CN108997975A - A kind of enhanced thermal conduction MOFs phase-changing energy storage material and preparation method thereof - Google Patents
A kind of enhanced thermal conduction MOFs phase-changing energy storage material and preparation method thereof Download PDFInfo
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- CN108997975A CN108997975A CN201710423500.XA CN201710423500A CN108997975A CN 108997975 A CN108997975 A CN 108997975A CN 201710423500 A CN201710423500 A CN 201710423500A CN 108997975 A CN108997975 A CN 108997975A
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Abstract
The present invention provides a kind of enhanced thermal conduction MOFs phase-changing energy storage material, and the organic phase change energy storage material by containing nano heat-conductive enhancing particle is formed as core material and MOFs material as wall material.Preparation method includes: the emulsion process of 1) organic phase change material；2) process of organic phase change material of the MOFs material vacuum absorption containing nano particle；3) products obtained therefrom process after taking-up vacuum suction.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, corrosion-free and preparation process is simple, low-cost technical characterstic.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 MOFs phase-changing 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 traditional phase-changing energy storage material is porous material, specifically includes expanded perlite, concave-convex
Stick soil, expanded graphite, expanded vermiculite, porous aluminas, active carbon etc.；Core material used by phase-changing energy storage material is organic phase-change
Material specifically includes long chain fatty acids, polyalcohol, paraffin, n-octadecane etc..
Research is found: core material is the organic phase change material deficiency slower there are thermal response rates, limits it more polo-neck
The application in domain.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.
Expanded graphite also has good heating conduction.
Above-mentioned material has preferable compatibility with organic matter.
In terms of wall material, metal organic framework compound (MOFs) is as a kind of novel hybrid inorganic-organic materials, in recent years
Widely to be paid close attention to.MOFs is the nothing formed by way of self assembly by metal ion or ion cluster and organic ligand
Limit lattice.Just because of its unique property, for example, stable nano pore, high-specific surface area, uniform and adjustable aperture,
Functional duct, can the outstanding properties such as surface is modified, it is numerous to determine that it possesses in gas storage, catalysis, sensing and detaching direction
Using.Therefore, in terms of sample preparation, MOFs presents big advantage and potential application.[ACS. Appl Mater.
Interfaces, 2014 ,6(13), pp 10196–10204]。
Summary of the invention
The present invention technical problem low for thermal coefficient of the existing technology, provides a kind of enhanced thermal conduction MOFs phase transformation
Energy storage material and preparation method thereof.Using novel MOFs material, the excellent heating conduction of its metallic element is utilized.The object of the invention
It is on the one hand to utilize the heating conduction of nano heat-conductive enhancing particle enhancing core material；On the other hand, it is led using MOFs material is excellent
Hot property, instead of the wall material of conventional phase change material, to improve the heating conduction of organic phase change energy storage material.
Realize that the technical solution of the object of the invention is as follows:
Enhanced thermal conduction MOFs phase-changing energy storage material, by enhanced thermal conduction organic phase change material as core material, MOFs material is as wall
Material, the enhanced thermal conduction organic phase change material contains boron nitride, carbon nanotube, expanded graphite and graphene oxide leads as nanometer
The mass ratio of heat enhancing particle, nano heat-conductive enhancing particle and phase-change material is that organic phase change material described in 0.03 ~ 0.05:9 is
Long chain fatty acids, polyalcohol, paraffin, n-octadecane；The MOFs material is Pt-MOFs, Cu-MOFs, Zn-MOFs, Zr-
MOFs and Pd-MOFs.
The preparation method of enhanced thermal conduction MOFs phase-changing energy storage material the following steps are included:
Step 1, nano heat-conductive enhancing particle is mixed ultrasound with organic phase change material first by the emulsion process of organic phase change material
Dispersion, forms uniform dispersion liquid, then after mixing by the dispersion liquid and emulsifier, solvent, at 40 ~ 70 DEG C, 1000 ~
Stirring and emulsifying under the conditions of 1500 RMP forms the lotion of stable and uniform, obtains the organic phase change material containing nano particle；
Step 2, the process of organic phase change material of the MOFs material absorption containing nano particle, contains nanometer for what step 1 obtained
The organic phase change material of particle is mixed with MOFs material, by uniform stirring process, in vacuum oven, 50 DEG C of condition
The vacuum suction of lower progress；
Step 3, products obtained therefrom cooled to room temperature after step 2 is adsorbed is taken out, enhanced thermal conduction MOFs phase-change accumulation energy material is obtained
Material.
The step 2 first carries out MOFs before MOFs material adsorbs the process of the organic phase change material containing nano particle
It is dry under the conditions of 110 DEG C to be put into vacuum oven by the preprocessing process of material for MOFs 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 ~ 150 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) 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 MOFs phase-changing energy storage material DSC figure in embodiment.
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
The preparation method of enhanced thermal conduction organic phase change energy storage material:
Step 1, the emulsion process of organic phase change material, first by nano particle and organic phase change material mixing ultrasonic disperse 30
Min forms uniform dispersion liquid.Then after mixing by the dispersion liquid and emulsifier, solvent, at 40 ~ 70 DEG C, 1000 ~
2 h of stirring and emulsifying under the conditions of 1500 RMP, forms the lotion of stable and uniform, obtains the organic phase change material containing nano particle；
Step 2, the beaker of clean dried is taken, MOFs material is added, it is 30 minutes dry in 110 DEG C of baking ovens；
Step 3, the drying MOFs material that the organic phase change material and step 2 containing nano particle step 1 obtained obtains into
Row mixing, 10 min of ultrasonic disperse are uniformly mixed phase-change material with MOFs material, and sample after mixing is put into 50 DEG C of vacuum and is dried
Case, vacuumizes 8 hours, during which promotes MOFs material to phase transformation material with the sample in glass bar uniform stirring beaker every 2 hours
The abundant absorption of material；
Step 4, sample is taken out, cooled to room temperature is to get prepared enhanced thermal conduction MOFs phase-changing energy storage material.
Gained enhanced thermal conduction MOFs phase-changing energy storage material is through DSC measuring, as a result as shown in Figure 1, latent heat of phase change 150.7
J/g。
Claims (9)
1. a kind of enhanced thermal conduction MOFs phase-changing energy storage material, it is characterised in that: by enhanced thermal conduction organic phase change material as core
Material, for MOFs material as wall material, the enhanced thermal conduction organic phase change material 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 nitridation
Boron, carbon nanotube, expanded graphite and graphene oxide.
3. phase-changing energy storage material according to claim 1, it is characterised in that: the nano heat-conductive enhancing particle and phase transformation
The mass ratio of material is 0.03 ~ 0.05:9.
4. phase-changing energy storage material according to claim 1, it is characterised in that: the organic phase change material is long-chain fat
Acid, polyalcohol, paraffin, n-octadecane.
5. phase-changing energy storage material according to claim 1, it is characterised in that: the MOFs material is Pt-MOFs, Cu-
MOFs, Zn-MOFs, Zr-MOFs and Pd-MOFs.
6. the preparation method of enhanced thermal conduction MOFs phase-changing energy storage material according to claim 1, it is characterised in that including with
Lower step:
Step 1, nano heat-conductive enhancing particle is mixed ultrasound with organic phase change material first by the emulsion process of organic phase change material
Dispersion, forms uniform dispersion liquid, then after mixing by the dispersion liquid and emulsifier, solvent, at 40 ~ 70 DEG C, 1000 ~
Stirring and emulsifying under the conditions of 1500 RMP forms the lotion of stable and uniform, obtains the organic phase change material containing nano particle；
Step 2, the process of organic phase change material of the MOFs material absorption containing nano particle, contains nanometer for what step 1 obtained
The organic phase change material of particle is mixed with MOFs material, is adsorbed under certain condition；
Step 3, products obtained therefrom cooled to room temperature after step 2 is adsorbed is taken out, enhanced thermal conduction MOFs phase-change accumulation energy material is obtained
Material.
7. preparation method according to claim 6, it is characterised in that: the step 2, the absorption of MOFs material contain nanometer
Before the process of the organic phase change material of grain, the preprocessing process of MOFs material is first carried out, MOFs material is put into vacuum drying
Case is dry under the conditions of 110 DEG C.
8. preparation method according to claim 6, it is characterised in that: the step 2, the absorption of MOFs material contain nanometer
It further include uniform stirring process during the organic phase change material of grain.
9. preparation method according to claim 6, it is characterised in that: the step 2, the absorption of MOFs material contain nanometer
The condition of the process of the organic phase change material of grain is the vacuum suction that carries out under conditions of 50 DEG C in vacuum oven.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810675A (en) * | 2019-01-28 | 2019-05-28 | 华南理工大学 | A method of addition inorganic porous material generates setting to hydrous salt phase change material and adjusts phase transition temperature |
| CN110484213A (en) * | 2019-08-19 | 2019-11-22 | 苏州阿德旺斯新材料有限公司 | A kind of sizing MOF base composite phase-change material and its preparation method and application |
| CN112175238A (en) * | 2020-10-22 | 2021-01-05 | 安徽大学 | Preparation method of boron nitride nanosheet-carbon nanotube heat-conducting filler and heat-conducting composite material |
| CN112920778A (en) * | 2021-01-28 | 2021-06-08 | 北京科技大学 | Hierarchical pore metal organic framework composite phase change material and preparation method thereof |
| CN114852958A (en) * | 2022-06-02 | 2022-08-05 | 集美大学 | MOFs composite hydrogen storage material based on 3D printing, preparation method thereof and application thereof in marine hydrogen storage |
| CN115058231A (en) * | 2022-07-14 | 2022-09-16 | 塔里木大学 | Phase-change material taking MOFs as carrier and preparation method thereof |
| CN115418194A (en) * | 2022-08-17 | 2022-12-02 | 浙江大学 | Efficient heat conduction enhanced composite phase change material and preparation method thereof |
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| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
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| CN101407714A (en) * | 2008-09-16 | 2009-04-15 | 上海第二工业大学 | Paraffinic based carbon nano-tube compound phase transformation heat accumulating material and preparation thereof |
| CN103756646A (en) * | 2014-02-11 | 2014-04-30 | 北京科技大学 | Preparation method of metal organic framework based composite phase-change material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810675A (en) * | 2019-01-28 | 2019-05-28 | 华南理工大学 | A method of addition inorganic porous material generates setting to hydrous salt phase change material and adjusts phase transition temperature |
| CN110484213A (en) * | 2019-08-19 | 2019-11-22 | 苏州阿德旺斯新材料有限公司 | A kind of sizing MOF base composite phase-change material and its preparation method and application |
| CN110484213B (en) * | 2019-08-19 | 2021-03-02 | 苏州阿德旺斯新材料有限公司 | Shaped MOF-based composite phase change material and preparation method and application thereof |
| CN112175238A (en) * | 2020-10-22 | 2021-01-05 | 安徽大学 | Preparation method of boron nitride nanosheet-carbon nanotube heat-conducting filler and heat-conducting composite material |
| CN112920778A (en) * | 2021-01-28 | 2021-06-08 | 北京科技大学 | Hierarchical pore metal organic framework composite phase change material and preparation method thereof |
| CN114852958A (en) * | 2022-06-02 | 2022-08-05 | 集美大学 | MOFs composite hydrogen storage material based on 3D printing, preparation method thereof and application thereof in marine hydrogen storage |
| CN115058231A (en) * | 2022-07-14 | 2022-09-16 | 塔里木大学 | Phase-change material taking MOFs as carrier and preparation method thereof |
| CN115058231B (en) * | 2022-07-14 | 2023-08-18 | 塔里木大学 | Phase change material taking MOFs as carrier and preparation method thereof |
| CN115418194A (en) * | 2022-08-17 | 2022-12-02 | 浙江大学 | Efficient heat conduction enhanced composite phase change material and preparation method thereof |
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