material
Gel can play thermally conductive skeleton in sizing thermal energy storage material, and the capacity of heat transmission is strong, and mass concentration is small, prepared
The thermal energy storage material capacity of heat transmission with higher of being formed and quick charge and discharge thermal energy power.And its size is controllable, shape is in grit shape,
Convenient for mixing and pouring with concrete, it is suitable for existing concrete construction technology and equipment.
(3) it is provided in an embodiment of the present invention forming heat accumulating preparation method, by will be formed thermal energy storage material and
Concrete is mixed in a certain proportion, and plays to maximizing the high heat storage capacity and quick charge and discharge thermal energy of sizing thermal energy storage material
The forming capacity of power and concrete.
(4) preparation method of forming heat accumulating provided in an embodiment of the present invention, is formed more used in thermal energy storage material
The hole of hole foam or aeroge can reach Nano grade, can effectively prevent part heat accumulating in heat accumulation application due to solid liquid phase
Change and liquid leakage occurs.And after sizing thermal energy storage material is mixed with concrete, poured, shaping, concrete can be into one
Step prevents part heat accumulating from liquid leakage occurring due to solid-liquid phase transition in heat accumulation application.
(5) preparation method of forming heat accumulating provided in an embodiment of the present invention, obtained porous foam or aeroge can
It arbitrarily arranges in pairs or groups with heat accumulating, universality is good.And can be porous foam or aeroge that a variety of highly heat-conductive materials are mixed to prepare,
Keep the performance of sizing thermal energy storage material and forming heat accumulating more various.
(6) preparation method of forming heat accumulating provided in an embodiment of the present invention, can be added heat filling in concrete, can
The heating conduction for further increasing forming heat accumulating prevents from being unfavorable for shaping heat accumulation because normal concrete itself thermal conductivity is low
The performance of material overall performance.
(7) preparation method of forming heat accumulating provided in an embodiment of the present invention is obtained shapes heat accumulating, has height
Heat storage capacity and quick charge and discharge thermal energy power, and can adjust according to actual needs and pour shape, size etc., ease of use is good, answers
It is wide with range.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is that redox graphene/carbon nanotube aerogel cross sectional scanning electron made from the embodiment of the present invention 1 is aobvious
Micro mirror (SEM) figure.
Fig. 2 is redox graphene/carbon nanotube made from the embodiment of the present invention 1/paraffin sizing thermal energy storage material
Section SEM figure.
Fig. 3 is redox graphene/carbon nanotube/paraffin/concrete forming heat accumulation material made from the embodiment of the present invention 1
The photo of material (sizing thermal energy storage material volume fraction is about 25vol%).
Fig. 4 is test temperature-time graph self-control test device schematic diagram in the embodiment of the present invention 1.
Fig. 5 is redox graphene/carbon nanotube/paraffin/concrete forming heat accumulation material made from the embodiment of the present invention 1
Material is with pure concrete to the influence curve of the adjusting of temperature.
Fig. 6 is the section SEM figure of redox graphene aeroge made from the embodiment of the present invention 2.
Fig. 7 is redox graphene made from the embodiment of the present invention 2/paraffin sizing thermal energy storage material section SEM
Figure.
Fig. 8 is redox graphene/carbon nanotube/paraffin/concrete forming heat accumulation material made from the embodiment of the present invention 3
The photo of material (sizing thermal energy storage material volume fraction is about 10vol%).
Fig. 9 is the short fibre/sodium sulphate of redox graphene/carbon fiber made from the embodiment of the present invention 4/concrete forming storage
The photo of hot material (sizing thermal energy storage material volume fraction is about 20vol%).
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Embodiment 1
A kind of redox graphene/carbon nanotube/paraffin/concrete forming heat accumulating preparation method, including under
State step:
By 75g carbon nanotube aqueous dispersions (mass fraction 1%) and 150g graphite oxide aqueous dispersions, (mass fraction is
2%) pass through mechanical stirring and ultrasonic treatment mixing 1h, the needle for being 0.5mm by diameter by slurry by peristaltic pump or extruder pump
Head squeeze out, be added dropwise in cetyl trimethylammonium bromide coagulating bath (mass fraction 1% of cetyl trimethylammonium bromide,
The mass fraction of water is 95%, the mass fraction of ethyl alcohol be 4%) in, obtain globular graphene oxide/carbon nanotube water-setting
Glue obtains graphene oxide/carbon nanotube aerogel after washing, being freeze-dried, it is heated to reduction in 200 DEG C of baking ovens
2-4h obtains redox graphene/carbon nanotube aerogel；Fig. 1 is its section SEM figure；
Using the vacuum impregnation stowage of vacuum aided, the paraffin of fusing is adsorbed onto reduction-oxidation through capillary action
In graphene/carbon nano-tube aeroge, redox graphene/carbon nanotube/paraffin sizing thermal energy storage material is obtained；Fig. 2
For its section SEM figure；
According to cement: quartz sand: water: graphene oxide=20:30:10:1 match ratio, by 30g cement, 45g quartz
Sand, 15g water and 1.5g graphene oxide are by being manually mixed 5min；
Redox graphene/carbon nanotube/paraffin sizing thermal energy storage material that quality is 15.6g is added to above-mentioned
20min is manually mixed in obtained mixed slurry (volume fraction of sizing thermal energy storage material is about 25vol%)；
Mixing mixture derived above is injected into diameter for 8.3cm, in the culture dish mold of a height of 1.4cm, by 2d
Hardening obtain forming heat accumulating, photo is as shown in Figure 3.
Using homemade test device (as shown in Figure 4), test device includes: infrared lamp (100W), attemperator, temperature
Test device (thermocouple and read-out display), sample (cylinder).It is provided with inside attemperator (a monolith insulating foam) straight
The large aperture cavity of diameter about 8.3cm, high about 1.4cm, the small-bore cavity with diameter about 7.5cm, high about 18cm.Wherein, macropore
Diameter cavity is for placing sample；Minor diameter cavity is test chamber, for being inserted into thermocouple, thermometric.
By the sample (i.e. above-mentioned mixed slurry) of the above-mentioned forming heat accumulating of the device to test and pure concrete, draw
Temperature-time curve figure, as a result as shown in Figure 5.When test, infrared lamp irradiation sample upper surface is opened, sample absorbs heat,
It is transmitted to lower surface, the air in the cavity of small-bore is heated, temperature is detected by thermocouple, and shown by read-out display.Such as Fig. 5
Shown, after heating in a period of time, heating caused by forming heat accumulating sample is slower than pure concrete sample, this is because forming
Paraffin in heat accumulating absorbs a part of heat and stores as latent heat, therefore slows down heat and enter test chamber.?
It is warming up to after 58 DEG C, heating caused by forming heat accumulating sample is faster than pure concrete sample, this is because forming heat accumulation material
Paraffin in material melts completely, does not reabsorb latent heat, and the highly heat-conductive material shaped in heat accumulating at this time improves heat
Across the speed of sample.A period of time after turning off the light, forming heat accumulating caused by cooling be faster than pure concrete, this be also by
Highly heat-conductive material in forming heat accumulating improves the speed that heat passes through sample.After temperature drops to 50 DEG C, forming
Cooling caused by heat accumulating will be slower than pure concrete, this is because the paraffin in forming heat accumulating discharges latent heat, wherein one
Part latent heat passes to test chamber air.These the result shows that setting heat accumulating have good heat accumulation, it is thermally conductive, quickly fill
The performances such as heat release.
Embodiment 2
A kind of preparation method of redox graphene/paraffin/concrete forming heat accumulating, includes the following steps:
By 240g graphite oxide aqueous dispersions (mass fraction 1%), slurry is passed through directly by peristaltic pump or extruder pump
Syringe needle that diameter is 0.5mm, which squeezes, to be switched to polyethyleneimine coagulating bath (polyethyleneimine mass fraction is 1%, and water quality score is
99%) in, granular graphene oxide hydrogel is obtained, obtains graphite oxide aerogel after washing, being freeze-dried,
It is heated into reductase 12 h in 200 DEG C of baking ovens, obtains redox graphene aeroge；Fig. 6 is its section SEM figure；
Using the vacuum impregnation stowage of vacuum aided, the paraffin of fusing is adsorbed onto reduction-oxidation through capillary action
In grapheme foam, redox graphene/paraffin sizing thermal energy storage material is obtained；Fig. 7 is its section SEM figure；
According to cement: river sand: water: graphene oxide=10:20:4:1 match ratio, and mixing quality is cement quality
0.3% water-reducing agent stirs 40g cement, 80g river sand, 16g water, 4g graphene oxide with 0.12g water-reducing agent by manually mixing
Mix 5min；
Redox graphene/paraffin sizing thermal energy storage material that quality is 19g is added to mixing obtained above
20min is manually mixed in slurry (volume fraction of sizing thermal energy storage material is about 30vol%)；
It is 8.3cm that mixing mixture derived above, which is poured into diameter, in the cylindrical die of a height of 1.4cm, is passed through
The hardening of 2d obtains forming heat accumulating.
Embodiment 3
A kind of redox graphene/carbon nanotube/paraffin/concrete forming heat accumulating preparation method, including under
State step:
By 70g carbon nanotube aqueous dispersions (mass fraction 1%) and 140g graphite oxide aqueous dispersions, (mass fraction is
2%) slurry is squeezed by peristaltic pump or extruder pump by the syringe needle that diameter is 0.5mm, and drips to polyethyleneimine coagulating bath (poly- second
Alkene imines mass fraction be 1%, water quality score be 99%) in, obtain granular graphene oxide/carbon nanotube water-setting
Glue obtains graphene oxide/carbon nanotube aerogel after washing, being freeze-dried, it is heated to reduction in 200 DEG C of baking ovens
2h obtains redox graphene/carbon nanotube aerogel；
Using the vacuum impregnation stowage of vacuum aided, the paraffin of fusing is adsorbed onto reduction-oxidation through capillary action
In graphene/carbon nano-tube aeroge, redox graphene/carbon nanotube/paraffin sizing thermal energy storage material is obtained；
According to cement: quartz sand: water: carbon nanotube=10:20:5:2 match ratio, by 40g cement, 80g quartz sand,
20g water and 8g carbon nanotube are by being manually mixed 5min；
Redox graphene/carbon nanotube/paraffin sizing thermal energy storage material that quality is 7g is added to above-mentioned obtain
To mixed slurry in 30min the volume fraction of thermal energy storage material (sizing be about 10vol%) is manually mixed；
It is 8.3cm that mixing mixture derived above, which is poured into diameter, in the cylindrical die of a height of 1.4cm, is passed through
The hardening of 3d obtains forming heat accumulating；Its photo is as shown in Figure 8.
Embodiment 4
A kind of preparation method of the short fibre/sodium sulphate/concrete forming heat accumulating of redox graphene/carbon fiber, packet
Include following step:
By the aqueous dispersions (mass fraction 10%) of the short fibre of 50g carbon fiber and 100g graphite oxide aqueous dispersions (quality
Score is 2%) by mechanical stirring and ultrasonic treatment mixing 1h, and it is 5mm that slurry, which is passed through diameter, by peristaltic pump or extruder pump
Tack needle be expressed into cetyl trimethylammonium bromide coagulating bath (mass fraction 1% of cetyl trimethylammonium bromide, water
Mass fraction be 99%) in and dissection be granulated, the short fine hydrogel of granular graphene oxide/carbon fiber is obtained, by washing
Wash, be freeze-dried after obtain the short fine foam of graphene oxide/carbon fiber, it is heated into reductase 12-4h in 250 DEG C of baking ovens, is obtained
The short fine foam of redox graphene/carbon fiber；
Using the vacuum impregnation stowage of vacuum aided, the sal glauberi of fusing is adsorbed onto also through capillary action
In the short fine foam of former graphene oxide/carbon fiber, the short fibre of redox graphene/carbon fiber/compound storage of sodium sulphate sizing is obtained
Hot material；
According to cement: quartz sand: water: the match ratio of the short fibre=10:15:2.5:5 of carbon fiber, by 40g cement, 60g quartz
Sand, 10g water and 20g carbon fiber are short fine by the way that 5min is manually mixed；
The short fibre of redox graphene/carbon fiber/sodium sulphate sizing thermal energy storage material that quality is 50g is added to
10min is manually mixed in the mixed slurry stated (volume fraction of sizing thermal energy storage material is about 20vol%)；
It is 8.3cm that mixing mixture derived above, which is poured into diameter, in the cylindrical die of a height of 1.4cm, is passed through
The hardening of 2d obtains forming heat accumulating；Its photo is as shown in Figure 9.
Embodiment 5
A kind of preparation method of boron nitride/magnesium nitrate/concrete forming heat accumulating, includes the following steps:
The aqueous dispersions (mass fraction 10%) of 5kg boron nitride nanosheet are led to slurry by peristaltic pump or extruder pump
Cross diameter be 3mm cylindrical mouth mold squeeze drip to diallyl dimethyl ammoniumchloride coagulating bath (diallyl dimethyl chlorine
Change ammonium mass fraction be 3%, water quality score be 97%) in, granular boron nitride hydrogel is obtained, by washing, freezing
Boron nitride foam is obtained after drying.
Using the vacuum impregnation stowage of vacuum aided, the magnesium nitrate of fusing is adsorbed onto boron nitride through capillary action
In foam, boron nitride/magnesium nitrate sizing thermal energy storage material is obtained.
According to cement: quartz sand: water: graphite powder=10:15:3.3:3.3 match ratio, and mixing quality is cement quality
0.5% water-reducing agent, by 1.2kg cement, 1.8kg quartz sand, 0.4kg water, 0.4kg graphite powder and 6g water-reducing agent by manually mixing
Close stirring 5min；
Boron nitride/magnesium nitrate sizing thermal energy storage material that quality is 0.9kg is added to mixed slurry obtained above
In 40min the volume fraction of thermal energy storage material (sizing be about 70vol%) is manually mixed；
Mixing mixture derived above is poured into 30 × 20 × 10cm3Rectangular mould in, by the hardening of 2d
Obtain forming heat accumulating.
Embodiment 6
A kind of preparation method of silicon nitride/sodium nitrate/concrete forming heat accumulating, includes the following steps:
By the mix moisture dispersion liquid of 2kg beta-silicon nitride nanowire and graphene oxide, (silicon nitride mass fraction is 5%, oxidation
Graphene mass fraction is 1%, and water quality score is 94%) to be attached separately in the ptfe autoclave of multiple 50ml, often
A reaction kettle fills about 20ml slurry, is then respectively put into 150 DEG C of baking oven and heats 8-24h, obtains block after hydro-thermal process
The nitridation silicone-hydrogel of shape, then freeze-drying obtains nitridation silica aerogel；
Using the vacuum impregnation stowage of vacuum aided, the sodium nitrate of fusing is adsorbed onto silicon nitride through capillary action
In aeroge, silicon nitride/sodium nitrate sizing thermal energy storage material is obtained；
According to cement: sea sand: water: aluminium oxide=10:20:3:5 match ratio, and it is cement quality 0.6% that quality, which is added,
Water-reducing agent, by 10kg cement, 20kg sea sand, 3kg water, 5kg aluminium oxide and 60g water-reducing agent pass through mechanical stirring be mixed
10min；
Silicon nitride/sodium nitrate sizing thermal energy storage material that quality is 1kg is added in above-mentioned mixed slurry manually
10min is mixed (volume fraction of sizing thermal energy storage material is about 40vol%)；
Mixing mixture derived above is poured in the mold with irregular cross-sectional shape that volume is 25L,
Forming heat accumulating is obtained by the hardening of 3d.
Embodiment 7
A kind of aluminium nitride/graphene oxide/calcium chloride hexahydrate/concrete forming heat accumulating preparation method, including under
State step:
By the mix moisture dispersion liquid of 20kg aluminium nitride and graphene oxide, (aluminium nitride mass fraction is 15%, graphite oxide
Alkene mass fraction 2%, water quality score 83%) it is squeezed by peristaltic pump or extruder pump by the syringe needle that diameter is 2mm and switches to poly- second
(mass fraction of polyethyleneimine is 2%, and the mass fraction of water is 93%, and the mass fraction of ethyl alcohol is in alkene imines coagulating bath
5%) aluminium nitride/graphene oxide hydrogel is obtained, aluminium nitride/graphene oxide foam is obtained after washing, being freeze-dried；
Using the vacuum impregnation stowage of vacuum aided, the calcium chloride hexahydrate of fusing is adsorbed onto nitrogen through capillary action
Change in aluminium/graphene oxide foam, obtains aluminium nitride/graphene oxide/calcium chloride hexahydrate sizing thermal energy storage material；
According to cement: river sand: water: aluminium powder=10:15:5:1 match ratio, by 20kg cement, the river 30kg sand, 10kg water and
2kg is by being manually mixed 30min；
Aluminium nitride/graphene oxide/calcium chloride hexahydrate sizing thermal energy storage material that quality is 65kg is added to above-mentioned
10min is manually mixed in obtained mixed slurry (volume fraction of sizing thermal energy storage material is about 50vol%)；
It is about 0.3m that mixing mixture derived above, which is poured into volume,2Truncated cone-shaped mold in, by the hardening of 3d
Obtain forming heat accumulating.
Embodiment 8
A kind of carbon nano-fiber/magnalium kirsite/concrete forming heat accumulating preparation method, includes the following steps:
The aqueous dispersions (mass fraction 5%) of the carbon nano-fiber of 500g surface oxidation are respectively placed in multiple 25ml
Ptfe autoclave in, each reaction kettle is packed into slurry and is no more than 10ml, is respectively placed in 200 DEG C of baking ovens and heats 8-
For 24 hours, block carbon nanofiber hydrogels are obtained, freeze-drying obtains carbon nano-fiber aeroge, then in 450 DEG C of vacuum tube
2h is heat-treated in formula furnace；
Using the vacuum impregnation stowage of vacuum aided, the magnalium kirsite of fusing is adsorbed onto carbon nano-fiber airsetting
In glue, carbon nano-fiber/magnalium kirsite sizing thermal energy storage material is obtained；
According to cement: quartz sand: water: expanded graphite=1:1.5:0.25:0.2 match ratio, and it is cement that quality, which is added,
The water-reducing agent of quality 0.7%, by 600g cement, 900g quartz sand, 150g water, 120g graphite and 4.2g water-reducing agent are by manually mixing
Close stirring 5min；
The carbon nano-fiber of quality about 250g/magnalium kirsite sizing thermal energy storage material is added to obtained above mixed
It closes and 15min is manually mixed in slurry (volume fraction of sizing thermal energy storage material is about 40vol%)；
Mixing mixture derived above is poured into 30 × 20 × 5cm3Rectangular mould in, obtained by the hardening of 2d
Shape heat accumulating.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method for shaping heat accumulating, comprising: highly heat-conductive material is prepared into foam or aeroge；Load heat accumulation
Material obtains sizing thermal energy storage material；Sizing thermal energy storage material is mixed with concrete, is shaped, forming heat accumulation material is obtained
Material.
2. preparation method according to claim 1, it is characterised in that: highly heat-conductive material is prepared into foam or aeroge
Method includes hydro-thermal self-assembly method, templating self-assembly method, chemical vapour deposition technique, 3D printing method, sol-gel method, solvent heat
Method, foaming, squeezes and cuts at least one of comminution granulation or presoma conversion method liquid phase extrusion molding；
And/or after melting heat accumulating, it is loaded into the foam or aeroge of highly heat-conductive material preparation；
And/or the method for loading heat accumulating includes at least one of adsorbing, injecting, squeeze into, be pressed into, instill or penetrate into.
3. preparation method according to claim 1, it is characterised in that: forming includes the following steps: the compound heat accumulation that will be formed
Material is poured with the mixture that concrete is mixed to get, and forming heat accumulating is obtained after hardened；
And/or sizing thermal energy storage material and concrete hybrid mode are included artificial stirring or carried out using blender mechanical
Stirring.
4. preparation method according to claim 3, it is characterised in that: sizing thermal energy storage material volume obtains after accounting for hardening
Forming heat accumulating total volume 1-70vol%；
And/or firm time 1-10d.
5. preparation method according to claim 1, it is characterised in that: mix sizing thermal energy storage material with concrete
When, it is additionally added heat filling.
6. preparation method according to claim 5, it is characterised in that: heat filling accounts for concrete and heat filling gross mass
1-60wt%；
And/or heat filling includes graphene, graphene oxide, graphite, carbon fiber, graphite fibre, expanded graphite, carbon nanometer
Pipe, carbon nano-fiber, silicon carbide, metal powder, metallic fiber, metal nano fiber, metal organic frame, copper nano-wire, richness
Strangle alkene, boron nitride, silicon nitride, aluminium nitride, silicon carbide, boron carbide, magnesium carbide, zirconium carbide, calcium carbide, chromium carbide, tungsten carbide, carbon
Change vanadium, aluminium oxide, zinc oxide, magnesia, copper, silver, aluminium, magnesium, iron, biomass conversion carbon material, macromolecule to convert in carbon material
At least one；
And/or concrete includes water, cement and aggregate；And at least one of additive or modifying agent.
7. preparation method according to claim 1, it is characterised in that: highly heat-conductive material include graphene, graphene oxide,
Graphite, carbon fiber, graphite fibre, expanded graphite, carbon nanotube, carbon nano-fiber, silicon carbide, metal powder, metallic fiber, gold
Belong to nanofiber, metal organic frame, copper nano-wire, fullerene, boron nitride, silicon nitride, aluminium nitride, silicon carbide, boron carbide, carbon
Change magnesium, zirconium carbide, calcium carbide, chromium carbide, tungsten carbide, vanadium carbide, aluminium oxide, zinc oxide, magnesia, biomass and converts carbon materials
At least one of material, macromolecule presoma conversion carbon material；
And/or heat accumulating includes the fusible heat accumulating of fusing point≤800 DEG C.
8. preparation method according to claim 7, it is characterised in that: heat accumulating include paraffin, higher aliphatic hydrocarbon, sugar or
Glycitols, alcohols, polyhydroxy carbonic acid class, polyolefins, polymeric polyalcohols, acetic acid, camphenilone, 1- bromine docosane, 15 ketone,
8- heptadecanone, cyanamide, 2- heptadecanone, 3- heptadecanone, pelargone amphene, acetamide, ethyl-lithium, high-density polyethylene
Alkene, catechol, antifebrin, butanedioic anhydride, urea, hydroquinone, crystalline hydrate salt, sodium sulphate, chlorate, nitrate,
At least one of carbonate, fluoride salt, hydroxide, complex salt, metal or alloy class..
9. the described in any item preparation methods of claim 1-8 are obtained to shape heat accumulating.
10. the described in any item preparation methods of claim 1-8 or forming heat accumulating as claimed in claim 9 are more than the industry
Heat, the storage of waste heat and natural heat energy and the application using field.
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