CN107523272A - Low co-melting hydrous salt phase change material of a kind of high heat conduction binary and preparation method thereof - Google Patents

Low co-melting hydrous salt phase change material of a kind of high heat conduction binary and preparation method thereof Download PDF

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CN107523272A
CN107523272A CN201610495551.9A CN201610495551A CN107523272A CN 107523272 A CN107523272 A CN 107523272A CN 201610495551 A CN201610495551 A CN 201610495551A CN 107523272 A CN107523272 A CN 107523272A
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change material
heat conduction
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CN107523272B (en
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刘雨时
杨英姿
高小建
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Harbin Institute of Technology
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    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063Materials absorbing or liberating heat during crystallisation; Heat storage materials

Abstract

Low co-melting hydrous salt phase change material of a kind of high heat conduction binary and preparation method thereof, it is related to a kind of inorganic hydrous salt phase transition material and preparation method thereof.There is the shortcomings that thermal conductivity is relatively low, and degree of supercooling height is with being mutually layered in existing phase transition temperature, the preparation process of the phase-change material is cumbersome and complex operation in use in 30 DEG C or so of hydrous salt phase change material.The solution that the present invention is made up of 23~26 parts of saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~1.5 part of nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer in parts by weight.Preparation method in the present invention is that the process of the low co-melting hydrous salt phase transition solution of high heat conduction binary is ultimately formed by ratio of weight and the number of copies by saltcake, disodium hydrogen phosphate dodecahydrate, nucleator, surfactant, multifunctional modification agent and stabilizer mixed dissolution one by one.The present invention is used in material chemistry technical field.

Description

Low co-melting hydrous salt phase change material of a kind of high heat conduction binary and preparation method thereof
Technical field
The present invention relates to a kind of inorganic phase-changing material and preparation method thereof, belong in material chemistry technical field.
Background technology
Phase-change material can absorb the heat energy of extraneous surplus during phase in version occurs, and need heat energy in the external world During supply, the heat energy of absorption is discharged, so as to reach the effect of adjusting ambient temperature.Building and agricultural greenhouse field, Requirement to environment temperature is higher, therefore generates excessive energy consumption.If phase-change material is applied to agricultural greenhouse and building In, due to the property of its energy storage and release energy, energy consumption can be not only reduced, plays a part of energy-conservation, and can also reach and change Kind and control greenhouse purpose.
In building and agricultural greenhouse field, the most frequently used phase-change material belongs to solid-liquid phase change material.Solid-liquid phase change material Two major classes are broadly divided into, one kind is organic phase change material, and another kind of is inorganic phase-changing material.Organic phase change material mainly includes Machine acid, alcohol and higher alkane etc., it is that phase transition temperature is controllable the advantages of organic phase change material, property is stable, almost without surfusion Mutually it is layered, corrosivity is smaller.But there is also some shortcomings:Thermal conductivity is very low, and latent heat of phase change is relatively low.Inorganic phase-changing material is main Halide, inorganic hydrated salt, metal and alloy including alkali and alkaline-earth metal.Wherein, in cryogenic applications field, inorganic hydrated salt Phase-change material is of great interest, its biggest advantage is that cheap, rich and easy to get, latent heat of phase change is high, but also has several lack Point:Surfusion, mutually layering and thermal conductivity are relatively low, wherein it is fatal, strong influence to be subcooled and be mutually layered the two shortcomings The application of inorganic hydrous salt phase transition material.If it can overcome its supercooling by suitable material modification and materials synthesis and mutually divide The shortcomings of layer, inorganic phase-changing material certainly will have broad application prospects.
At this stage, the research for inorganic hydrous salt phase transition is still less, especially water of the phase transition temperature at 30 DEG C or so It is more rare to close salt phase-change material.Relatively common at present, the inorganic hydrous salt phase transition material of the temperature range mainly has six water Calcium chloride, washing soda and sal glauberi.Regrettably, they have that thermal conductivity is relatively low, supercooling and are mutually layered scarce Put and be difficult to overcome.
The content of the invention
It is an object of the invention to provide low co-melting hydrous salt phase change material of a kind of high heat conduction binary and preparation method thereof, with solution Certainly existing phase transition temperature has that thermal conductivity is relatively low, and degree of supercooling is high in 30 DEG C or so of hydrous salt phase change material in use The shortcomings that being mutually layered, the preparation process of the phase-change material is cumbersome and the problem of complex operation.
The present invention adopts the technical scheme that to solve above-mentioned technical problem:
A kind of low co-melting hydrous salt phase change material of high heat conduction binary, the low co-melting hydrous salt phase change material of the high heat conduction binary are It is 23~26 parts of saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~1.5 part of nucleator, 1 by parts by weight The solution of~2.25 parts of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer composition.
A kind of preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary, the preparation method is according to following steps Carry out:
Step 1:Weigh in parts by weight 23~26 parts saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5 ~1.5 parts of nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer;
Step 2:23~26 parts of saltcake and 70~75 parts of disodium hydrogen phosphate dodecahydrate are poured into container and mixed, It is heated to melting completely under conditions of 50~70 DEG C, is stirred for uniformly being prepared into low co-melting hydration salting liquid;
Step 3:It is low it is co-melting hydration salting liquid stirring condition under, sequentially add 0.5~1.5 part nucleator, 1~ 2.25 parts of surfactant is completely dissolved up to the two, forms preliminary modified solution;
Step 4:3~4.5 parts of multifunctional modification agent is added in preliminary modified solution, it is ultrasonic after stirring, make it scattered Uniformly, whole modified solution is formed;
Step 5:1~2.25 part of stabilizer is added in whole modified solution, stirs to being completely dissolved, ultimately forms height The low co-melting hydrous salt phase transition solution of heat conduction binary.
The invention has the advantages that:
1st, this preparation method is simple and easy, and it adds nucleator, multifunctional modification agent, surfactant in operation And stabilizer.Wherein, nucleator and multifunctional modification agent are used in mixed way the degree of supercooling that can greatly reduce low co-melting hydrated salt, The thermal conductivity of the low co-melting hydrous salt phase change material of high heat conduction binary can also be increased to 1.27W/m by multifunctional modification agent simultaneously K.Surfactant can make multifunctional modification agent have preferable dispersion effect, and stabilizer can improve the heat of phase-change material Cyclical stability.
2nd, the latent heat of phase change of the low co-melting hydrous salt phase change material of high heat conduction binary prepared by this preparation method is very big, energy Enough reach 256.9~262.1kJ/kg, phase transition temperature is 31.4~31.6 DEG C, and solid-state and liquid heat conductive coefficient respectively reach 0.64 ~0.71W/mK and 1.00~1.27W/mK, it is the Inorganic phase change energy storage material of excellent performance, before there is wide application Scape.
3rd, the energy storage and release heat process of the low co-melting hydrous salt phase change material of high heat conduction binary is steady in the present invention, no mistake Cold and phase lamination, prolonged application stable performance.
4th, the present invention in the low co-melting hydrous salt phase change material of high heat conduction binary it is cheap, nontoxic and corrosion-free, It is easy to use, safe and reliable.It is adapted to promote the use of.
Brief description of the drawings
Fig. 1 is the FB(flow block) of preparation method in the present invention;
Fig. 2 is the cooling curve schematic diagram of the low co-melting hydrous salt phase change material of high heat conduction binary, and curve a is embodiment in figure Cooling curve in one, curve b are the cooling curve in embodiment two;
Fig. 3 is the DSC curve schematic diagram of the low co-melting hydrous salt phase change material of high heat conduction binary in embodiment one;
Fig. 4 is the DSC curve schematic diagram of the low co-melting hydrous salt phase change material of high heat conduction binary in embodiment two;
Fig. 5 is the liquid thermal conductivity of the low co-melting hydrous salt phase change material of high heat conduction binary with α-Al2O3Nano-particle quality point The schematic diagram of number change;
Fig. 6 is that the solid-state thermal conductivity of the low co-melting hydrous salt phase change material of high heat conduction binary changes with α-Al2O3Nano-particle matter Measure the schematic diagram of fraction change;
Fig. 7 is DSC curve signal of the low co-melting hydrous salt phase change material of high heat conduction binary before and after 100 cold cyclings Scheme, curve c is the DSC curve before cold cycling in figure, and the fusion temperature of the DSC curve is 31.6 DEG C, and latent heat of phase change value is 256.9J/g;Curve d is the DSC curve after cold cycling, and the fusion temperature of the DSC curve is 31.5 DEG C, and latent heat of phase change value is 254.8J/g。
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment Any combination.
Embodiment one:Illustrate present embodiment with reference to Fig. 1, the low co-melting water of the high heat conduction binary in present embodiment Close salt phase-change material be by parts by weight be 23~26 parts saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~ 1.5 parts of nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer composition Solution.
Saltcake is Na in the present invention2SO4·10H2O, disodium hydrogen phosphate dodecahydrate Na2HPO4·12H2O。
Embodiment two:Present embodiment is the further restriction of embodiment one, awns in present embodiment Ratio of weight and number between nitre and disodium hydrogen phosphate dodecahydrate is 1: 3.This ratio is drawn by multiple sampling test Optimal ratio of weight and number between saltcake and disodium hydrogen phosphate dodecahydrate.
Embodiment three:Illustrate present embodiment with reference to Fig. 1, the preparation method is according to following in present embodiment What step was carried out:
Step 1:Weigh by ratio of weight and the number of copies 23~26 parts saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~1.5 part of nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilization Agent;
Step 2:23~26 parts of saltcake and 70~75 parts of disodium hydrogen phosphate dodecahydrate are poured into container and mixed, It is heated to melting completely under conditions of 50~70 DEG C, is stirred for uniformly being prepared into low co-melting hydration salting liquid;
Step 3:It is low it is co-melting hydration salting liquid stirring condition under, sequentially add 0.5~1.5 part nucleator, 1~ 2.25 parts of surfactant is completely dissolved up to the two, forms preliminary modified solution;
Step 4:3~4.5 parts of multifunctional modification agent is added in preliminary modified solution, it is ultrasonic after stirring, make it scattered Uniformly, whole modified solution is formed;
Step 5:1~2.25 part of stabilizer is added in whole modified solution, stirs to being completely dissolved, ultimately forms height The low co-melting hydrous salt phase transition solution of heat conduction binary.
Embodiment four:Present embodiment is the further restriction of embodiment three, and nucleator is borax, silicon One kind or wherein several combinations in sour sodium or potassium carbonate.
Embodiment five:Present embodiment is the further restriction of embodiment four, and surfactant is sea One kind or wherein several combinations in mosanom, sodium carboxymethylcellulose or sodium lignin sulfonate.
Embodiment six:Present embodiment be embodiment five further restriction, the multifunctional modification Agent is α-Al2O3Nano-particle.
Embodiment seven:Present embodiment is the further restriction of embodiment six, and the stabilizer is hydroxyl One kind or wherein several combinations in ethyl cellulose or PVP.
Beneficial effects of the present invention are verified by following examples:
Embodiment one:
Step 1:By Na2HPO4·12H2O and Na2SO4·10H2O powder mixes according to 75wt%: 25wt% ratio, It is placed in beaker, melts it under 60 DEG C of condition of water bath heating complete, and 1000rmp constant temperature stirs at 60 DEG C by solution Until uniform;
Step 2:1.00wt% boraxs and 1.50wt% sodium alginates are sequentially added into Na2SO4·10H2O-Na2HPO4· 12H2In the low hydration salting liquids molten altogether of O, solution temperature constant magnetic stirring 2 hours at 60 DEG C.Then, by 4.50wt% nanometers α- Al2O3Powder is added in solution, and 1500rmp stirs a hour, then under 120W power, ultrasonic half an hour.Most Afterwards, 1.50wt% hydroxyethyl celluloses are added in solution, and 1500rmp is stirred 2 hours, and it is low common to obtain high heat conduction binary Melt hydrous salt phase change material.
Embodiment two:
Step 1:By Na2HPO4·12H2O and Na2SO4·10H2O powder mixes according to 75wt%: 25wt% ratio, It is placed in beaker, melts it under 60 DEG C of condition of water bath heating complete, and 1000rmp constant temperature stirs at 60 DEG C by solution Until uniform;
Step 2:1.00wt% boraxs and 1.00wt% sodium alginates are sequentially added into Na2SO4·10H2O-Na2HPO4· 12H2In the low hydration salting liquids molten altogether of O, solution temperature constant magnetic stirring 2 hours at 60 DEG C.Then, by 3.00wt% nanometers α- Al2O3Powder is added in solution, and 1500rmp stirs a hour, then under 120W power, ultrasonic half an hour.Most Afterwards, 1.00wt% hydroxyethyl celluloses are added in solution, and 1500rmp is stirred 2 hours, and it is low common to obtain high heat conduction binary Melt hydrous salt phase change material.
It can be seen from general knowledge known in this field, the degree of supercooling of phase-change material is less than 3 DEG C and all can use, and it is smaller more that angle value is subcooled It is good.As shown in Figure 2, the degree of supercooling of embodiment one and embodiment two is 1.6 DEG C and 1.2 DEG C respectively, shows preferable low mistake Cold property, surfusion is being reduced to a certain degree.
By Fig. 3 and Fig. 4, the fusion temperature of embodiment one is 31.6 DEG C, and latent heat of phase change value is 256.9J/g.Implement The fusion temperature of example two is 31.4 DEG C, and latent heat of phase change value is 262.1J/g.It is low that high heat conduction binary can be obtained according to Fig. 3 and Fig. 4 The fusion temperature of co-melting hydrous salt phase change material is suitable, and latent heat of phase change is very high.
It can be seen from Fig. 5 and Fig. 6, co-melting hydrated salt low compared to unmodified binary, embodiment one and embodiment two 21.7% and 10.3% has been respectively increased in liquid thermal conductivity, and solid-state thermal conductivity improves 61.3% and 26.8%, shown respectively Larger thermal conductivity lifting, the low co-melting hydrous salt phase change material of high heat conduction binary obtained by the preparation method of the present invention can Embody higher energy storage and release energy efficiency.
It can be seen from Fig. 7, the low co-melting hydrous salt phase change material of high heat conduction binary is before cold cycling, the song in embodiment one Line c fusion temperature is 31.6 DEG C, and latent heat of phase change value is 256.9J/g, after 100 cold cyclings, curve d fusing temperature Degree is 31.5 DEG C, and latent heat of phase change value is 254.8J/g, it follows that the low co-melting hydrous salt phase change material of high heat conduction binary passes through 100 cold cyclings, thermal property are not almost lost.Therefore, the low co-melting hydrous salt phase change material of high heat conduction binary has preferable Cold cycling durability, have the long period working life.
Embodiment three:
Step 1:By Na2HPO4·12H2O and Na2SO4·10H2O powder mixes according to 75wt%: 25wt% ratio, It is placed in beaker, melts it under 60 DEG C of condition of water bath heating complete, and 1000rmp constant temperature stirs at 60 DEG C by solution Until uniform;
Step 2:1.00wt% boraxs and 2.25wt% sodium alginates are sequentially added into Na2SO4·10H2O-Na2HPO4· 12H2In the low hydration salting liquids molten altogether of O, solution temperature constant magnetic stirring 2 hours at 60 DEG C.Then, by 4.50wt% nanometers α- Al2O3Powder is added in solution, and 1500rmp stirs a hour, then under 120W power, ultrasonic half an hour.Most Afterwards, 2.25wt% hydroxyethyl celluloses are added in solution, and 1500rmp is stirred 2 hours, and it is low common to obtain high heat conduction binary Melt hydrous salt phase change material.
Example IV:
Step 1:By Na2SO4·10H2O-Na2HPO4·12H2O powder mixes according to 75wt%: 25wt% ratio, puts In beaker, melt it under 60 DEG C of condition of water bath heating complete, and 1000rmp constant temperature stirs directly at 60 DEG C by solution To uniform;
Step 2:1.00wt% boraxs and 1.50wt% sodium alginates are sequentially added into Na2SO4·10H2O-Na2HPO4· 12H2In the low hydration salting liquids molten altogether of O, solution temperature constant magnetic stirring 2 hours at 60 DEG C.Then, by 3.00wt% nanometers α- Al2O3 powder is added in solution, and 1500rmp stirs a hour, then under 120W power, ultrasonic half an hour.Most Afterwards, 1.50wt% hydroxyethyl celluloses are added in solution, and 1500rmp is stirred 2 hours, and it is low common to obtain high heat conduction binary Melt hydrous salt phase change material.

Claims (7)

  1. A kind of 1. low co-melting hydrous salt phase change material of high heat conduction binary, it is characterised in that:The low co-melting hydrated salt of the high heat conduction binary Phase-change material be by parts by weight be 23~26 parts saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~1.5 part Nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer composition it is molten Liquid.
  2. A kind of 2. low co-melting hydrous salt phase change material of high heat conduction binary according to claim 1, it is characterised in that:Saltcake and Ratio of weight and number between disodium hydrogen phosphate dodecahydrate is 1: 3.
  3. A kind of 3. preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary, it is characterised in that:The preparation method be by Carried out according to following steps:
    Step 1:Weigh in parts by weight 23~26 parts saltcake, 70~75 parts of disodium hydrogen phosphate dodecahydrate, 0.5~1.5 The nucleator, 1~2.25 part of surfactant, 3~4.5 parts of multifunctional modification agent and 1~2.25 part of stabilizer of part;
    Step 2:23~26 parts of saltcake and 70~75 parts of disodium hydrogen phosphate dodecahydrate are poured into container and mixed, 50~ It is heated to melting completely under conditions of 70 DEG C, is stirred for uniformly being prepared into low co-melting hydration salting liquid;
    Step 3:It is low it is co-melting hydration salting liquid stirring condition under, sequentially add 0.5~1.5 part nucleator, 1~2.25 part Surfactant until the two be completely dissolved, form preliminary modified solution;
    Step 4:3~4.5 parts of multifunctional modification agent is added in preliminary modified solution, it is ultrasonic after stirring, make it scattered equal It is even, form whole modified solution;
    Step 5:1~2.25 part of stabilizer is added in whole modified solution, stirs to being completely dissolved, ultimately forms high heat conduction The low co-melting hydrous salt phase transition solution of binary.
  4. 4. a kind of preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary according to claim 3, its feature It is:Nucleator is one kind or wherein several combinations in borax, sodium metasilicate or potassium carbonate.
  5. 5. a kind of preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary according to claim 4, its feature It is:Surfactant is one kind or wherein several groups in sodium alginate, sodium carboxymethylcellulose or sodium lignin sulfonate Close.
  6. 6. a kind of preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary according to claim 5, its feature It is:Multifunctional modification agent is α-Al2O3Nano-particle.
  7. 7. a kind of preparation method of the low co-melting hydrous salt phase change material of high heat conduction binary according to claim 6, its feature It is:Stabilizer is hydroxyethyl cellulose or one kind in PVP or wherein several combinations.
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CN108456509A (en) * 2018-03-13 2018-08-28 青海大学 A kind of inorganic hydrous salt phase transition energy-storing material and preparation method thereof
CN108456509B (en) * 2018-03-13 2020-11-06 青海大学 Inorganic hydrated salt phase change energy storage material and preparation method thereof
CN108531138A (en) * 2018-04-23 2018-09-14 西北大学 Low degree of supercooling quaternary disodium hydrogen phosphate base phase change heat storage material
CN108570311A (en) * 2018-04-23 2018-09-25 西北大学 The ternary disodium hydrogen phosphate base phase change heat storage material that can be encapsulated with aluminium
CN108822802A (en) * 2018-04-23 2018-11-16 西北大学 The quaternary disodium hydrogen phosphate base phase change heat storage material that can be encapsulated with aluminium
CN113549428A (en) * 2021-06-18 2021-10-26 张雨新 Preparation method of modified DHPD and eutectic hydrated salt thereof

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