CN106047302B - A kind of Inorganic phase change energy storage material and preparation method thereof - Google Patents
A kind of Inorganic phase change energy storage material and preparation method thereof Download PDFInfo
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- CN106047302B CN106047302B CN201610387127.2A CN201610387127A CN106047302B CN 106047302 B CN106047302 B CN 106047302B CN 201610387127 A CN201610387127 A CN 201610387127A CN 106047302 B CN106047302 B CN 106047302B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 42
- 230000008859 change Effects 0.000 title claims abstract description 24
- 239000011232 storage material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000013538 functional additive Substances 0.000 claims abstract description 16
- 239000002667 nucleating agent Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 230000005496 eutectics Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical class [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 4
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000012782 phase change material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 238000004781 supercooling Methods 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001631 strontium chloride Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of Inorganic phase change energy storage material, the energy storage material includes following components: 94-97 parts of energy storage basis material, 0.2-1.0 parts of functional additive, 2.0-3.5 parts of nucleating agent, 0.8-1.5 parts of surfactant.Resulting materials performance of the present invention is stable, cheap, abundant raw material, preparation is convenient, latent heat of phase change is big, nontoxic, thermal conductivity is high, allows to be widely used in the multiple fields such as solar energy low-temperature heat accumulating system, the daily heat preservation of family, domestic hot water's energy-storage system.
Description
Technical field
The invention belongs to technical field of phase change energy storage, in particular it relates to a kind of Inorganic phase change energy storage material and its
Preparation method.
Background technique
In technical field of phase change energy storage, phase-change material be basis, therefore, first have to research and development latent heat of phase change it is big, property
It can the stable and high phase-change material of cost performance.There are many type of phase-change material, from the point of view of the mode of phase transformation, can be divided into solid-solid,
Four major class of solid-liquid, liquid-gas and solid-gas phase-change material, since solid-gas and liquid-gas phase-change material are adjoint a large amount of in phase transition process
The presence of gas makes material volume variation very greatly, therefore, although their latent heats of phase change are larger, seldom application in practice.?
In practical application, phase-change material is divided into organic species (paraffin, fatty acid etc.) by the general difference for pressing materials chemistry constituent
With inorganic species (inorganic hydrated salt, fuse salt, metal etc.).Inorganic hydrated salt be in, one kind important in low-temperature phase-change material,
Provide nearly 70 kind alternative phase-change material of the fusing point from several degrees Celsius to more than 100 degrees Celsius.
Inorganic hydrated salt has many advantages, such as that use scope is wide, cheap, unit volume thermal storage density is big.But there is also not
Foot place: supercooling, mutually separation and heat conduction efficiency are relatively low.These defects be directly related to phase-change material service efficiency and
Service life, therefore the key in terms of preferably solving these problems as phase-change material application study.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Inorganic phase change energy storage material, the materials
Energy is stable, cheap, abundant raw material, preparation is convenient, latent heat of phase change is big, nontoxic, thermal conductivity is high, allows to be widely applied
In multiple fields such as solar energy low-temperature heat accumulating system, the daily heat preservation of family, domestic hot water's energy-storage systems.
In order to achieve the above objectives, present invention employs the following technical solutions:
A kind of Inorganic phase change energy storage material, the energy storage material includes following components: 94-97 parts of energy storage basis material, function
It can 0.2-1.0 parts of additive, 2.0-3.5 parts of nucleating agent, 0.8-1.5 parts of surfactant.
Preferably, the energy storage basis material be selected from calcium chloride hexahydrate, calcium chloride hexahydrate and magnesium chloride hexahydrate eutectic salts,
One of calcium chloride hexahydrate and the eutectic salts of four water-calcium nitrate.
Preferably, the functional additive is oxidation expanded graphite.The oxidation expanded graphite can be common oxidizing process
The oxidation expanded graphite of preparation or the oxidation expanded graphite of modified Hummer method preparation.
Preferably, the nucleating agent is at least one of six water strontium chlorides, strontium carbonate and borax.
Preferably, the surfactant is neopelex, cetyl trimethylammonium bromide or dodecane
Base sodium sulfonate.
The present invention also provides a kind of preparation methods of Inorganic phase change energy storage material, the described method comprises the following steps:
1) energy storage basis material and nucleating agent are weighed in proportion, 40~50 DEG C of heating stirrings under air-proof condition, until complete
It melts；
2) surfactant is added after melting, ultrasonic disperse forms stable emulsion；
3) functional additive is added in stable emulsion, stirs to obtain Inorganic phase change energy storage material.
Preferably, the energy storage basis material be selected from calcium chloride hexahydrate, calcium chloride hexahydrate and magnesium chloride hexahydrate eutectic salts,
One of calcium chloride hexahydrate and the eutectic salts of four water-calcium nitrate.
Preferably, the functional additive is oxidation expanded graphite.
Preferably, the nucleating agent is at least one of six water strontium chlorides, strontium carbonate and borax.
Preferably, the surfactant is neopelex, cetyl trimethylammonium bromide or dodecane
Base sodium sulfonate.
Compared with the prior art, the invention has the advantages that:
1) functional additive is added in the present invention during the preparation process, can further decrease or eliminate on the basis of nucleating agent
Its degree of supercooling accelerates the heat transfer of phase-change material at the same time it can also promote the thermal conductivity of phase-change material.In addition, in surface-active
Under the interaction of agent, the phenomenon of phase separation of phase-change material can be prevented, repeatability preferably, stablize by performance, can be used for a long time, have
Have wide practical use.
2) functional additive type of the present invention is less, and contained ratio is smaller, and avoid that additive excessively interacts asks
Topic, the stability of guarantee system.
3) present invention has 20-29 DEG C of phase transition temperature, and degree of supercooling is less than 2 DEG C, and potential heat value with higher, has
Excellent heat-conductive characteristic, while there is high phase transformation stability.
4) raw material sources of the present invention are abundant, nontoxic, corrosion-free, preparation method is simple to operation, are easy to encapsulate.
Specific embodiment
The present invention is further elaborated below by part embodiment, but the contents of the present invention cannot be limited.
Embodiment 1
1) energy storage basis material (CaCl is weighed in proportion2·6H2O) 95 parts, nucleating agent (SrCl2·6H2O) 3.0 parts,
(40~50 DEG C) heating stirring under air-proof condition, until melting completely；
2) 1.0 parts of surfactants (neopelex, SDBS), ultrasonic disperse are added thereto after melting
30min forms stable emulsion；
3) be added in stable emulsion 1.0 parts of functional additives (modified Hummer method institute oxygenerating expanded graphite,
EGO), stirring 30min obtains Inorganic phase change energy storage material；
4) gained phase-changing energy storage material is poured into container and is packaged test.
Test result:
Degree of supercooling is 0.6 DEG C；
Thermal conductivity is 1.832W/mK；
Latent heat of phase change value is 174.51J/g.
Embodiment 2
1) 94 parts of energy storage basis material (eutectic salts of calcium chloride hexahydrate and magnesium chloride hexahydrate), nucleating agent are weighed in proportion
3.5 parts of (strontium carbonate), (40~50 DEG C) heating stirring under air-proof condition, until melting completely；
2) 1.5 parts of surfactants (cetyl trimethylammonium bromide), ultrasonic disperse are added thereto after melting
30min forms stable emulsion；
3) be added in stable emulsion 1.0 parts of functional additives (modified Hummer method institute oxygenerating expanded graphite,
EGO), stirring 30min obtains Inorganic phase change energy storage material；
4) gained phase-changing energy storage material is poured into container and is packaged test.
Test result:
Degree of supercooling is 1.0 DEG C；
Thermal conductivity is 2.017W/mK；
Latent heat of phase change value is 109.76J/g.
Embodiment 3
1) 97 parts of energy storage basis material (eutectic salts of calcium chloride hexahydrate and four water-calcium nitrate), nucleating agent are weighed in proportion
2.0 parts of (borax), (40~50 DEG C) heating stirring under air-proof condition, until melting completely；
2) 0.8 part of surfactant (dodecyl sodium sulfate) is added thereto after melting, ultrasonic disperse 30min,
Form stable emulsion；
3) 0.2 part of functional additive (common oxidizing process institute oxygenerating expanded graphite, EGO) is added in stable emulsion,
Stirring 30min obtains Inorganic phase change energy storage material；
4) gained phase-changing energy storage material is poured into container and is packaged test.
Test result:
Degree of supercooling is 1.3 DEG C；
Thermal conductivity is 0.743W/mK；
Latent heat of phase change value is 117.42J/g.
Comparative example 1
1) example weighs energy storage basis material (CaCl in mass ratio2·6H2O) 96 parts, nucleating agent (SrCl2·6H2O) 3 parts,
(40~50 DEG C) heating stirring under air-proof condition, until melting completely；
2) 1 part of surfactant (neopelex, SDBS), ultrasonic disperse are added thereto after melting
30min forms stable emulsion；
3) 1.2 parts of functional additives (oxidation expanded graphite, EGO) is added in stable emulsion, stirring 30min obtains inorganic
Phase-changing energy storage material；
4) gained phase-changing energy storage material is poured into container and is packaged test.
The results show that improving containing for functional additive (oxidation expanded graphite, EGO) in the case where respective components are constant
Amount, the degree of supercooling by phase-change material known to cooling curve test are 3.4 DEG C, and degree of supercooling increases, and the reality for being unfavorable for material is answered
With.Show in the phase-changing energy storage material system content of functional additive (oxidation expanded graphite, EGO) should control 0.2~
Within 1.0 parts.
Comparative example 2
1) example weighs energy storage basis material (CaCl in mass ratio2·6H2O) 96 parts, nucleating agent (SrCl2·6H2O) 3 parts,
(40~50 DEG C) heating stirring under air-proof condition, until melting completely；
2) gained phase-changing energy storage material in above-mentioned (1) is poured into container and is packaged test.
In the case where energy storage basis material and nucleating agent constant rate, functional additive (oxidation expansion stone is not added
Ink, EGO) when, the degree of supercooling by phase-change material known to cooling curve test is 2.8 DEG C, and thermal conductivity test is 0.314W/m
K, latent heat of phase change value are 158.97J/g.The addition of functions additive (oxidation expanded graphite, EGO), to a certain extent may be used
To further decrease the degree of supercooling of phase-change material, while the thermal conductivity of phase-change material can also be improved, improve the storage of phase-change material
Hot property.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (2)
1. a kind of Inorganic phase change energy storage material, which is characterized in that the energy storage material is composed of the following components: energy storage basis material
94-97 parts, 0.2-1.0 parts of functional additive, 2.0-3.5 parts of nucleating agent, 0.8-1.5 parts of surfactant；The energy storage matrix
Material is selected from being total to for calcium chloride hexahydrate, the eutectic salts of calcium chloride hexahydrate and magnesium chloride hexahydrate, calcium chloride hexahydrate and four water-calcium nitrate
One of brilliant salt；The functional additive is oxidation expanded graphite；The nucleating agent is six water strontium chlorides, strontium carbonate and borax
At least one of；The surfactant is neopelex, cetyl trimethylammonium bromide or dodecyl
Sodium sulfonate.
2. a kind of preparation method of Inorganic phase change energy storage material described in claim 1, the described method comprises the following steps:
1) energy storage basis material and nucleating agent are weighed in proportion, 40~50 DEG C of heating stirrings under air-proof condition, until melting completely；
2) surfactant is added after melting, ultrasonic disperse forms stable emulsion；
3) functional additive is added in stable emulsion, stirs to obtain Inorganic phase change energy storage material.
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| CN106532024B (en) * | 2016-12-10 | 2019-02-22 | 浙江大学 | Graphene supports the preparation method of the negative electrode material of the lithium ion battery of nanometer boron |
| CN106978144A (en) * | 2017-03-20 | 2017-07-25 | 新奥泛能网络科技股份有限公司 | A kind of composite phase-change material and preparation method thereof and a kind of construction material |
| CN107686719B (en) * | 2017-09-20 | 2020-07-24 | 中国科学院青海盐湖研究所 | High-thermal-conductivity hydrated salt phase-change material and preparation method thereof |
| CN113429939B (en) * | 2021-06-23 | 2022-12-02 | 杭州鲁尔新材料科技有限公司 | Low super-cooling degree inorganic salt phase change energy storage material |
| CN113372884A (en) * | 2021-06-30 | 2021-09-10 | 中国地质大学（北京） | Expanded graphite composite inorganic hydrated salt phase-change material and preparation method thereof |
| CN114058339A (en) * | 2021-12-09 | 2022-02-18 | 中国科学院青海盐湖研究所 | High-thermal-conductivity hydrated nitrate composite phase-change material and preparation method thereof |
| CN114836177B (en) * | 2022-06-13 | 2023-08-22 | 西安建筑科技大学 | Method for improving thermal performance of eutectic hydrated salt phase change material and modified product thereof |
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| CN103205242A (en) * | 2013-05-07 | 2013-07-17 | 中国科学院青海盐湖研究所 | Phase change energy storage material for heat preservation at night and preparation method |
| CN104087254A (en) * | 2014-07-29 | 2014-10-08 | 江苏启能新能源材料有限公司 | High-heat-conductivity inorganic phase-change energy storage material |
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