CN103468216A - Phosphate inorganic nano phase change energy storage material and preparation method thereof - Google Patents
Phosphate inorganic nano phase change energy storage material and preparation method thereof Download PDFInfo
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- CN103468216A CN103468216A CN2013103872816A CN201310387281A CN103468216A CN 103468216 A CN103468216 A CN 103468216A CN 2013103872816 A CN2013103872816 A CN 2013103872816A CN 201310387281 A CN201310387281 A CN 201310387281A CN 103468216 A CN103468216 A CN 103468216A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 50
- 239000011232 storage material Substances 0.000 title claims abstract description 41
- 230000008859 change Effects 0.000 title claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 13
- 239000010452 phosphate Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000011162 core material Substances 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000741 silica gel Substances 0.000 claims abstract description 7
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002775 capsule Substances 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 235000019800 disodium phosphate Nutrition 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012782 phase change material Substances 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 239000004566 building material Substances 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000004087 circulation Effects 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910001629 magnesium chloride Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to a phosphate inorganic nano phase change energy storage material and a preparation method thereof, and belongs to the technical field of building low carbon and energy saving. The phosphate nano phase change energy storage material is prepared by taking silica gel, zirconium oxide and manganese dioxide powder which are hydrolyzed by ethyl orthosilicate, zirconium n-butoxide and manganous nitrate as a nano rubber power wall material, taking disodium hydrogen phosphate Na2HPO4.12H2O as a nano inorganic salt hydrate core material, and encapsulating the core material with the wall material. The phase change temperature is 34.6 DEG C; the capsule property is stable; and the phase change temperature is very suitable for a household phase change energy storage material.
Description
Technical field
The invention belongs to building low-carbon energy-saving technical field, specifically a kind of phosphate inorganic nano phase change energy storage material and preparation method thereof.
Background technology
In physical environment, produce a large amount of heats every day, as: sun power, animal body loses heat, the combustion heat, heat of friction, object running heat etc.Phase-changing energy storage material is in the process undergone phase transition at itself, absorbs the material of these heats, and to environment, discharges when needed, and reach, controls ambient temperature and energy-conservation purpose.By its chemical constitution, can be divided into: organic phase change energy storage material, combined phase-change energy storage material and inorganic-phase variable energy storage material.Organic phase change energy storage material has that chemical stability is good, suitable phase transition temperature, without the advantage such as being separated, yet the organic phase change energy storage material thermal conductivity is lower, causes its heat transfer property in the application of accumulator system poor, thereby reduced the usefulness of system; The combined phase-change energy storage material has advantages of adjustable within the specific limits, but easily aging, through just losing the energy storage effect after circulation several times; The inorganic-phase variable energy storage material has that use range is wide, thermal conductivity is large, heat of fusion than large, the storage heat density is large, the advantages such as the phase transformation volume change is little, toxicity is little, low price, firmly get people's favor, therefore the preparation of the inorganic energy storage material of this class and to be applied in the patent application aspect more and more, as: " a kind of preparation technology of organic salt/ceramic base high temperature phase-changing energy-storing material ", application number 200510120619.7; " a kind of inorganic-phase variable energy storage material ", application number 201210037753; " a kind of preparation technology of organic salt/ceramic base high temperature phase-changing energy-storing material ", application number CN200810065301.7; " a kind of high-performance medium-temperature inorganic-phase variable energy storage material and preparation method thereof ", application number 201210557115 etc.There is cold, non-homogeneous melting and the phenomenon such as be separated usually in the inorganic-phase variable energy storage material, caused not energy storage should energy storage the time, should discharge can the time do not discharge can, obvious layering, the large lossy of enthalpy of phase change appear in system.In order to address the above problem, the contriver puts forward various plans, and as " a kind of heat-storage medium and uses thereof ", application number 200610104583.8, propose magnesium nitrate, and magnesium chloride and water form the salt water chemical compound of eutectic, " a kind of inorganic-phase variable energy storage material ", application number 201210037753.0, adopt and add nucleator and dispersion agent in inorganic salt hydrate, " a kind of preparation method of inorganic hydrous salt phase transition energy-storing material ", application number 200810065301.7, employing adds in inorganic salt hydrate prevented the cryogen sodium tetraborate, although these methods have some effects, but also be confined to some system, there is certain limitation at the phase-changing energy storage material choice and operation, the inventor studies discovery, the inorganic salt hydrate phase-changing energy storage material is distributed to nano_scale particle, be rolled into capsule of nano, can solve well the mistake cold-peace problem of phase separation of phase-changing energy storage material, the contriver develops a series of nano inorganic phase-changing energy storage materials according to this discovery and design, the present invention is exactly one of this inorganic-phase variable energy storage material of exploitation.
Summary of the invention
The object of the invention is to the inorganic salt hydrate phase-changing energy storage material is distributed to nano_scale particle, and be wrapped in capsule of nano, overcome the mistake cold-peace problem of phase separation of phase-changing energy storage material, develop a series of inorganic-phase variable energy storage materials unlike the prior art, meet different insulations, heat insulation, energy storage, the requirement of temperature adjustment object to different inorganic phase-changing material performances.
A kind of phosphate inorganic nano phase change of the present invention energy storage material is to do the wall material with the inorganic nano rubber powder, make core with the nano inorganic hydrous salt phase change material, form the inorganic nano energy storage material by nanometer rubber powder wall material parcel nano inorganic salt hydrate phase change material core, the indication inorganic adhesive powder is by tetraethoxy, silica gel, zirconium white, manganese dioxide powder that tetrabutyl zirconate and manganous nitrate hydrolysis form, amount to into oxide compound and meet SiO
2/ ZrO
2/ MnO
2intermolecular ratio is 2: 0.5: 1, and the nano inorganic salt hydrate of indication is Sodium phosphate dibasic Na
2hPO
412H
2o, the weight ratio of wall material and core is 6: 4, product yardstick 80 nanometers, 34.6 ℃ of transformation temperatures; The cooling curve proof is without crossing the cold-peace problem of phase separation; Energy storage density 260J/g; The capsule stable in properties, insoluble in PH5-9 solution, after carrying out 80 high temperature trickle circulations and heating freeze cycle 25 times, mass loss is less than 1%; Do not find that cold-peace was separated.
The preparation method of a kind of phosphate inorganic nano phase change of the present invention energy storage material follows these steps to processing successively:
(1) get industrial raw material 12 water Sodium phosphate dibasics and add water and be mixed with saturated aqueous solution, remove by filter impurity, filtrate adds the long-pending dehydrated alcohol of diploid, stirs, and obtains nano-scale phase-changing Na
2hPO
412H
2o core precipitation;
(2) take tetraethoxy, tetrabutyl zirconate and manganous nitrate, amount to into oxide compound and meet SiO
2/ ZrO
2/ MnO
2between minute, ratio is 2: 0.5: 1;
(3) step (2) is taken to thing and add one by one step (1), the limit edged stirs, and step (2) gained oxide compound gross weight and step (1) raw material weight ratio are 6: 4;
(4) mixture of step (3) is stirred to 1-3 hour at the 600-1000r/min rotating speed, make nanometer wall material silica gel, zirconium white, Manganse Dioxide by nanometer core material Na
2hPO
412H
2o is wrapped up;
(5) centrifuge dehydration, solid drying is product.
Filtrate Distillation recovery ethanol after above-mentioned steps (5) centrifuge dehydration separates.
The application of a kind of phosphate inorganic nano phase change of the present invention energy storage material is to design time application for building materials according to parameter provided by the invention.Be mainly used in sandwich boards for construction, building materials weighting agent or be processed into the section bar temperature of going bail for, heat insulation, energy storage is used.
The principle of the invention is with nano grade inorganic phase change material 12 water Sodium phosphate dibasic Na
2hPO
412H
2o is core, and with tetraethoxy, nano level silica gel is produced in tetrabutyl zirconate and manganous nitrate hydrolysis, and zirconium white and Manganse Dioxide are as the wall material, by nano level rubber powder wall material parcel nanometer grade inorganic salt phase-changing energy storage material 12 water Sodium phosphate dibasic Na
2hPO
412H
2o, overcome phase-changing energy storage material 12 water Sodium phosphate dibasic Na
2hPO
412H
2that O exists is excessively cold, layering and the problems such as be separated, thereby makes it to become stable phase-changing energy storage material, and as house insulation, lagging material, due to 12 water Sodium phosphate dibasic Na
2hPO
412H
2o can separate out Na more than 30 ℃
2hPO
47H
2o, the whole course of processing is controlled at below 30 ℃ carries out.
The invention effect:
1. product transformation temperature of the present invention is 34.6 ℃, and storage density 160-500J/g is nontoxic, corrosion-free, is particularly suitable for the house insulation, heat insulation, energy storage, temperature adjustment.
2. Product Process of the present invention is simple, and the cost inferior quality is easily controlled, stable.
3. Reusability is without being separated.
4. the present invention, by rapid reaction, is dispersed into rapidly nano_scale particle by inorganic salt hydrate, and is wrapped up by aluminum phosphate, the inorganic salt crystal water is difficult for scattering and disappearing, the particulate molecular motion suffers restraints, and effectively controlled and crossed the phenomenon that cold-peace is separated, be a kind of good phase-changing energy storage material.
The accompanying drawing explanation
Fig. 1 is product fusing of the present invention--freezing curve, from scheming, and 34.6 ℃ of product transformation temperatures of the present invention.
Embodiment
Embodiment 1
Follow these steps to processing:
(1) get 400g industrial raw material 12 water Sodium phosphate dibasic Na
2hPO
412H
2o) add water and be mixed with saturated aqueous solution, remove by filter impurity, filtrate adds the long-pending dehydrated alcohol of diploid, stirs, and obtains nano-scale phase-changing Na
2hPO
412H
2o core precipitation;
(2) take tetraethoxy Si (OC
2h
5)
4317g, tetrabutyl zirconate Zr (0C
4h
9)
4146g and manganous nitrate 136.2g, amount to into oxide compound and meet SiO
2/ ZrO
2/mnO
2between minute, ratio is 2: 0.5: 1;
(3) step (2) is taken to thing and add one by one step (1), the limit edged stirs, and step (2) gained oxide compound gross weight and step (1) raw material weight ratio are 6: 4;
(4) mixture of step (3) is stirred 2 hours with the 600r/min rotating speed under 20 ℃ of conditions, make nanometer wall material silica gel, zirconium white, Manganse Dioxide by nanometer core material Na
2hPO
412H
2o is wrapped up;
(5) centrifuge dehydration, solid drying is product.Filtrate Distillation recovery ethanol.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any type of restriction, any disengaging technical solution of the present invention content, according to technical spirit of the present invention, above embodiment is done to any simple modification, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any type of restriction, any disengaging technical solution of the present invention content, according to technical spirit of the present invention, above embodiment is done to any simple modification, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (5)
1. a phosphate inorganic nano phase change energy storage material, it is characterized in that doing the wall material with the inorganic nano rubber powder, make core with the nano inorganic hydrous salt phase change material, form the inorganic nano energy storage material by nanometer rubber powder wall material parcel nano inorganic salt hydrate phase change material core, the indication inorganic adhesive powder is by tetraethoxy, silica gel, zirconium white, manganese dioxide powder that tetrabutyl zirconate and manganous nitrate hydrolysis form, amount to into oxide compound and meet SiO
2/ ZrO
2/ MnO
2intermolecular ratio is 2: 0.5: 1, and the nano inorganic salt hydrate of indication is Sodium phosphate dibasic Na
2hPO
412H
2o, the weight ratio of wall material and core is 6: 4, product yardstick 80 nanometers, 34.6 ℃ of transformation temperatures; The cooling curve proof is without crossing the cold-peace problem of phase separation; Energy storage density 260J/g; The capsule stable in properties, after carrying out 80 high temperature trickle circulations and heating freeze cycle 25 times, mass loss is less than 1%; Do not find that cold-peace was separated.
2. according to the preparation method of a kind of phosphate inorganic nano phase change energy storage material claimed in claim 1, it is characterized in that following these steps to successively processing:
(1) get industrial raw material 12 water Sodium phosphate dibasics and add water and be mixed with saturated aqueous solution, remove by filter impurity, filtrate adds the long-pending dehydrated alcohol of diploid, stirs, and obtains nano-scale phase-changing Na
2hPO
412H
2o core precipitation;
(2) take tetraethoxy, tetrabutyl zirconate and manganous nitrate, amount to into oxide compound and meet SiO
2/ ZrO
2/ MnO
2between minute, ratio is 2: 0.5: 1;
(3) step (2) is taken to thing and add one by one step (1), the limit edged stirs, and step (2) gained oxide compound gross weight and step (1) raw material weight ratio are 6: 4;
(4) mixture of step (3) is stirred to 1-3 hour at the 600-1000r/min rotating speed, make nanometer wall material silica gel, zirconium white, Manganse Dioxide by nanometer core material Na
2hPO
412H
2o is wrapped up;
(5) centrifuge dehydration, solid drying is product.
3. a kind of preparation method of phosphate inorganic nano phase change energy storage material according to claim 1, is characterized in that the centrifugate Distillation recovery ethanol after step (5) centrifuge dehydration separates.
4. a kind of application of phosphate inorganic nano phase change energy storage material according to claim 1, application while it is characterized in that designing for building materials according to parameter provided by the invention.
5. a kind of application of phosphate inorganic nano phase change energy storage material according to claim 1, is characterized in that being mainly used in sandwich boards for construction, building materials weighting agent or be processed into the section bar temperature of going bail for, and heat insulation, energy storage is used.
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| CN108484024A (en) * | 2018-03-09 | 2018-09-04 | 湖北工业大学 | A kind of preparation method of the early strong frost-resistant concrete of the micro-nano heat accumulation capsule of addition |
| CN109082267A (en) * | 2018-10-11 | 2018-12-25 | 上海第二工业大学 | A method of addition manganese dioxide particle improves n-octadecane/polystyrene phase microcapsules hot property |
| CN109135683A (en) * | 2018-08-22 | 2019-01-04 | 北京科技大学 | A method of preparing fused salt-ceramics phase-change heat-storage material |
| CN112375545A (en) * | 2020-11-16 | 2021-02-19 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107556970A (en) * | 2017-08-15 | 2018-01-09 | 河北炫坤节能科技股份有限公司 | A kind of phase-change microcapsule and preparation method of the coating hydrous salt of inorganic, metal oxide |
| CN108484024A (en) * | 2018-03-09 | 2018-09-04 | 湖北工业大学 | A kind of preparation method of the early strong frost-resistant concrete of the micro-nano heat accumulation capsule of addition |
| CN109135683A (en) * | 2018-08-22 | 2019-01-04 | 北京科技大学 | A method of preparing fused salt-ceramics phase-change heat-storage material |
| CN109135683B (en) * | 2018-08-22 | 2021-01-12 | 北京科技大学 | Method for preparing molten salt-ceramic phase change heat storage material |
| CN109082267A (en) * | 2018-10-11 | 2018-12-25 | 上海第二工业大学 | A method of addition manganese dioxide particle improves n-octadecane/polystyrene phase microcapsules hot property |
| CN112375545A (en) * | 2020-11-16 | 2021-02-19 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
| CN112375545B (en) * | 2020-11-16 | 2021-07-02 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
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| CN103468216B (en) | 2016-04-13 |
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