CN108997976A - A kind of enhanced thermal conduction Inorganic phase change energy storage material and preparation method thereof - Google Patents
A kind of enhanced thermal conduction Inorganic phase change energy storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of enhanced thermal conduction Inorganic phase change energy storage materials, it is made of as core material and the melamine resin for containing nano heat-conductive enhancing particle as wall material inorganic phase-changing material, the nano heat-conductive enhancing particle is boron nitride modified, carbon nanotube and graphene oxide.Preparation method includes: the modification of 1) nano heat-conductive enhancing particle；2) preparation of the wall material prepolymer of nano heat-conductive enhancing particle of the addition Jing Guo modification；3) fusing of inorganic phase-changing material；4) preparation of enhanced thermal conduction Inorganic phase change energy storage material.The invention has the following advantages that 1) hot corresponding speed is fast, i.e., heat-conductive characteristic is high；2) storage density is big；3) there is good thermal cycling stability；4) materials safety, nontoxic, is not easy the technical characterstic revealed.Therefore, the present invention has more excellent thermal conductivity and stability, improves energy use efficiency, has broad application prospects.
Description
Technical field
The present invention relates to organic high molecular compound its preparation or chemical process technology field in phase-change material technical field,
Specifically a kind of enhanced thermal conduction Inorganic phase change energy storage material and preparation method thereof.
Technical background
With the development of economy with the progress of science and technology, traditional energy consumes at an amazing speed, and the mankind are faced with
Unprecedented energy shortage problem.There are two the Basic Ways for solving this problem: first is that exploitation renewable energy；Second is that mentioning
High-energy source service efficiency.Therefore, the storage of energy is particularly important.Thermal energy storage system provides possibility for energy storage, and
Latent heat storage is thermal energy storage most effective way.Phase-changing energy storage material (Phase Change Material, PCM) is benefit
With heat absorption and exothermic character of the substance in phase transition process, carries out heat storage and temperature adjusts the material of control, help to mention
High-energy source service efficiency is a very active forward position research direction in energy science and materials science field in recent years.
The phase transition process of phase-change material is carried out in capsule, externally remains solid-state, can effectively solve phase transformation storage
The leakage of energy material, mutually separation and corrosion problems, improve the stability and durability of phase transformation core material, are conducive to improve phase transformation
The application performance of material.Wall material used by phase-changing energy storage material uses melamine resin, can effectively wrap up phase change material inside, but
It is limited to the characteristic of organic matter, heating conduction is to be improved.Such generally existing thermal response rates of phase-change material are slower not
Foot, limits it in the application in higher field.
Therefore, technical problem of the existing technology is the heat-conductive characteristic for needing to improve phase-change material, to improve micro-
The durability and thermal stability of capsule composite phase-change energy storage material in use.
It is huge for the specific surface area faced blocks material of nano material, therefore adds minimal amount of nano material and arrive
Great interface and huge heat conduction network can be generated in matrix, and nano heat-conductive particle has stronger heating conduction, it can
Increase the thermal stability and heating conduction of material.
The study found that boron nitride has special layer structure and biggish specific surface area, durability is good and adsorption capacity
Greatly, and thermal coefficient is up to 400 W/(m K), it is a kind of material of potential application.Meanwhile boron nitride nanosheet is with huge
Heat transfer area can effectively reduce its interface resistance between polymer, and its chemical stability is good, heat-resist, is conducive to improve
The heating conduction of composite phase-change energy storage material for microcapsule, thermal response rates and apply persistence.But boron nitride is in chemical inertness,
Reactivity is low, therefore need to modify boron nitride, improves its dispersibility and the compatibility with resin matrix.
Carbon nanotube is made of the graphite flake crimped, to have the characteristics that graphite guide heating rate height and huge draw ratio.Through
It calculates, when temperature is 100K, the thermal conductivity of single-root carbon nano-tube is 37000 W/mK, 6600 W/mK can be reached at room temperature, this
One data are almost 2 times of thermal conductivity (3320 W/mK) under reported Diamond at Room Temperature.
Two scientists of Britain in 2004 have found new carbon family member-graphene.By to the further of graphene
Understand discovery: graphene is nano material most thin, most hard in the world today, has the good transparency and lipophilicity, leads
Hot coefficient is up to 5300 W/mK.The structure of its derivative graphene oxide is similar with graphene, still maintains layer structure,
Different to be, the surface of graphene oxide has a variety of oxygen-containing functional groups, such as hydroxyl, has preferable hydrophily.
Expanded graphite also has good heating conduction.
Above-mentioned material has preferable compatibility with the synthon of wall material melamine resin after modified.
Summary of the invention
The present invention technical problem low for thermal coefficient of the existing technology, provides a kind of enhanced thermal conduction organic phase-change
Energy storage material and preparation method thereof.
Realize that the technical solution of the object of the invention is as follows:
Enhanced thermal conduction Inorganic phase change energy storage material as core material and contains nano heat-conductive enhancing particle comprising inorganic phase-changing material
For melamine resin as wall material, the nano heat-conductive enhancing particle is boron nitride modified, carbon nanotube and graphite oxide
Alkene, the inorganic phase-changing material are sal glauberi, calcium chloride hexahydrate, four aqueous magnesium chlorides, epsom salt, ten phosphate dihydrates
Hydrogen sodium and washing soda Sodium acetate trihydrate.
The preparation method of enhanced thermal conduction Inorganic phase change energy storage material, comprising the following steps:
Step 1, the modification of nano heat-conductive enhancing particle, when nano heat-conductive enhancing particle is boron nitride, modification
Method is that boron nitride is added to soda lye, after high temperature bath, is filtered, dry；The nano heat-conductive enhances particle
When carbon nanotube, the method for modification is after carbon nanotube to be added to concentrated sulfuric acid mixing, to add concentrated nitric acid mixing
Stirring, reacts under the conditions of 130 DEG C, through cooling, dilutes, filters, dry；The nano heat-conductive enhancing particle is graphene oxide
When, the method for modification is the mixed solution that natural graphite is added to potassium permanganate, the concentrated sulfuric acid and concentrated phosphoric acid, in 80 DEG C of items
It is reacted under part, hydrogen peroxide is added after being cooled to room temperature after solution becomes faint yellow, is washed in turn with hydrochloric acid and distilled water
It washs after neutral, it is dry；
Step 2, the preparation of the wall material prepolymer of nano heat-conductive enhancing particle of the addition Jing Guo modification, nano heat-conductive is enhanced
Particle is mixed with the monomeric melamines of melamine resin and formaldehyde, is ultrasonically formed prepolymer；
Step 3, the fusing of inorganic phase-changing material is heated straight after mixing inorganic phase-changing material with the nucleating agent of its mass fraction 1%
It is completely melt to inorganic phase-changing material；
Step 4, the preparation of enhanced thermal conduction Inorganic phase change energy storage material, by the inorganic phase-changing material of fusing obtained by step 3 to be added dropwise
Speed is to react in 2 mL/min addition step 2 gained prepolymer, and process is added dropwise and reaction process carries out magnetic agitation, can obtain
To enhanced thermal conduction Inorganic phase change energy storage material.
Compared to the prior art, advantageous effects through experimental tests of the invention discovery:
1) hot corresponding speed is fast, i.e., heat-conductive characteristic is high；
2) storage density is big, range of the heat accumulation latent heat of phase change up to 130 ~ 190 J/g；
3) there is good thermal cycling stability, 20 DSC thermal cycles are carried out to it, hot property is held essentially constant；
4) by carrying out the polymerization of wall material while addition inorganic phase-changing material, phase-change material effectively can be sealed in melamine
Inside resin, the leakage of phase-change material is prevented；
5) materials safety, nontoxic, corrosion-free and preparation process is simple, low in cost.
Therefore, the present invention has more excellent thermal conductivity and stability compared with prior art, improves the energy and uses effect
Rate has broad application prospects.
Detailed description of the invention
Fig. 1 is the enhanced thermal conduction Inorganic phase change energy storage material DSC figure in embodiment 1；
Fig. 2 is the enhanced thermal conduction Inorganic phase change energy storage material DSC figure in embodiment 2；
Fig. 3 is the enhanced thermal conduction Inorganic phase change energy storage material DSC figure in embodiment 3.
Specific embodiment
The present invention is described in further detail the content of present invention below in conjunction with Figure of description, by embodiment, but not
It is limitation of the invention.
Embodiment 1
The preparation method of enhanced thermal conduction Inorganic phase change energy storage material:
Step 1, boron nitride, is added 60% sodium hydroxide solution, in 90 DEG C of conditions by the modification of nano heat-conductive enhancing particle
It is filtered after lower 2 h of water-bath, dry 20 h under the conditions of 90 DEG C；
Step 2, the preparation of the wall material prepolymer of nano heat-conductive enhancing particle of the addition Jing Guo modification, nano heat-conductive is enhanced
Particle is mixed with the monomeric melamines of melamine resin and formaldehyde, is ultrasonically formed prepolymer；
Step 3, the fusing of inorganic phase-changing material is heated straight after mixing inorganic phase-changing material with the nucleating agent of its mass fraction 1%
It is completely melt to inorganic phase-changing material；
Step 4, the preparation of enhanced thermal conduction Inorganic phase change energy storage material, by the inorganic phase-changing material of fusing obtained by step 3 to be added dropwise
Speed is to react in 2 mL/min addition step 2 gained prepolymer, and process is added dropwise and reaction process carries out magnetic agitation, can obtain
To enhanced thermal conduction Inorganic phase change energy storage material.
Gained enhanced thermal conduction organic phase change energy storage material is through DSC measuring, as a result as shown in Figure 1, latent heat of phase change 184.0
J/g。
Embodiment 2
The preparation method of enhanced thermal conduction Inorganic phase change energy storage material:
Not specified step is same as Example 1, the difference is that: step 1, nano heat-conductive enhances at the modification of particle
Reason, after 50 mL concentrated sulfuric acids mixing magnetic agitation 30min is added in 1.2 grams of carbon nanotubes, ultrasonic 2h adds 50mL concentrated nitric acid
Magnetic agitation 30min is mixed, reacts 2h under the conditions of 130 DEG C, through cooling, dilutes, filters, it is dry.
Gained enhanced thermal conduction organic phase change energy storage material is through DSC measuring, as a result as shown in Fig. 2, latent heat of phase change 137.9
J/g。
Embodiment 3
The preparation method of enhanced thermal conduction Inorganic phase change energy storage material:
Not specified step is same as Example 1, the difference is that: step 1, nano heat-conductive enhances at the modification of particle
The mixed solution of 20 grams of potassium permanganate, the 350mL concentrated sulfuric acid and 50mL concentrated phosphoric acid is added, in 80 DEG C of conditions in 3 grams of natural graphites by reason
Lower reaction 10h adds the hydrogen peroxide of 5mL 30% after solution becomes faint yellow, with hydrochloric acid and steaming after being cooled to room temperature
Hereafter distilled water washs 3 in turn, dry under the conditions of 90 DEG C.
Gained enhanced thermal conduction organic phase change energy storage material is through DSC measuring, as a result as shown in figure 3, latent heat of phase change 167.6
J/g。
Claims (8)
1. a kind of enhanced thermal conduction Inorganic phase change energy storage material, comprising inorganic phase-changing material as core material and melamine resin as wall
Material, it is characterised in that: the melamine resin contains nano heat-conductive enhancing particle.
2. phase-changing energy storage material according to claim 1, it is characterised in that: the nano heat-conductive enhancing particle is to pass through
Modified boron nitride, carbon nanotube and graphene oxide.
3. phase-changing energy storage material according to claim 1, it is characterised in that: the inorganic phase-changing material is ten water sulfuric acid
Sodium, calcium chloride hexahydrate, four aqueous magnesium chlorides, epsom salt, ten hydrogen phosphate dihydrate sodium and washing soda Sodium acetate trihydrate.
4. the preparation method of enhanced thermal conduction Inorganic phase change energy storage material according to claim 1, it is characterised in that including with
Lower step:
Step 1, the modification of nano heat-conductive enhancing particle；
Step 2, the preparation of the wall material prepolymer of nano heat-conductive enhancing particle of the addition Jing Guo modification, nano heat-conductive is enhanced
Particle is mixed with the monomeric melamines of melamine resin and formaldehyde, is ultrasonically formed prepolymer；
Step 3, the fusing of inorganic phase-changing material is heated straight after mixing inorganic phase-changing material with the nucleating agent of its mass fraction 1%
It is completely melt to inorganic phase-changing material；
Step 4, the preparation of enhanced thermal conduction Inorganic phase change energy storage material, by the inorganic phase-changing material of fusing obtained by step 3 to be added dropwise
Speed is to react in 2 mL/min addition step 2 gained prepolymer, and enhanced thermal conduction Inorganic phase change energy storage material can be obtained.
5. the preparation method according to claim 4, it is characterised in that: it is nitridation that nano heat-conductive described in step 1, which enhances particle,
Boron, the method for modification is that boron nitride is added to soda lye, after high temperature bath, is filtered, dry.
6. the preparation method according to claim 4, it is characterised in that: the enhancing particle of nano heat-conductive described in step 1 is received for carbon
Mitron, the method for modification are after carbon nanotube to be added to concentrated sulfuric acid mixing, to add concentrated nitric acid mixing,
It is reacted under the conditions of 130 DEG C, through cooling, dilutes, filter, it is dry.
7. the preparation method according to claim 4, it is characterised in that: it is oxidation that nano heat-conductive described in step 1, which enhances particle,
Graphene, the method for modification is the mixed solution that natural graphite is added to potassium permanganate, the concentrated sulfuric acid and concentrated phosphoric acid, 80
It is reacted under the conditions of DEG C, hydrogen peroxide is added after being cooled to room temperature after solution becomes faint yellow, with hydrochloric acid and distillation water wheels
Stream washing is dry after neutral.
8. the preparation method according to claim 4, it is characterised in that: dropwise addition process and reaction process described in step 4 carry out
Magnetic agitation.
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| CN109913178A (en) * | 2019-03-19 | 2019-06-21 | 北京服装学院 | A kind of preparation method of the modified phase-change microcapsule material of graphene |
| CN110157385A (en) * | 2019-06-10 | 2019-08-23 | 常州港华燃气有限公司 | It is a kind of using modified resin as the phase-transition heat-storage particle and its preparation process of shell material |
| CN111013509A (en) * | 2019-12-11 | 2020-04-17 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN111662688A (en) * | 2020-07-01 | 2020-09-15 | 桂林电子科技大学 | Boron nitride/graphene double-heat-conduction-base aerogel composite phase-change material and preparation method thereof |
| WO2020253094A1 (en) * | 2019-06-17 | 2020-12-24 | 中国科学院深圳先进技术研究院 | Boron nitride nanotube aerogel/phase change heat conductive composite material and preparation method therefor |
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| CN114806513A (en) * | 2022-06-28 | 2022-07-29 | 忻州师范学院 | Carbon-based phase-change energy storage material for direct solar-thermal conversion and preparation method thereof |
| CN115947982A (en) * | 2023-01-06 | 2023-04-11 | 温州荟养生物科技有限公司 | Aloe cold-storage heat-conduction elastomer and preparation method and application thereof |
| CN116814223A (en) * | 2023-06-09 | 2023-09-29 | 东莞理工学院 | Modified boron nitride stable hydrated salt/organic phase change material reverse Pickering emulsion and preparation method thereof |
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| CN106085368A (en) * | 2016-06-22 | 2016-11-09 | 桂林电子科技大学 | Composite phase-change energy storage material for microcapsule that a kind of nano heat-conductive strengthens and preparation method thereof |
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Patent Citations (1)
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| CN106085368A (en) * | 2016-06-22 | 2016-11-09 | 桂林电子科技大学 | Composite phase-change energy storage material for microcapsule that a kind of nano heat-conductive strengthens and preparation method thereof |
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| CN109913178A (en) * | 2019-03-19 | 2019-06-21 | 北京服装学院 | A kind of preparation method of the modified phase-change microcapsule material of graphene |
| CN110157385A (en) * | 2019-06-10 | 2019-08-23 | 常州港华燃气有限公司 | It is a kind of using modified resin as the phase-transition heat-storage particle and its preparation process of shell material |
| WO2020253094A1 (en) * | 2019-06-17 | 2020-12-24 | 中国科学院深圳先进技术研究院 | Boron nitride nanotube aerogel/phase change heat conductive composite material and preparation method therefor |
| CN111013509B (en) * | 2019-12-11 | 2021-08-10 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN111013509A (en) * | 2019-12-11 | 2020-04-17 | 中国科学院化学研究所 | Inorganic salt phase change energy storage microcapsule and preparation method and application thereof |
| CN111662688A (en) * | 2020-07-01 | 2020-09-15 | 桂林电子科技大学 | Boron nitride/graphene double-heat-conduction-base aerogel composite phase-change material and preparation method thereof |
| CN112920604A (en) * | 2021-02-07 | 2021-06-08 | 许鹏天 | Method for preparing heat dissipation film based on large-sheet-diameter graphene oxide |
| CN114610132A (en) * | 2022-03-25 | 2022-06-10 | 武汉东湖学院 | Computer CPU cooling system combining air cooling and phase-change material |
| CN114610132B (en) * | 2022-03-25 | 2022-11-15 | 武汉东湖学院 | Computer CPU cooling system combining air cooling and phase-change material |
| CN114806513A (en) * | 2022-06-28 | 2022-07-29 | 忻州师范学院 | Carbon-based phase-change energy storage material for direct solar-thermal conversion and preparation method thereof |
| CN115947982A (en) * | 2023-01-06 | 2023-04-11 | 温州荟养生物科技有限公司 | Aloe cold-storage heat-conduction elastomer and preparation method and application thereof |
| CN115947982B (en) * | 2023-01-06 | 2023-08-18 | 温州荟养生物科技有限公司 | Aloe cold-storage heat-conduction elastomer and preparation method and application thereof |
| CN116814223A (en) * | 2023-06-09 | 2023-09-29 | 东莞理工学院 | Modified boron nitride stable hydrated salt/organic phase change material reverse Pickering emulsion and preparation method thereof |
| CN116814223B (en) * | 2023-06-09 | 2023-12-26 | 东莞理工学院 | Modified boron nitride stable hydrated salt/organic phase change material reverse Pickering emulsion and preparation method thereof |
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