CN109135683A - A method of preparing fused salt-ceramics phase-change heat-storage material - Google Patents
A method of preparing fused salt-ceramics phase-change heat-storage material Download PDFInfo
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
Abstract
Fused salt-ceramics phase-change heat-storage material method is prepared the invention discloses a kind of, belongs to phase-change heat-storage material field.Method includes the following steps: preparing high-temperature molten salt particle；Eutectic salt particle is coated in precursor sol gel process；Compacting sintering is carried out to fused salt phase-change material sample.Preparation method of the present invention is simple, and cost is relatively low, is easily mass produced.It solves the problems, such as that the hygroscopicity of high-temperature molten salt phase-change material is strong, thermal structure intensity is weak, use environment is expanded to high-temperature phase-change heat storage material and is of great significance.
Description
Technical field
The present invention relates to phase-change heat-storage material fields, prepare fused salt-ceramics phase-change heat-storage material more particularly to a kind of
Method.
Background technique
Energy storage technology aims to solve the problem that the discontinuous problem of energy supply over time and space, is to improve energy utilization rate
Effective way.All have in terms of space flight and aviation, utilization of new energy resources, the heat recycle process of industry and civil buildings wide
Wealthy application prospect.Meanwhile compared to chemical electric power storage, heat-storage technology has the advantages such as big, the strong, environmental protection of stability of stored energy capacitance,
Also have broad application prospects in power system operation." peak load shifting " is the peak load for reducing power grid, and it is negative to improve low ebb
Lotus, smooth load curve stablize the important means of operation of power networks；Select suitable heat accumulating be applied to power supply industry to close weight
It wants.
Heat-storage technology mainly includes three kinds of sensible heat, latent heat and reaction heat heat accumulation modes.Wherein, with solid the one of phase-change material
Gu, solid-liquid phase-changeable latent heat it is most universal also most important to store the latent heat type energy storage mode of heat.Phase-change heat-storage material has phase
Become that latent heat is big, storage density is high, inhales exothermic process approximation isothermal, the advantages that process is easy to control.Phase-change heat-storage material is according to using
Temperature range, and high temperature type and low form phase-change heat-storage material can be divided into；Or organic can be divided into according to material type again
With inorganic phase-change heat-storage material.There is fused salt phase-change heat-storage material storage density height, charge and discharge thermal process to be similar to constant temperature, heat accumulation
Density is high, cost performance height, is easy to run the advantages that control and management, has great advantage in phase-change material field.But it is molten
Salt phase-change heat-storage material there are hygroscopicity serious, the problem that fused salt is easily revealed and thermal structure intensity is low.In order to solve these
Problem needs to be packaged fused salt phase-change material, TEAP and EPS Ltd (Pendyala S. Macroencapsulation
of Phase Change Materials for Thermal Energy Storage[J]. Dissertations &
Theses-Gradworks, 2012.) it is utilized respectively polymer and fused salt is encapsulated into sphere by metal material, can make to melt
Salt and ambient humidity are environmentally isolated and provide a stable planform, but the not single preparation cost of this method it is larger and
And complex process；Lower use temperature range, the high conductivity of metal material of polymer are seriously limited in electric heating
Application environment.The present invention is directed to fused salt phase-change heat-storage material (halide, nitrate, sulfate, carbonate and multi-element eutectic
Salt) the case where moisture absorption leads to mechanical properties decrease and then seriously affects service life cycle is easy under use environment, utilization is molten
Sol-gel coats fused salt particle, and is mixed into ceramic matrix particle (MgO, Al2O3) compacting sintering.In sintering process
The superfine powder of fused salt particle surface completely coats fused salt particle wherein, make fused salt particle and external environment thoroughly every
From solving the problems, such as that fused salt is easy to moisture absorption, fused salt is easily revealed under high temperature.And stable knot can be provided after ceramic particle is sintered
Structure；Anti- moisture absorption may finally be prepared, mechanical behavior under high temperature is good, the phase-change heat-storage material of high comprehensive performance.
Summary of the invention
In order to solve problem above, fused salt-ceramics phase-change heat-storage material method is prepared the present invention provides a kind of, passed through
Fused salt particle is coated using sol-gal process, and using ceramics as basis material, provides a kind of pair of fused salt phase transformation
The method that heat accumulating is packaged.
It is according to the present invention to prepare fused salt-ceramics phase-change heat-storage material method, comprising the following steps:
Step (1) selects heat-storage medium, is mixed to prepare mixture；
Step (2), by mixture made from step (1) be warming up to mixture melting temperature or more than so that mixture is become liquid molten
Salt, it is cooling broken after held for some time, prepare high-temperature molten salt particle；Or mixture made from step (1) is dissolved in deionization
It after water, is dried, is crushed after drying and prepares high-temperature molten salt particle；
Step (3) is mixed to obtain mixed liquor according to presoma butyl titanate and dehydrated alcohol 1:2 to 1:4 volume ratio,
High-temperature molten salt particle prepared by step (2) is added in the mixed liquor；
Distilled water, glacial acetic acid mixed liquor of the pH value between 2-3 is added in step (4), and hydrolysis hair occurs and answers, generates gel cladding
Onto the high-temperature molten salt particle；
Step (5) calcines the high-temperature molten salt particle coated, spare after cooling；
Particle made from step (5) and ceramic particle are carried out compound suppressing, prepare fused salt-ceramics phase-change thermal storage by step (6)
Material.
Further, the heat-storage medium in step (1) is halide, nitrate, sulfate, carbonate and polynary total
One or more of brilliant salt powder.
Further, the halide includes: NaCl, MgCl2、CaCl2、KCl、BaCl2、LiCl；The nitrate packet
It includes: NaNO3、KNO3、LiNO3；The sulfate includes: Na2SO4、K2SO4；The carbonate includes Na2CO3、K2CO3、BaCO3、
CaCO3、Li2CO3；The multi-element eutectic salt includes: NaNO3-KNO3、Na2CO3-K2CO3、NaNO3-LiNO3、Na2CO3-Li2CO3。
Further, the high-temperature molten salt particle being added in step (3) is not dissolved in described according to presoma butyl titanate
The mixed liquor being mixed with dehydrated alcohol 1:2 to 1:4 volume ratio.
Further, the ceramic particle in the step (6) includes: MgO, Al2O3、SiO2。
Further, the high-temperature molten salt particle size range prepared in the step (2) is in 0.1mm-10mm.
Further, after the step (4) further include: active carbon powder is added, continues to stir, temperature is controlled 50
DEG C -70 DEG C, liquid phase is made to become sticky.
Further, the active carbon powder accounts for the 9%-12% of fused salt granular mass score.
Further, the material being coated on high-temperature molten salt particle includes: TiO2 、Al2O3。
Further, the method for preparing particle includes: compacting preparation, is granulated preparation, is crushed preparation.
Beneficial effects of the present invention:
(1) present invention using sol-gal process encapsulate high-temperature molten salt particle phase-change material, and by after encapsulation particle and ceramics
It is compound that high temperature energy-storage is made by encapsulation to fused salt particle and with the mixing compacting sintering of basis material in Particles dispersed sintering
Ceramics, the material mechanical performance finally prepared is excellent, meets the mechanics bearing capacity of sample at high temperature.
(2) it relative to conventional high-temperature fused salt heat accumulating, is carried out in fused salt phase-change material outer surface by sol-gal process
Cladding helps to solve the problems, such as that the hygroscopicity of high-temperature molten salt phase-change material is strong, fused salt is easily revealed, expands high-temperature phase-change heat storage
The use environment range of material.
(3) during collosol and gel coats, it is selectively added active carbon particle；In subsequent high-temperature heat treatment
In, active carbon inevitably loses a part, and being left behind some spaces can be swollen to the volume in fused salt solid-liquid phase-change process
Swollen offer buffering；Remaining next part active carbon particle can promote the thermal conductivity of sample.
(4) preparation method of the present invention is simple, and cost is relatively low, is easily mass produced.Solves high-temperature molten salt phase-change material
The problem that hygroscopicity is strong, thermal structure intensity is weak expands use environment to high-temperature phase-change heat storage material and is of great significance.
Detailed description of the invention
Fig. 1 shows the reactiveness figure according to the present invention for preparing fused salt-ceramics phase-change heat-storage material method；
Fig. 2 shows the flow charts according to the present invention for preparing fused salt-ceramics phase-change heat-storage material method.
Specific embodiment
Below in conjunction with specific attached drawing the present invention is described in detail specific embodiment.It should be noted that in following embodiments
The combination of the technical characteristic or technical characteristic of description is not construed as isolated, they can be combined with each other to reaching
To superior technique effect.In the drawings of the following embodiments, the identical label that each attached drawing occurs represent identical feature or
Person's component, can be apply to different embodiments.
As shown in Figure 1, the present invention for fused salt phase-change heat-storage material (halide, nitrate, sulfate, carbonate and
Multi-element eutectic salt) the problem of humidity environment fails, high-temperature molten salt particle is coated using sol-gal process, and is mixed into
Ceramic matrix material (MgO, Al2O3) be sintered.Superfine powder (the titanium dioxide/oxidation of fused salt particle surface in sintering process
Aluminium clad) fused salt particle is completely coated wherein, fused salt particle is isolated thoroughly with external environment, solves moisture absorption and asks
Topic.And stable structure can be provided after ceramic particle is sintered；Anti- moisture absorption, high performance phase-change thermal storage may finally be prepared
Material.
Fig. 2 shows the flow charts according to the present invention for preparing fused salt-ceramics phase-change heat-storage material method.Such as Fig. 2 institute
Show, it is according to the present invention prepare fused salt-ceramics phase-change heat-storage material method the following steps are included:
Step 102, heat-storage medium is selected, mixture is mixed to prepare；
Step 104, by mixture made from step 102 be warming up to mixture melting temperature or more than make mixture become liquid to melt
Salt, it is cooling broken after held for some time, prepare high-temperature molten salt particle；Or after mixture made from step 102 is dissolved in water, into
Row drying, is crushed after drying and prepares high-temperature molten salt particle；
Step 106, it is mixed to obtain mixed liquor according to presoma butyl titanate and dehydrated alcohol 1:2 to 1:4 volume ratio,
High-temperature molten salt particle prepared by step 104 is added in the mixed liquor；
Step 108, distilled water, glacial acetic acid mixed liquor of the pH value between 2-3 is added, hydrolysis hair occurs and answers, generates gel cladding
Onto the high-temperature molten salt particle；
Step 110, the high-temperature molten salt particle coated is calcined, it is spare after cooling；
Step 112, particle made from step 110 and ceramic particle are subjected to compound suppressing, prepare fused salt-ceramics phase-change thermal storage
Material.
Example 1:
Step 1: preparing high-temperature molten salt particle
Step 1.1 selects Na2CO3 and K2CO3 as heat-storage medium, will be mixed with the ratio of 52:48, with ball mill with ball material
Than 1:1,110 revs/min of speed ball milling 30min, it is uniformly mixed Na2CO3 with K2CO3 to be used to prepare hydration eutectic salts.
Mixed mixture is heated to 720 DEG C by step 1.2, at molten state；Heat preservation 2 hours, prepares melting eutectic
Salt.
Powder, is placed on the ball of different-diameter by step 1.3, the broken, grind into powder by the melting eutectic salts prepared
Micro water is added in shape grinding tool, the pressure of 10Mpa is taken to be suppressed, the condition by the fused salt particle suppressed at 680 DEG C
The fused salt particle of different-grain diameter is prepared in lower sintering, in case using.
Step 2: coating eutectic salt particle in sol-gel process
Step 2.1 is mixed to obtain yellow solution according to the volume ratio of presoma butyl titanate and dehydrated alcohol 1:2,
The fused salt particle of preparation is added in mixed liquor；The eutectic salt particle is not dissolved in mixed liquor.
Step 2.2 (arrives pH value adjustment the mixed liquor of distilled water and glacial acetic acid with concentrated nitric acid in the case where being vigorously stirred effect
It 2-4) is added drop-wise to dropwise in step 2.1 gained intermediate, and continues to stir.
Suitable active carbon powder (account for fused salt granular mass score 9%) is added in step 2.3, continues to stir, temperature control
System makes liquid phase become sticky at 60 DEG C.
Step 2.4 post-processes the fused salt particle coated, and above-mentioned product is put into temperature of the Muffle furnace at 400 DEG C
It is calcined under degree environment, it is spare after cooling.
Step 3: carrying out compacting sintering to fused salt phase-change material sample
Particle after cladding is uniformly mixed with the mass ratio of 6:4 and MgO ceramic particle and is put into mold by step 3.1, is applied
The pressure of 2000N, pressure maintaining demould after five minutes, prepare block materials.
Block materials are put into Muffle furnace by step 3.2, and sintering temperature is set as 720 DEG C, and heating rate is that room temperature 60 is divided
Clock is warming up to 650 DEG C for 120 minutes after being then warming up to 410 DEG C within 90 minutes to 100 DEG C, is warming up within last 120 minutes 720 DEG C, protects
Temperature is after 120 minutes, furnace cooling.
Example 2:
Step 1: preparing high-temperature molten salt particle
Step 1.1 selects Na2CO3 and K2CO3 as heat-storage medium, will be mixed with the ratio of 52:48, with ball mill with ball material
Than 1:1,110 revs/min of speed ball milling 30min, it is uniformly mixed Na2CO3 with K2CO3 to be used to prepare hydration eutectic salts.
Mixed mixture is heated to 720 DEG C by step 1.2, at molten state；Heat preservation 2 hours, prepares melting eutectic
Salt.
Powder, is placed on the ball of different-diameter by step 1.3, the broken, grind into powder by the melting eutectic salts prepared
Micro water is added in shape grinding tool, the pressure of 10Mpa is taken to be suppressed, the condition by the fused salt particle suppressed at 680 DEG C
The fused salt particle of different-grain diameter is prepared in lower sintering, in case using.
Step 2: coating eutectic salt particle in sol-gel process
Step 2.1 is mixed to obtain yellow solution according to the volume ratio of presoma butyl titanate and dehydrated alcohol 1:2,
The fused salt particle of preparation is added in mixed liquor；The eutectic salt particle is not dissolved in mixed liquor.
Step 2.2 (arrives pH value adjustment the mixed liquor of distilled water and glacial acetic acid with concentrated nitric acid in the case where being vigorously stirred effect
It 2-4) is added drop-wise to dropwise in step 2.1 gained intermediate, and continues to stir.
Step 2.3 continues to stir, and temperature is controlled at 60 DEG C, and liquid phase is made to become sticky.
Step 2.4 post-processes the fused salt particle coated, and above-mentioned product is put into temperature of the Muffle furnace at 400 DEG C
It is calcined under degree environment, it is spare after cooling.
Step 3: carrying out compacting sintering to fused salt phase-change material sample
Particle after cladding is uniformly mixed with the mass ratio of 6:4 and MgO ceramic particle and is put into mold by step 3.1, is applied
The pressure of 2000N, pressure maintaining demould after five minutes, prepare block materials.
Block materials are put into Muffle furnace by step 3.2, and sintering temperature is set as 720 DEG C, and heating rate is that room temperature 60 is divided
Clock is warming up to 650 DEG C for 120 minutes after being then warming up to 410 DEG C within 90 minutes to 100 DEG C, is warming up within last 120 minutes 720 DEG C, protects
Temperature is after 120 minutes, furnace cooling.
Example 3:
Step 1: preparing high-temperature molten salt particle
Step 1.1 selects KCl and NaCl as heat-storage medium, will be mixed with the ratio of 49.4:50.6, with ball mill with ball material
Than 1:1,110 revs/min of speed ball milling 30min, it is uniformly mixed KCl with NaCl to be used to prepare eutectic salts.
Mixed mixture is carried out pre-burning by step 1.2, and sintering temperature is 680 DEG C, preparation melting eutectic salts.
The eutectic salts prepared are crushed, are ground up, sieved by step 1.3, select powder diameter in 70 mesh between 100 mesh
Particle in case use.
Step 2: coating eutectic salt particle in sol-gel process
Step 2.1 is mixed to obtain yellow solution according to presoma butyl titanate and dehydrated alcohol 1:4 volume ratio,
The fused salt particle of preparation is added in mixed liquor；The eutectic salt particle is not dissolved in mixed liquor.
Step 2.2 (arrives pH value adjustment the mixed liquor of distilled water and glacial acetic acid with concentrated nitric acid in the case where being vigorously stirred effect
It 2-4) is added drop-wise to dropwise in step 2.1 gained intermediate, and continues to stir.
Suitable active carbon powder (account for fused salt granular mass score 9%) is added in step 2.3, continues to stir, temperature control
System makes liquid phase become sticky in room temperature.
Step 2.4 post-processes the fused salt particle coated, and above-mentioned product is put into temperature of the Muffle furnace at 400 DEG C
It is calcined under degree environment, it is spare after cooling.
Step 3: carrying out compacting sintering to fused salt phase-change material sample
Particle after cladding is uniformly mixed with the mass ratio of 6:4 and Al2O3 ceramic particle and is put into mold by step 3.1, is applied
Add the pressure of 2000N, pressure maintaining demoulds after five minutes, prepares block materials.
Block materials are put into Muffle furnace by step 3.2, and sintering temperature is set as 720 DEG C, and heating rate is that room temperature 60 is divided
Clock is warming up to 650 DEG C for 120 minutes after being then warming up to 410 DEG C within 90 minutes to 100 DEG C, is warming up within last 120 minutes 720 DEG C, protects
Temperature is after 120 minutes, furnace cooling.
Example 4:
Step 1: preparing high-temperature molten salt particle
Step 1.1 selects Na2CO3 and K2CO3 as heat-storage medium, will be mixed with the ratio of 52:48, with ball mill with ball material
Than 1:1,110 revs/min of speed ball milling 30min, it is uniformly mixed Na2CO3 with K2CO3 to be used to prepare hydration eutectic salts.
Mixed mixture is dissolved in deionized water by step 1.2, is placed after mixing evenly in an oven, drying 72
Hour, prepare hydration eutectic salts.
The hydration eutectic salts prepared are crushed, are ground to powder by step 1.3, and powder is placed on to the ball of different-diameter
Micro water is added in shape grinding tool, the pressure of 10Mpa is taken to be suppressed, the condition by the fused salt particle suppressed at 680 DEG C
The fused salt particle of different-grain diameter is prepared in lower sintering, in case using.
Step 2: coating eutectic salt particle in sol-gel process
Step 2.1 is mixed to obtain yellow solution according to the volume ratio of presoma butyl titanate and dehydrated alcohol 1:2,
The fused salt particle of preparation is added in mixed liquor；The eutectic salt particle is not dissolved in mixed liquor.
Step 2.2 (arrives pH value adjustment the mixed liquor of distilled water and glacial acetic acid with concentrated nitric acid in the case where being vigorously stirred effect
It 2-4) is added drop-wise to dropwise in step 2.1 gained intermediate, and continues to stir.
Suitable active carbon powder (account for fused salt granular mass score 9%) is added in step 2.3, continues to stir, temperature control
System makes liquid phase become sticky at 60 DEG C.
Step 2.4 post-processes the fused salt particle coated, and above-mentioned product is put into temperature of the Muffle furnace at 400 DEG C
It is calcined under degree environment, it is spare after cooling.
Step 3: carrying out compacting sintering to fused salt phase-change material sample
Particle after cladding is uniformly mixed with the mass ratio of 6:4 and MgO ceramic particle and is put into mold by step 3.1, is applied
The pressure of 2000N, pressure maintaining demould after five minutes, prepare block materials.
Block materials are put into Muffle furnace by step 3.2, and sintering temperature is set as 720 DEG C, and heating rate is that room temperature 60 is divided
Clock is warming up to 650 DEG C for 120 minutes after being then warming up to 410 DEG C within 90 minutes to 100 DEG C, is warming up within last 120 minutes 720 DEG C, protects
Temperature is after 120 minutes, furnace cooling.
It is not in showing for structural failure that experiment, which shows that this composite phase-change heat-storage material can work under humidity environment,
As there is certain structural strength in hot environment, since fused salt particle encapsulate and having been answered in sol-gel process
Ceramic matrix is closed, so reducing fused salt leakage problem and the corrosion strength to ambient enviroment.
Although the embodiment of the present invention is had been presented for herein, it will be appreciated by those of skill in the art that not taking off
In the case where from spirit of that invention, the embodiments herein can be changed.Above-described embodiment is only exemplary, should not be with
Restriction of the embodiments herein as interest field of the present invention.
Claims (10)
1. a kind of prepare fused salt-ceramics phase-change heat-storage material method, which comprises the following steps:
Step (1) selects heat-storage medium, is mixed to prepare mixture；
Step (2), by mixture made from step (1) be warming up to mixture melting temperature or more than so that mixture is become liquid molten
Salt, it is cooling broken after held for some time, prepare high-temperature molten salt particle；Or mixture made from step (1) is dissolved in deionization
It after water, is dried, is crushed after drying and prepares high-temperature molten salt particle；
Step (3) is mixed to obtain mixed liquor according to presoma butyl titanate and dehydrated alcohol 1:2 to 1:4 volume ratio,
High-temperature molten salt particle prepared by step (2) is added in the mixed liquor；
Distilled water, glacial acetic acid mixed liquor of the pH value between 2-3 is added in step (4), and hydrolysis hair occurs and answers, generates gel cladding
Onto the high-temperature molten salt particle；
Step (5) calcines the high-temperature molten salt particle coated, spare after cooling；
Particle made from step (5) and ceramic particle are carried out compound suppressing, prepare fused salt-ceramics phase-change thermal storage by step (6)
Material.
2. the method according to claim 1, wherein the heat-storage medium in the step (1) be halide,
One or more of nitrate, sulfate, carbonate and multi-element eutectic salt powder.
3. according to the method described in claim 2, it is characterized in that, the halide include: NaCl, MgCl2, CaCl2, KCl,
BaCl2,LiCl；The nitrate includes: NaNO3, KNO3, LiNO3；The sulfate includes: Na2SO4, K2SO4；The carbon
Hydrochlorate includes Na2CO3, K2CO3, BaCO3, CaCO3, Li2CO3；The multi-element eutectic salt includes: NaNO3-KNO3, Na2CO3-
K2CO3、NaNO3-LiNO3、Na2CO3-Li2CO3。
4. the method according to claim 1, wherein the high-temperature molten salt particle being added in the step (3) is insoluble
The mixed liquor being mixed described in Xie Yu according to presoma butyl titanate and dehydrated alcohol 1:2 to 1:4 volume ratio.
5. the method according to claim 1, wherein the ceramic particle in the step (6) include: MgO,
Al2O3、SiO2。
6. the method according to claim 1, wherein the high-temperature molten salt grain diameter prepared in the step (2)
Range is in 0.1mm-10mm.
7. the method according to claim 1, wherein after the step (4) further include: active powdered carbon is added
End continues to stir, and temperature is controlled at 50 DEG C to 70 DEG C, and liquid phase is made to become sticky.
8. the method according to the description of claim 7 is characterized in that the active carbon powder accounts for the 9% of fused salt granular mass score
To 12%.
9. the method according to claim 1, wherein the material being coated on high-temperature molten salt particle includes: TiO2 、
Al2O3。
10. being granulated system the method according to claim 1, wherein the method for preparing particle includes: compacting preparation
It is standby, it is crushed preparation.
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