CN110551487B - Graphene composite heat storage material - Google Patents
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Abstract
The invention provides a graphene composite heat storage material which comprises the following components in parts by weight: 50-80 parts of a polymer matrix, 5-20 parts of reduced graphene, 0.5-2 parts of a modifier and 5-10 parts of inorganic nanoparticles. The surface structure of the graphene is modified, and inorganic nano-ions are mixed in gaps, so that the thermal conductivity of the composite material can be obviously improved.
Description
Technical Field
The invention relates to a graphene composite heat storage material.
Background
Phase change thermal storage is a high and new energy storage technology based on phase change energy storage materials, and due to the advantages of constant temperature and high thermal storage density, the phase change thermal storage technology is widely researched. The phase change heat storage system is one of the important ways to improve the energy utilization rate as an effective means for solving the contradiction between the energy supply time and the space.
With the development of graphene research, the two-dimensional material shows good application prospect in the field of phase change heat storage due to excellent thermal conductivity, thermal stability and easy dispersibility.
Graphene is a single-layer two-dimensional planar structure formed by carbon atoms passing through sp2The orbitals are hybridized and are closely arranged in a regular hexagon. The unique structure of graphene enables the graphene to have a plurality of excellent characteristics, such as higher thermal conductivity (5000W/(m.K)), extremely high electrical conductivity (6000S/m), and high theoretical specific surface area (2630 m)2/g) and high electron mobility (2x 10)5cm2V.s). Graphene is the two-dimensional nanomaterial with the thinnest thickness, the largest strength, the highest thermal conductivity and the best electrical conductivity in the current material boundary. Due to the ultrahigh thermal conductivity and the ultrahigh specific surface area of the graphene, the graphene nanosheets stacked by the multi-layer graphene provide an excellent heat conduction channel for heat transfer in the polymer, so that the thermal conductivity, the mechanical strength, the electric conductivity and other physical properties of the polymer can be effectively improved, and a foundation is laid for the application of the graphene in the field of energy storage.
In recent years, research on the application of graphene/polymer composite heat conduction materials to the fields of electronic devices, heat dissipation and the like by improving the heat conductivity of polymers through graphene has been greatly advanced.
For example, the prior art discloses a stearic acid/graphene oxide composite phase-change heat storage material, which is prepared by using stearic acid as a heat storage medium and graphene oxide as a matrix and adopting a liquid phase intercalation method. The graphene oxide can maintain the shape and mechanical properties of the material, stearic acid is embedded in a graphene oxide matrix with a lamellar structure, energy is absorbed or released through phase change, the heat storage, heat conduction and cycle performance of the material are improved, and the problem of seepage and leakage of the stearic acid during phase change is solved (Zhoujianwei and the like, "research on stearic acid/graphene oxide composite phase change heat storage materials", new materials in chemical industry, volume 41, 6 th phase, pages 47-49, 2013). However, the research has the problems that one is to use graphene oxide as a matrix, and oxygen-containing groups in the graphene oxide influence the heat conducting performance of the composite material; the other is that the influence of the thermal interface resistance between the polymer and the graphene on the thermal conductivity is not considered.
Graphene Oxide (GO), a layered material obtained by oxidizing graphite, is used. After the graphite is oxidized, a separated graphene oxide lamellar structure is easily formed through a heating or ultrasonic stripping process in water. The structural detection shows that the graphene oxide contains a large number of oxygen-containing functional groups including hydroxyl, epoxy functional groups, carbonyl, carboxyl and the like, and carbon atoms in graphite lattices are changed from sp by organic groups in the chemical oxidation process2To sp3The hybridization of (2) destroys the electron transport, resulting in a decrease in the electrical and thermal conductivity of graphene oxide.
When Graphene and polymers are used to prepare Composites, there is significant interfacial Thermal resistance between Graphene and polymers, which has a great influence on energy transport of the Composites, and the interfacial Thermal resistance and the Thermal contact resistance between each other cause severe scattering of phonons at the interface, significantly reducing the system heat transfer (BIGDELI M b. fasano M. Thermal transmission in graphics Based Networks for Polymer Matrix Composites [ J ]. International Journal of Thermal Science,2017,117, 98-105). Therefore, the advantage of ultrahigh thermal conductivity of graphene is difficult to effectively exert due to high thermal resistance between interfaces, and the method for reducing the thermal resistance at the interfaces is an important way for improving the thermal conductivity of the graphene/polymer composite material.
In addition, when the graphene sheet layer is assembled, a larger gap is generated, the gap can not only form thermal resistance, but also influence the density of the graphene composite material, so that the heat transfer efficiency of the graphene/polymer composite material is reduced.
Therefore, how to improve the thermal conductivity of the graphene/polymer composite thermal conductive material is still a problem to be solved urgently.
Disclosure of Invention
Therefore, the invention provides the graphene composite heat storage material, and the interface thermal resistance can be reduced and the thermal conductivity of the composite material can be obviously improved by modifying the surface structure of the graphene and mixing inorganic nano-ions in gaps.
The graphene composite heat storage material comprises the following components in parts by weight: 50-80 parts of a polymer matrix, 5-20 parts of reduced graphene, 0.5-2 parts of a modifier and 5-10 parts of inorganic nanoparticles.
The components of the graphene composite heat storage material of the present invention are described in detail below.
1. Polymer matrix
The polymer matrix is a modified polyvinyl alcohol copolymer. Specifically, the modified polyvinyl alcohol copolymer is a graft copolymer of polyvinyl alcohol grafted glycidyl methacrylate.
Polyvinyl alcohol and glycidyl methacrylate are polymerized in the presence of a free radical initiator to obtain the modified polyvinyl alcohol copolymer.
Wherein, the weight percentage of the polyvinyl alcohol and the glycidyl methacrylate can be 80-95: 5-20.
The free radical initiator may be azobisisobutyronitrile, dibenzoyl peroxide, acid cerium ion solution, etc.
The solvent used in the polymerization reaction can be ethyl acetate, ethanol, isopropanol, chloroform, tetrahydrofuran, n-hexane, etc.
In the polymerization, 2-mercaptobenzimidazole, dilauryl thiodipropionate or 2, 6-di-tert-butyl-p-cresol may be used as stabilizer.
2. Reduced graphene
The structure of graphene affects thermal conductivity and other physical properties. The graphene obtained by different preparation methods has different structures, which are mainly expressed in crystal structures, layer numbers, impurities, oxygen content, other organic groups and the like. At present, the methods for preparing graphene mainly include a micro-mechanical stripping method, a chemical vapor deposition method, an epitaxial growth method, a microwave reduction method, a chemical oxidation method and the like, wherein the chemical oxidation method is widely concerned due to low cost and simple process, and becomes one of effective ways for mass production of graphene.
However, graphene oxide is a layered material obtained by oxidizing graphite, which has been oxidized to have a graphite interlayer distance of from that before oxidation
Will increase to
The separated graphene oxide lamellar structure is easily formed through a heating or ultrasonic stripping process in water. The structural detection shows that the graphene oxide contains a large number of oxygen-containing functional groups including hydroxyl, epoxy functional groups, carbonyl, carboxyl and the like, and carbon atoms in graphite lattices are changed from sp by organic groups in the chemical oxidation process2To sp3The hybridization of (2) destroys the electron transport, resulting in a decrease in the electrical and thermal conductivity of graphene oxide.
Therefore, in the invention, the reduced graphene is obtained by reducing the graphene oxide with the reducing agent, so that the oxygen-containing functional groups on the surface of the graphene oxide can be effectively removed, and the conductivity of the reduced graphene is improved.
Wherein the reduced graphene is prepared by the following method:
(1) graphite powder is used as an initial raw material, potassium permanganate and concentrated sulfuric acid are used as oxidants, and an improved Hummers liquid-phase oxidation method is adopted to obtain graphene oxide;
(2) using NaBH4As a reducing agent, barium chloride was used as a catalyst to reduce graphene oxide to reduced graphene.
Preferably, the graphene of the present invention is further subjected to a thermal annealing treatment.
Sp of graphene nanoplatelets3Hybridization proved to be detrimental for increasing thermal conductivity, for eliminating sp3And defects, the thermal annealing treatment of the graphene can improve the thermal conductivity.
Therefore, the method for preparing reduced graphene according to the present invention further includes: and annealing the reduced graphene in a furnace at the temperature of 700-1000 ℃ for 1-3 hours under the argon atmosphere.
Wherein, the whole thermal annealing process is carried out in argon atmosphere, the temperature rising and reducing process can be controlled in the range of 5 ℃/min, and the temperature is kept for 1-3 hours, preferably 1 hour at the highest annealing temperature.
The distribution state of the graphene nanosheets in the polymer, such as the formation of a two-dimensional or three-dimensional structure, determines the phonon transmission path in the matrix, the thermal resistance and the thermal conductivity of the system. High temperature annealing process under argon atmosphere to eliminate sp3And the defect is that a three-dimensional network structure is formed, so that the thermal conductivity can be obviously improved.
3. Modifying agent
The modifier used in the present invention is a copolymer of glycidyl methacrylate and 4-vinylpyridine.
Researches show that thermal resistance exists on an interface between a graphene nanosheet layer and a polymer matrix, and the thermal resistance has a great influence on energy transmission of the nanocomposite. The graphene nanosheet layer is modified, so that the acting force with the polymer matrix interface can be improved, the interface phonon heat transfer is promoted, and the heat conducting performance of the composite material is improved.
In the graphene/polymer composite heat conduction material, the main mode of heat conduction is phonons, and the phonons inevitably pass through the interface of polymer resin and filler in the transmission process, so that the interface bonding degree is increased, the phonon transmission is facilitated, and the heat conduction performance of the composite material is improved. The combination between the graphene and the matrix can reduce phonon scattering at the interface, thereby being beneficial to enhancing the thermal conductivity of the composite material.
According to the invention, the graphene is functionalized by using the copolymer of glycidyl methacrylate and 4-vinylpyridine, the modifier contains a pyridine group and an epoxy group, wherein the pyridine group is firmly adsorbed on the graphene nanosheet by pi-pi acting force, and the epoxy group of the glycidyl methacrylate promotes the compatibility and acting force of the graphene nanosheet and a polymer matrix, so that the thermal resistance can be effectively reduced, and the thermal conductivity and the thermal stability of the graphene can be improved.
The graphene modifier used in the invention not only improves the dispersion of graphene in a polymer matrix, but also enables the graphene and the polymer to form a cross-linked structure, enhances the interface coupling strength, and reduces the thermal resistance, thereby improving the thermal stability and the thermal conductivity of the graphene.
Copolymers of glycidyl methacrylate and 4-vinylpyridine can be prepared by copolymerizing glycidyl methacrylate and 4-vinylpyridine in the presence of a free radical initiator.
The weight percentage of glycidyl methacrylate and 4-vinylpyridine may be 60-90: 10-40.
The radical initiator may be azobisisobutyronitrile, dibenzoyl peroxide, etc.
The solvent for polymerization reaction can be anhydrous methanol, anhydrous ethanol, isopropanol, tetrahydrofuran, n-hexane, etc.
4. Inorganic nanoparticles
When the graphene sheet layer is assembled, larger interlayer gaps and interlayer gaps are generated, and the gaps form thermal resistance, so that the heat transfer efficiency of the graphene composite material is reduced. If these gaps can be filled effectively, the thermal conductivity of the composite material can be greatly improved.
According to the invention, the inorganic nanoparticles are used for filling the gap, and the mixed nanoparticles can form more heat conduction paths, establish a mutually overlapped heat conduction network, fully exert a synergistic heat conduction effect and effectively improve the heat conductivity of the polymer.
The inorganic nano particles are selected from boron nitride, aluminum oxide, titanium dioxide, carbon nano tubes and the like.
The invention also provides a method for preparing the graphene composite heat storage material, which comprises the following steps:
(1) modification of reduced graphene
Adding a modifier into a solvent, stirring for 1-2 hours under heating, then adding reduced graphene, continuing stirring for 3-5 hours, and then ultrasonically mixing for 30-60 minutes;
(2) preparation of graphene composite heat storage material
And (2) adding the polymer matrix and the inorganic nanoparticles into the reaction liquid obtained in the step (1), violently stirring for 5-10 hours, then ultrasonically mixing for 30-60 minutes, filtering, and drying to obtain the graphene composite heat storage material.
Wherein, in the step (1), the solvent is ethanol, dimethylformamide, dichloromethane, n-hexane, dimethyl sulfoxide, chloroform, ethyl acetate, benzene, acetone, tetrahydrofuran, etc.
The modifier is a copolymer of glycidyl methacrylate and 4-vinylpyridine, is firmly adsorbed on the graphene nanosheets through pyridine groups under pi-pi acting force, promotes compatibility and acting force between the graphene nanosheets and polymers through epoxy groups, and can effectively improve thermal conductivity and thermal stability of graphene.
In the step (2), the raw materials are uniformly dispersed through strong stirring, the graphene nanosheets are coupled in the polymer matrix to form a heat conducting network, and meanwhile, the inorganic nanoparticles are filled in the gaps.
To aid in the dispersion of the reaction components, a stabilizer, which may be p-toluenesulfonamide, cetyltrimethylammonium bromide, or the like, may be further added.
According to the preparation method, the graphene composite heat storage material is obtained by a physical mixing method, the graphene nanosheets are uniformly dispersed in the polymer matrix, the epoxy group of the glycidyl methacrylate can promote the compatibility and acting force of the graphene and the polymer matrix, and the graphene nanosheets are embedded in the polymer matrix to form a heat conducting network.
The invention has the advantages of
1. The modified polyvinyl alcohol copolymer is used as a polymer matrix, and the hydroxyl in the matrix can promote the compatibility and acting force of the polymer matrix and graphene, so that the thermal stability and the thermal conductivity are improved.
2. The surface structure of the graphene nanosheet is modified by using the modifier, so that the interface acting force of the graphene and the polymer matrix is improved, the interface heat transfer is promoted, the interface thermal resistance is reduced, and the heat conducting performance of the composite material is improved.
3. Inorganic nanoparticles are used for filling gaps between layers and in-layer gaps generated when the graphene sheet layers are assembled, and mixed nanoparticles can form more heat conduction paths, so that the synergistic heat conduction effect is fully exerted, and the heat conductivity of the polymer is effectively improved.
Detailed Description
The graphene composite heat storage material of the present invention will be described in detail with reference to the following examples.
Firstly, material preparation
1. Preparation of reduced graphene
(1) Pre-oxidation of graphite
Under the condition of stirring, 5g of graphite powder, 2g of potassium persulfate and 5g of phosphorus pentoxide are added into a three-necked flask filled with 15mL of concentrated sulfuric acid, the mixture is reacted for 4 hours at 70-80 ℃, then the reaction is continued for 5 hours at room temperature, and the mixture is filtered, washed to be neutral by deionized water and dried to obtain pre-oxidized graphite.
(2) Preparation of graphene oxide
Under the condition of stirring, 1g of the prepared pre-oxidized graphite is added into a three-necked bottle filled with 30mL of concentrated sulfuric acid, the three-necked bottle is placed in an ice water bath, 2.5g of potassium permanganate is added to react for 1 hour, then the reaction is carried out for 2 hours at 40 ℃, 100mL of deionized water is added to continue to react for 1 hour at 40 ℃, finally 30% of hydrogen peroxide is added until no bubbles are generated, the filtration is carried out, the washing is carried out by using 5% of hydrochloric acid and deionized water in sequence, and the product is subjected to ultrasonic oscillation for 1 hour and vacuum drying to obtain the graphene oxide.
(3) Preparation of reduced graphene
2.56g of NaBH4And 1.2g of BaCl2Added to 220mL of a graphene oxide suspension (0.5mg/mL), stirred at room temperature for 10 hours, filtered, and removedWashing the graphene oxide with ionized water to be neutral, and drying to obtain the reduced graphene.
2. High temperature annealing of graphene
The reduced graphene was annealed at a high temperature in a furnace at 800 ℃ for 1 hour under an argon atmosphere. Wherein the temperature rising and reducing processes are controlled within the range of 5 ℃/min.
3. Preparation of graft copolymer of polyvinyl alcohol grafted glycidyl methacrylate
Adding 35g of polyvinyl alcohol, 5g of glycidyl methacrylate, 0.30g of dibenzoyl peroxide and 0.15g of 2-mercaptobenzimidazole into a high-pressure container, then adding 50ml of ethyl acetate, covering the cover of the high-pressure container, reacting at 170 ℃ for 12 hours, then cooling, opening the high-pressure container, washing the product with acetone three times, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the graft copolymer of the polyvinyl alcohol grafted glycidyl methacrylate.
4. Preparation of copolymer of glycidyl methacrylate and 4-vinylpyridine
150mL of anhydrous methanol, 75g of glycidyl methacrylate and 25g of 4-vinylpyridine are added into a 500mL five-neck flask provided with a reflux condenser tube and an electric stirrer, nitrogen is introduced, the mixture is heated to 60 ℃ for reflux, then 0.5g of azobisisobutyronitrile dissolved in 20mL of anhydrous methanol is added dropwise for 30 minutes, the reaction is continued for 5 hours, then the temperature is raised to 80 ℃ for 4 hours, the reaction solution is poured into distilled water while hot for precipitation, filtered, washed with water and dried in vacuum, and the copolymer of glycidyl methacrylate and 4-vinylpyridine is obtained.
Preparation of graphene composite heat storage material
Example 1
(1) Modification of reduced graphene
Adding 8mg of modifier into 200ml of dimethylformamide, stirring for 2 hours under the heating of a water bath, then adding 150mg of reduced graphene, continuing stirring for 5 hours, and then performing ultrasonic oscillation for 30 minutes.
The modifier is a copolymer of glycidyl methacrylate 4-vinylpyridine.
(2) Polymer/graphene composite material
Adding 650mg of the copolymer of polyvinyl alcohol grafted glycidyl methacrylate, 70mg of boron nitride and 50mg of p-toluenesulfonamide (p-TSA) into the reaction solution obtained in the step (1), stirring vigorously at 70 ℃ for 8 hours, then filtering by ultrasonic mixing for 30 minutes, and drying at 100 ℃ for 12 hours to obtain the polymer/graphene composite material.
Example 2
A polymer/graphene composite material was prepared in the same manner as in example 1, except that reduced graphene subjected to a high-temperature annealing treatment was used instead of the reduced graphene.
Comparative example 1
A polymer/graphene composite material was prepared in the same manner as in example 1, except that the reduced graphene was not modified using a modifier.
Comparative example 2
A polymer/graphene composite was prepared in the same manner as in example 1, except that the inorganic nanoparticles were not used for filling.
Second, evaluation of Performance
Thermal conductivity is an important parameter of phase change materials, and is used for measuring the ability of the materials to conduct heat.
The in-plane thermal conductivity of the polymer/graphene composite materials prepared in examples 1 to 2 of the present invention and comparative examples 1 to 2 was measured using a thermal conductivity meter, and the measurement temperature was 25 ℃. The results are shown in Table 1.
TABLE 1
| Examples | Thermal conductivity (W/(m.K)) |
| Example 1 | 1.95 |
| Example 3 | 2.37 |
| Comparative example 1 | 1.24 |
| Comparative example 2 | 1.16 |
| Polyvinyl alcohol film | 0.72 |
As can be seen from the results in table 1, the thermal conductivity of the polyvinyl alcohol film used in the present invention was 0.72W/(m · K), and comparative examples 1 to 2 did not consider the problems of interfacial thermal resistance and voids, and although the thermal conductivity was improved as compared with the polyvinyl alcohol film, the improvement range was limited. According to the invention, the surface structure of the graphene is modified, and inorganic nano ions are mixed in gaps, so that the thermal conductivity of the composite material is obviously improved.
Claims (6)
1. A graphene composite heat storage material comprises the following components in parts by weight: 50-80 parts of a polymer matrix, 5-20 parts of reduced graphene, 0.5-2 parts of a modifier and 5-10 parts of inorganic nanoparticles;
wherein the polymer matrix is a graft copolymer of polyvinyl alcohol grafted glycidyl methacrylate, wherein the weight percentage of the polyvinyl alcohol and the glycidyl methacrylate is 80-95: 5-20;
the modifier is a copolymer of glycidyl methacrylate and 4-vinylpyridine, wherein the weight percentage of the glycidyl methacrylate to the 4-vinylpyridine is 60-90: 10-40;
and carrying out high-temperature annealing treatment on the reduced graphene, and modifying the reduced graphene by the modifier.
2. The graphene composite heat storage material of claim 1, wherein the inorganic nanoparticles are one or more selected from boron nitride, aluminum oxide, titanium dioxide, and carbon nanotubes.
3. The method for preparing the graphene composite heat storage material of any one of claims 1-2, comprising:
(1) modification of reduced graphene
Adding a modifier into a solvent, stirring for 1-2 hours under heating, then adding reduced graphene, continuing stirring for 3-5 hours, and then ultrasonically mixing for 30-60 minutes;
wherein the reduced graphene is subjected to high-temperature annealing treatment;
(2) preparation of graphene composite heat storage material
And (2) adding the polymer matrix and the inorganic nanoparticles into the reaction liquid obtained in the step (1), violently stirring for 5-10 hours, then ultrasonically mixing for 30-60 minutes, filtering, and drying to obtain the graphene composite heat storage material.
4. The method of claim 3, wherein the reduced graphene is prepared by:
(1) graphite powder is used as an initial raw material, potassium permanganate and concentrated sulfuric acid are used as oxidants, and an improved Hummers liquid-phase oxidation method is adopted to obtain graphene oxide;
(2) using NaBH4As a reducing agent, barium chloride was used as a catalyst to reduce graphene oxide to reduced graphene.
5. The method of claim 3, wherein the polymer matrix is prepared by:
polyvinyl alcohol and glycidyl methacrylate are polymerized in the presence of a free radical initiator to obtain a modified polyvinyl alcohol copolymer, wherein the weight percentage of the polyvinyl alcohol and the glycidyl methacrylate is 80-95: 5-20.
6. The process of claim 3, wherein the modifier is prepared by polymerizing glycidyl methacrylate and 4-vinylpyridine in the presence of a free radical initiator in a weight percent of 60-90: 10-40.
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