CN113173864B - Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof - Google Patents
Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene synergistic photo-thermal energy storage composite material and a preparation method and application thereof. The composite material comprises trifluoromethylazobenzene and reduced graphene oxide, wherein the trifluoromethylazobenzene is grafted on the surface of a sheet layer of the reduced graphene oxide in a covalent coupling mode. The graphene synergistic photo-thermal energy storage composite material at least has low-temperature heat release performance, and also has excellent energy storage density, so that compared with the traditional trifluoromethyl azobenzene molecule, the graphene synergistic photo-thermal energy storage composite material has a great improvement in low-temperature heat release and energy density, and has a wide application prospect in the fields of solar energy utilization and photo-thermal conversion in the future.
Description
Technical Field
The invention belongs to the field of heat storage functional materials, and relates to a graphene synergistic photo-thermal energy storage composite material, and a preparation method and application thereof.
Background
As is well known, solar energy is one of renewable natural energy sources with very rich content, and has the outstanding advantages of low cost, safety, environmental protection, inexhaustible use and the like. Along with the continuous advancement of modern steps, the energy demand of various industries is continuously increasing, but the traditional series of fossil fuels cannot meet the current urgent problem of huge energy demand, and the dependence on fossil fuels is reduced in various countries around the world due to a series of problems caused by fossil fuels, such as climate change, environmental deterioration and the like, and various clean and renewable energy sources are greatly developed. In a series of clean energy sources, the development and utilization of solar energy have been increasingly studied and focused by people worldwide in recent years. Under the background, the development and utilization of solar energy are one of the key problems of the current research in China, and particularly, the method has important practical application value in the aspects of deep research on the conversion and storage of solar energy and heat energy.
The mechanism of dihydroazepine-vinylheptene (DHA-VHF) as a photoisomerization response material and its potential for use in photothermal storage are described in detail by the Jeffrey C.Grossman subject group of the Massa institute of technology (Kanai, Y., srinivasan, V., meier, S.K., vollhardt, K.P.C., and Grossman, J.C. (2010), mechanism of Thermal Reversal of the (Fulvalene) tetracarbonyldiruthenium Photoisomerization: toward Molecular Solar-Thermal Energy storage Chemie International Edition, 49:8926-8929). However, the energy density of the material is low, and the practical application cost is high. In addition, the prior art CN110305635a also discloses a formed heat storage material and a preparation method thereof, and the material has the advantage of wider heat storage application range, but the material uses graphene as an auxiliary material, and the excellent heat conducting property of the graphene is not utilized.
Azobenzene is one of photosensitive dye and photoresponsive material which is widely researched, and more researches and concerns are brought to researchers in the field of solar heat storage in recent years. Azobenzene has both cis and trans isomers. An isomerization conversion phenomenon from a trans configuration to a cis configuration occurs under the irradiation of light with a specific wavelength; then under the action of external stimulus (such as illumination, heating) and the like, the isomerization reversion phenomenon from cis-form to trans-form can occur. There is a certain energy difference between the two different isomers of azobenzene, and a certain amount of energy can be stored in a chemical energy manner during the transition from the trans configuration to the cis configuration, whereas the stored energy can be released in a heat form during the transition from the cis configuration to the trans configuration.
In the prior art, the graphene composite energy storage material grafted with azobenzene exists, however, the exothermic temperature of the energy storage material is as high as 80 ℃, and the exothermic of the material under the condition of lower external temperature is greatly limited. Therefore, providing a composite material of azobenzene graft graphene with at least low-temperature heat release performance becomes a technical problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a graphene synergistic photo-thermal energy storage composite material, which comprises trifluoromethylazobenzene and reduced graphene oxide, wherein the trifluoromethylazobenzene is grafted on the surface of a sheet of the reduced graphene oxide in a covalent coupling manner.
According to an embodiment of the invention, a trifluoromethyl azobenzene molecule is grafted on the surface of the sheet layer of the reduced graphene oxide, wherein the average number of carbon atoms is 20-40; for example, an average of 25 to 35 carbon atoms per molecule of trifluoromethylated azobenzene; for example, a trifluoromethylated azobenzene molecule is grafted with an average of 27-32 carbon atoms. Illustratively, an average of one trifluoromethylated azobenzene molecule is grafted per 20, 22, 24, 25, 26, 28, 30, 31, 32, 33, 34, 35, 37, 39, or 40 carbon atoms.
According to the embodiment of the invention, the trifluoromethyl azobenzene is covalently coupled and grafted on the surface of a sheet layer of reduced graphene oxide in an array form.
According to an embodiment of the present invention, the trifluoromethylated azobenzene has a structure as shown in formula (I):
according to an embodiment of the invention, the graphene synergistic photo-thermal energy storage composite material has a structure substantially as shown below:
according to the embodiment of the invention, the energy density of the graphene synergistic photo-thermal energy storage composite material is not lower than 100 kJ.kg -1 For example, an energy density of 110-400 kJ.kg -1 Exemplary is 120 kJ.kg -1 ，129.3kJ·kg -1 ，179.2kJ·kg -1 ，200kJ·kg -1 ，221.5kJ·kg -1 ，246.8kJ·kg -1 ，300kJ·kg -1 ，334.5kJ·kg -1 ，360kJ·kg -1 。
According to an embodiment of the invention, the exothermic temperature span of the graphene synergistic photo-thermal energy storage composite material (referring to the temperature difference range from the beginning of the exotherm to the end of the exotherm) is 40-60 ℃, for example 42-58 ℃, and is exemplified by 45 ℃, 50 ℃, 55 ℃.
According to an embodiment of the invention, the initial exothermic temperature of the graphene synergistic photo-thermal energy storage composite is 30-40 ℃, e.g. 32-38 ℃, exemplary 30 ℃, 32 ℃, 34 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃.
According to an embodiment of the invention, the termination exotherm temperature of the graphene synergistic photo-thermal energy storage composite is 80-90 ℃, e.g. 82-88 ℃, exemplary 80 ℃, 82 ℃, 84 ℃,85 ℃, 86 ℃, 88 ℃, 90 ℃.
The invention also provides a preparation method of the graphene synergistic photo-thermal composite energy storage material, which comprises the following steps:
(1) Preparing an azobenzene diazonium salt solution: coupling trifluoromethylThe nitrogen benzene is evenly dispersed in dilute sulfuric acid water solution, and NaNO is added into the dilute sulfuric acid water solution under the low temperature condition 2 Dispersing to obtain an azobenzene diazonium salt solution;
(2) Dispersing the azobenzene diazonium salt solution in a reduced graphene oxide aqueous solution, and stirring for reaction to obtain the graphene synergistic photo-thermal composite energy storage material.
According to an embodiment of the present invention, in step (1), the trifluoromethylated azobenzene and NaNO 2 The molar ratio of (2) is 1 (0.8-1.2), preferably 1:1. Preferably, the trifluoromethylated azobenzene is used in an amount of 3-15 mole parts, for example 4-12 mole parts, exemplified by 3 mole parts, 5 mole parts, 6 mole parts, 8 mole parts, 10 mole parts.
According to an embodiment of the invention, in step (1), the concentration of sulfuric acid in the dilute aqueous sulfuric acid solution is 0.5-3mol/L, for example 1-2mol/L.
According to an embodiment of the present invention, in step (1), the NaNO 2 In the form of an aqueous solution thereof, preferably NaNO 2 The aqueous solution was added in a slow drop-wise fashion. For example NaNO 2 NaNO in aqueous solution 2 The concentration of (C) is 50-100mg/mL, for example 60-90mg/mL, and exemplary is 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL.
According to an embodiment of the present invention, in step (1), the trifluoromethylated azobenzene and H 2 SO 4 The molar ratio of (2.5-5), for example 1 (3-4), is exemplified by 1:2.5, 1:3.5.
According to an embodiment of the invention, in step (1), the low temperature conditions are provided by an ice bath.
According to an embodiment of the invention, in step (1), the time of dispersion is between 0.5 and 2 hours, for example 1 hour. Preferably, the dispersion is a stirred dispersion to uniformly disperse the trifluoromethylated azobenzene in the dilute aqueous sulfuric acid solution.
According to an embodiment of the present invention, the preparation process of the trifluoromethylated azobenzene includes the steps of:
(a) 3-amino-5- (trifluoromethyl) benzoic acid was mixed with dilute sulfuric acid aqueous solution, to which NaNO was slowly added 2 The aqueous solution of the water-soluble polymer,dispersing to obtain diazonium salt solution;
(b) Slowly dropwise adding the diazonium salt solution into an aqueous solution of 3, 5-dimethoxy aniline, regulating the pH value of the system by using alkali after the dropwise adding is completed, and stirring for reaction to obtain a crude product of trifluoromethyl azobenzene;
(c) The crude product is purified to obtain the trifluoromethyl azobenzene.
Preferably, in step (a), the molar ratio of 3-amino-5- (trifluoromethyl) benzoic acid to sodium nitrite is 1 (0.9-2), for example 1 (1-1.5); for example, 3-amino-5- (trifluoromethyl) benzoic acid is used in an amount of 3 to 25 parts by mole, for example 5 to 20 parts by mole, and exemplified by 5 parts by 7 parts by mole and 10 parts by mole;
preferably, in step (a), H is present in a mixture of 3-amino-5- (trifluoromethyl) benzoic acid and dilute sulfuric acid in water 2 SO 4 And 3-amino-5- (trifluoromethyl) benzoic acid in a molar ratio of 1 (5-10), preferably 1 (2-8), for example 1:5, 1:6, 1:7, 1:8;
preferably, H in the dilute sulfuric acid aqueous solution 2 SO 4 The concentration of (C) is 0.3-1mol/L, for example 0.5mol/L.
Preferably, in step (a), the time of dispersion is from 0.5 to 2 hours, for example 1 hour.
Preferably, in step (a), the NaNO 2 The addition of the aqueous solution and the dispersion to obtain the diazonium salt solution are carried out at low temperature, preferably as provided by an ice bath.
Preferably, in step (b), the molar ratio of 3-amino-5- (trifluoromethyl) benzoic acid to 3, 5-dimethoxyaniline is 1 (0.8-1.2), preferably 1:1;
preferably, in step (b), the base is at least one of sodium hydroxide, potassium hydroxide, etc., preferably sodium hydroxide; preferably, the base is added as an alkaline solution; preferably, the concentration of the base is 0.5 to 1mol/L;
preferably, in step (b), the pH of the system is adjusted to a pH of 4-6;
preferably, in step (b), the stirring speed of the stirring reaction is 500-600 revolutions per minute; preferably, the reaction is stirred for a period of 1 to 5 hours.
Preferably, in step (b), the process of slowly adding dropwise the aqueous solution of 3, 5-dimethoxyaniline in the diazonium salt solution and stirring the reaction is carried out under low temperature conditions, preferably under low temperature conditions provided by an ice bath.
Preferably, in step (b), the stirring reaction is carried out under an inert atmosphere, for example under an argon atmosphere.
Preferably, in step (b), the purification may be carried out using purification methods known in the art, such as column chromatography.
The preparation route of the trifluoromethyl azobenzene is as follows:
according to an embodiment of the present invention, in step (2), the reduced graphene oxide is added in the form of an aqueous reduced graphene oxide solution. Preferably, the concentration of the reduced graphene oxide aqueous solution is 0.5-2mg/mL, for example 1mg/mL.
According to an embodiment of the invention, in step (2), the stirring reaction is carried out under an inert atmosphere, for example under an argon atmosphere.
Preferably, the stirred reaction comprises two stages: a low temperature reaction stage and a room temperature reaction stage. For example, the low temperature reaction stage is carried out firstly, and stirring is carried out for 3-7 hours, such as 5 hours, under the ice water bath condition; the reaction is continued at room temperature for a further 20-30 hours, for example 25 hours, with stirring.
According to an embodiment of the present invention, in step (2), the preparation process of the reduced graphene oxide includes: and adopting sodium borohydride to perform reduction treatment on the graphene oxide, and washing to obtain the reduced graphene oxide.
Preferably, sodium borohydride is added to an aqueous solution of graphene oxide having a pH of 8 to 10, and the reduction treatment is performed under an inert atmosphere (e.g., argon). Preferably, the pH of the aqueous solution of graphene oxide may be achieved by adding a saturated aqueous sodium bicarbonate solution thereto.
Preferably, the mass ratio of graphene oxide to sodium borohydride is 1 (5-20), for example 1 (7-15), and exemplary is 1:9.
Preferably, the temperature of the reduction treatment is 80-100 ℃; preferably, the time of the reduction treatment is 1 to 5 hours.
In the present invention, the "molar part" may refer to 1mmol or 1mol.
The invention also provides application of the graphene synergistic photo-thermal energy storage composite material in a solar energy storage device.
The invention has the beneficial effects that:
the graphene synergistic photo-thermal energy storage composite material is prepared by grafting trifluoromethyl azobenzene onto the surface of reduced graphene oxide in a covalent coupling mode. After observing the structure of the material by a scanning electron microscope, the trifluoromethyl azobenzene molecule is successfully grafted on the surface of the reduced graphene oxide. The graphene synergistic photo-thermal energy storage composite material at least has low-temperature heat release performance, and also has excellent energy storage density, so that compared with the traditional trifluoromethyl azobenzene molecule, the graphene synergistic photo-thermal energy storage composite material has a great improvement in low-temperature heat release and energy density, and has a wide application prospect in the fields of solar energy utilization and photo-thermal conversion in the future.
Drawings
Fig. 1 is a scanning electron micrograph of reduced graphene oxide prepared according to the present invention.
Fig. 2 is a scanning electron microscope photograph of the graphene synergistic photo-thermal energy storage composite material prepared by the invention.
FIG. 3 is a nuclear magnetic characterization map of the trifluoromethylated azobenzene compound of the present invention.
Fig. 4 is an infrared signature of the graphene synergistic photo-thermal energy storage composite material prepared by the invention.
Fig. 5 is a differential scanning calorimetric spectrogram of the graphene synergistic photo-thermal energy storage composite material prepared by the invention.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Wherein in the synthesis process of the trifluoromethyl azobenzene, the equivalent weight and the equivalent weight are one time and 2 times of the mole amount of the 3-amino-5- (trifluoromethyl) benzoic acid based on the mole amount of the 3-amino-5- (trifluoromethyl) benzoic acid.
Energy density testing procedure for each composite in the following examples:
firstly, uniformly dispersing the graphene synergistic photo-thermal energy storage composite material in acetone, and then irradiating a sample by using an 365nm LED light source to store energy. After the energy storage is completed, the test is performed by DSC. The initial temperature of the DSC was first set to 10deg.C and stabilized for 15 minutes, after which the DSC was heated to 140deg.C at a rate of 10deg.C/min to complete the full energy density test procedure.
Example 1
1) 5mmol of 3-amino-5- (trifluoromethyl) benzoic acid was weighed out and homogeneously dispersed in 10ml of deionized water and 50ml of 0.5 mol.L were added -1 H of (2) 2 SO 4 After the solution is stirred uniformly under ice bath condition, 5mL of 70 mg.mL of the solution is slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to give a diazonium salt solution. Then the diazonium salt solution is slowly added dropwise to 0.765g of 3, 5-dimethoxyaniline in water, followed by 0.5 mol.L -1 And (3) regulating the pH value of the system to 4, continuing ice bath stirring for 1 hour under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate, thereby obtaining a crude product of the trifluoromethyl azobenzene. And (3) separating the crude product by column chromatography to obtain the final trifluoromethyl azobenzene product.
2) Preparation of reduced graphene oxide: by means of saturated NaHCO 3 300mL of 1mg/mL of the aqueous solution -1 The pH of the aqueous solution of the uniformly dispersed graphene oxide was adjusted to 9, and the solution was sonicated for 2 hours to separate the graphene oxideUniformly dispersing, adding 2.7g of sodium borohydride, reacting for 2 hours under the argon atmosphere and at the temperature of 85 ℃, washing the product with deionized water and absolute ethyl alcohol for 3 times to obtain target reduced graphene oxide rGO, and then re-dispersing the target reduced graphene oxide rGO into deionized water to obtain a reduced graphene oxide aqueous solution.
3) Preparation of graphene synergistic photo-thermal energy storage composite material: 3mmol of trifluoromethylated azobenzene was uniformly dispersed in 10ml of deionized water and 7.5ml of 1mol L was added -1 H of (2) 2 SO 4 Stirring uniformly under ice bath condition, slowly adding 3mL 70 mg.multidot.mL -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to obtain an azobenzene diazonium salt solution. Then slowly dropwise adding 75mL of 1 mg-mL of uniformly dispersed azobenzene diazonium salt solution -1 In the reduced graphene oxide aqueous solution, ice bath stirring is continued for 1 hour under the argon atmosphere, then the reaction is continued for 5 hours at 25 ℃, and finally the trifluoromethyl azobenzene is grafted on the surface of the reduced graphene oxide in a covalent coupling mode, and an average of every 37 carbon atoms is grafted with one trifluoromethyl azobenzene molecule. And (3) after centrifuging, washing the product for a plurality of times by deionized water and acetone respectively, and then carrying out vacuum drying to obtain the graphene synergistic photo-thermal energy storage composite material. The energy density is 129.3 kJ.kg -1 。
Example 2
1) 10mmol of 3-amino-5- (trifluoromethyl) benzoic acid was weighed out and homogeneously dispersed in 20ml of deionized water and 60ml of 0.5 mol.L were added -1 H of (2) 2 SO 4 The solution was stirred uniformly under ice bath conditions and then 12mL of 70mg/mL was slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to give a diazonium salt solution. Then the diazonium salt solution is slowly added dropwise to 1.53g of an aqueous solution of 3, 5-dimethoxyaniline, followed by 0.6 mol.L -1 And (3) regulating the pH value of the system to 4.5, continuing ice bath stirring for 2 hours under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate, thereby obtaining a crude product of the trifluoromethyl azobenzene. And (3) separating the crude product by column chromatography to obtain the final trifluoromethyl azobenzene product.
2) Preparation of reduced graphene oxide: by means of saturated NaHCO 3 450mL of 1mg/mL of the aqueous solution -1 The pH value of the uniformly dispersed graphene oxide aqueous solution is adjusted to 9, the uniformly dispersed graphene oxide aqueous solution is subjected to ultrasonic treatment for 2 hours to obtain uniform dispersion, 3.15g of sodium borohydride is added, the reaction is carried out for 3 hours under the condition of argon atmosphere and 90 ℃, the product is washed for 3 times by deionized water ionized water and absolute ethyl alcohol to obtain target reduced graphene oxide rGO, and then the target reduced graphene oxide rGO is redispersed in deionized water to obtain reduced graphene oxide aqueous solution.
3) Preparation of graphene synergistic photo-thermal energy storage composite material: 6mmol of trifluoromethylated azobenzene was uniformly dispersed in 20ml of deionized water and 18ml of 1mol L was added -1 H of (2) 2 SO 4 After stirring evenly under ice bath condition, 6mL 70 mg.mL is slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to obtain an azobenzene diazonium salt solution. Then slowly dropping the azobenzene diazonium salt solution into 150mL of 1 mg-mL of uniformly dispersed solution -1 In the reduced graphene oxide aqueous solution, ice bath stirring is continued for 2 hours under the argon atmosphere, then the reaction is continued for 10 hours at 25 ℃, finally, the trifluoromethyl azobenzene is grafted on the surface of the reduced graphene oxide in a coupling mode, every 28 carbon atoms are grafted with a trifluoromethyl azobenzene molecular product on average, and after centrifugation, the graphene synergistic photo-thermal energy storage composite material is obtained after washing for a plurality of times through deionized water and acetone respectively, and then vacuum drying is carried out. Energy density 246.8 kJ.kg -1 。
Example 3
1) 15mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and homogeneously dispersed in 30ml of deionized water and 105ml of 0.5 mol.L are added -1 H of (2) 2 SO 4 The solution was stirred uniformly under ice bath conditions and then 21mL of 70mg/mL was slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to give a diazonium salt solution. Then the diazonium salt solution is slowly added dropwise to 2.295g of an aqueous solution of 3, 5-dimethoxyaniline, followed by 0.7 mol.L -1 The pH of the system is adjusted to 5 by NaOH aqueous solution, ice bath stirring is continued for 3 hours under argon atmosphere, and after the reaction is finished, the system is stood and decompressedAnd (3) carrying out suction filtration to obtain a precipitate, and obtaining a crude product of the trifluoromethyl azobenzene. And (3) separating the crude product by column chromatography to obtain the final trifluoromethyl azobenzene product.
2) Preparation of reduced graphene oxide: by means of saturated NaHCO 3 450mL of 1mg/mL of the aqueous solution -1 The pH value of the uniformly dispersed graphene oxide aqueous solution is adjusted to 9, the uniformly dispersed graphene oxide aqueous solution is subjected to ultrasonic treatment for 2 hours to obtain uniform dispersion, 3.15g of sodium borohydride is added, the reaction is carried out for 3 hours under the condition of argon atmosphere and 90 ℃, the product is washed for 3 times by deionized water ionized water and absolute ethyl alcohol to obtain target reduced graphene oxide rGO, and then the target reduced graphene oxide rGO is redispersed in deionized water to obtain reduced graphene oxide aqueous solution.
3) Preparation of graphene synergistic photo-thermal energy storage composite material: 9mmol of trifluoromethylated azobenzene was uniformly dispersed in 30ml of deionized water and 31.5ml of 1mol L was added -1 H of (2) 2 SO 4 After stirring uniformly under ice bath condition, 9mL 70mg/mL was slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to obtain an azobenzene diazonium salt solution. Then slowly dropping the azobenzene diazonium salt solution into 225mL of 1 mg.mL of evenly dispersed solution -1 In the reduced graphene oxide aqueous solution, ice bath stirring is continued for 3 hours under the argon atmosphere, then the reaction is continued for 15 hours at 25 ℃, and finally the trifluoromethyl azobenzene is grafted on the surface of the reduced graphene oxide in a coupling mode, and an average of every 22 carbon atoms is grafted with one trifluoromethyl azobenzene molecule. And (3) after centrifuging, washing the product for a plurality of times by deionized water and acetone respectively, and then carrying out vacuum drying to obtain the graphene synergistic photo-thermal energy storage composite material. The energy density is 334.5 kJ.kg -1 。
Example 4
1) 20mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and homogeneously dispersed in 40ml of deionized water and 160ml of 0.5 mol.L are added -1 H of (2) 2 SO 4 The solution was stirred uniformly under ice bath conditions and then 36mL of 70mg/mL was slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to give a diazonium salt solution. The diazonium salt solution is then slowly added dropwise to 3.06gIn an aqueous solution of 3, 5-dimethoxyaniline, followed by 0.8 mol.L -1 And (3) regulating the pH value of the system to 5.5, continuing ice bath stirring for 4 hours under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate, thereby obtaining a crude product of the trifluoromethyl azobenzene. And (3) separating the crude product by column chromatography to obtain the final trifluoromethyl azobenzene product.
2) Preparation of reduced graphene oxide: by means of saturated NaHCO 3 600mL of 1mg/mL of the aqueous solution -1 The pH value of the uniformly dispersed graphene oxide aqueous solution is adjusted to 9, the uniformly dispersed graphene oxide aqueous solution is subjected to ultrasonic treatment for 2 hours to obtain uniform dispersion, then 5.4g of sodium borohydride is added, the reaction is carried out for 4 hours under the condition of argon atmosphere and 95 ℃, the product is washed for 3 times by deionized water ionized water and absolute ethyl alcohol to obtain target reduced graphene oxide rGO, and then the target reduced graphene oxide rGO is redispersed in deionized water to obtain reduced graphene oxide aqueous solution.
3) Preparation of graphene synergistic photo-thermal energy storage composite material: 12mmol of trifluoromethylated azobenzene was uniformly dispersed in 40ml of deionized water and 48ml of 1mol L was added -1 H of (2) 2 SO 4 After stirring evenly under ice bath condition, 12mL 70 mg.mL is slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to obtain an azobenzene diazonium salt solution. Then slowly adding the azobenzene diazonium salt solution into 300mL of 1 mg-mL evenly dispersed solution in a dropwise manner -1 In the reduced graphene oxide aqueous solution, ice bath stirring is continued for 4 hours under the argon atmosphere, then the reaction is continued for 20 hours at 25 ℃, finally, the trifluoromethyl azobenzene is grafted on the surface of the reduced graphene oxide in a coupling mode, an average of every 31 carbon atoms is grafted with a trifluoromethyl azobenzene molecular product, after centrifugation, deionized water and acetone are respectively used for washing for a plurality of times, and then vacuum drying is carried out, so that the graphene synergistic photo-thermal energy storage composite material is obtained. The energy density is 221.5 kJ.kg -1 。
Example 5
1) 25mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and homogeneously dispersed in 50ml of deionized water and 250ml of 0.5 mol.L are added -1 H of (2) 2 SO 4 Stirring the solution under ice bath conditionAfter being evenly stirred, 50mL 70 mg.mL is slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to give a diazonium salt solution. Then the diazonium salt solution is slowly added dropwise to 3.825g of an aqueous solution of 3, 5-dimethoxyaniline, followed by 1 mol.L -1 And (3) regulating the pH value of the system to 6, continuing ice bath stirring for 5 hours under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate, thereby obtaining a crude product of the trifluoromethyl azobenzene. And (3) separating the crude product by column chromatography to obtain the final trifluoromethyl azobenzene product.
2) Preparation of reduced graphene oxide: by means of saturated NaHCO 3 750mL of 1mg/mL of the aqueous solution -1 The pH value of the uniformly dispersed graphene oxide aqueous solution is adjusted to 9, the uniformly dispersed graphene oxide aqueous solution is subjected to ultrasonic treatment for 2 hours to obtain uniform dispersion, 7.5g of sodium borohydride is added, the reaction is carried out for 5 hours under the condition of argon atmosphere and 100 ℃, the product is washed for 3 times by deionized water ionized water and absolute ethyl alcohol to obtain target reduced graphene oxide rGO, and then the target reduced graphene oxide rGO is redispersed in deionized water to obtain reduced graphene oxide aqueous solution.
3) Preparation of graphene synergistic photo-thermal energy storage composite material: 15mmol of trifluoromethylated azobenzene was uniformly dispersed in 50ml of deionized water and 75ml of 1mol L was added -1 H of (2) 2 SO 4 After stirring uniformly under ice bath conditions, 15mL of 70 mg.multidot.mL was slowly added -1 NaNO of (C) 2 The aqueous solution was stirred under ice bath conditions for 1 hour to obtain an azobenzene diazonium salt solution. Then the azobenzene diazonium salt solution was slowly dropped into the uniformly dispersed 375mL of 1 mg.mL -1 In the reduced graphene oxide aqueous solution, ice bath stirring is continued for 5 hours under the argon atmosphere, then the reaction is continued for 25 hours at 25 ℃, and finally the trifluoromethyl azobenzene is grafted on the surface of the reduced graphene oxide in a coupling mode, and an average of every 33 carbon atoms is grafted with one trifluoromethyl azobenzene molecule. And (3) after centrifuging, washing the product for a plurality of times by deionized water and acetone respectively, and then carrying out vacuum drying to obtain the graphene synergistic photo-thermal energy storage composite material. The energy density was 179.2 kJ.kg -1 。
FIG. 3 shows the preparation of any one of the above examplesNuclear magnetic spectrum of the trifluoromethylated azobenzene product. As can be seen from the figures of the drawing, 1 H NMR(400MHz,DMSO-d 6 ) Delta 12.95 (s, 1H), 8.43 (s, 1H), 8.17 (s, 1H), 7.99 (s, 1H), 6.23 (s, 2H), 3.93 (s, 6H), which have the same number and kind of hydrogen atoms in the molecule, proved successful preparation of the trifluoromethyl azobenzene compound with the structure as shown in formula (I) from the nuclear magnetism result.
Characterization is performed on the graphene synergistic photo-thermal energy storage composite material prepared in the embodiment 3. Fig. 4 is an infrared spectrum of the graphene synergistic photo-thermal energy storage composite material prepared in any of the above embodiments. The successful preparation of the target graphene synergistic photo-thermal energy storage composite material is proved by the following characteristic peaks: 3142cm -1 The absorption peak at the location is the characteristic absorption peak of-OH in-COOH, 1708cm -1 The absorption peak at the position is the characteristic absorption peak of carbonyl in-COOH and is 1399cm -1 The absorption peak at the position is a characteristic absorption peak of-N=N-, 1148cm -1 The absorption peak at this point is the characteristic absorption peak of-C-F.
In addition, as shown in fig. 2, it can be clearly seen that the graphene synergistic photo-thermal energy storage composite material prepared in example 3 has clear wrinkles, and the surface of the graphene synergistic photo-thermal energy storage composite material shows an obvious coarse structure; the surface of the reduced graphene oxide shown in fig. 1 is smoother, and the interlayer dispersibility is good, which also proves that the structure of the reduced graphene oxide is obviously changed after the reduced graphene oxide is grafted by the trifluoromethyl azobenzene, namely the trifluoromethyl azobenzene is successfully grafted to the surface of the reduced graphene oxide, and the graphene synergistic photo-thermal energy storage composite material is successfully prepared.
FIG. 5 is a differential scanning calorimetric diagram of a graphene synergistic photo-thermal energy storage composite material of example 3, from which it is seen that the material begins to release heat at 35℃and ends at 85℃and at a lower ambient temperature can begin to release all of its stored energy, and the resulting heat storage density reaches 334.5 kJ.kg -1 . The results show that the graphene synergistic photo-thermal energy storage composite material has excellent energy density and low-temperature heat release performance, and has wide application prospects in the fields of solar energy utilization and photo-thermal conversion in the future.
According to the technical parameters recorded in the invention, the preparation of the trifluoromethyl azobenzene/graphene composite material can be realized, and basically consistent energy storage and release performances are shown.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The graphene synergistic photo-thermal energy storage composite material is characterized by comprising trifluoromethyl azobenzene and reduced graphene oxide, wherein the trifluoromethyl azobenzene is grafted on the surface of a sheet layer of the reduced graphene oxide in a covalent coupling manner;
the surface of the sheet layer of the reduced graphene oxide is grafted with a trifluoromethyl azobenzene molecule every 20-40 carbon atoms on average;
the trifluoromethylated azobenzene has a structure as shown in formula (I):
2. the composite material of claim 1, wherein the trifluoromethylated azobenzene is covalently coupled grafted in an array to a platelet surface of reduced graphene oxide.
3. The composite of claim 1, wherein the graphene synergistic photo-thermal energy storage composite has a structure substantially as shown below:
4. a complex as claimed in any one of claims 1 to 3The composite material is characterized in that the energy density of the graphene synergistic photo-thermal energy storage composite material is not lower than 100 kJ.kg -1 ；
The initial exothermic temperature of the graphene synergistic photo-thermal energy storage composite material is 30-40 ℃;
the final exothermic temperature of the graphene synergistic photo-thermal energy storage composite material is 80-90 ℃.
5. The composite material of claim 4, wherein the graphene synergistic photo-thermal energy storage composite material has an energy density of 110-400 kJ-kg -1 。
6. The preparation method of the graphene synergistic photo-thermal composite energy storage material as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) Preparing an azobenzene diazonium salt solution: uniformly dispersing trifluoromethyl azobenzene in dilute sulfuric acid water solution, and adding NaNO into the solution under low temperature condition 2 Dispersing to obtain an azobenzene diazonium salt solution;
(2) Dispersing the azobenzene diazonium salt solution in a reduced graphene oxide aqueous solution, and stirring for reaction to obtain the graphene synergistic photo-thermal composite energy storage material.
7. The method according to claim 6, wherein in the step (1), the trifluoromethylated azobenzene and NaNO 2 The molar ratio of (2) is 1 (0.8-1.2);
and/or, in the step (1), the concentration of sulfuric acid in the dilute sulfuric acid aqueous solution is 0.5-3mol/L;
and/or, in step (1), the NaNO 2 Added in the form of an aqueous solution thereof;
and/or, in step (1), the trifluoromethylated azobenzene and H 2 SO 4 The molar ratio of (2.5-5) is 1;
and/or, in step (1), the low temperature condition is provided by an ice bath;
and/or, in step (1), the dispersing time is 0.5-2 hours.
8. The method according to claim 7, wherein the NaNO is 2 The aqueous solution was added in a slow drop-wise fashion.
9. The preparation method according to claim 6 or 7, wherein the preparation process of the trifluoromethylated azobenzene comprises the following steps:
(a) 3-amino-5- (trifluoromethyl) benzoic acid was mixed with dilute sulfuric acid aqueous solution, to which NaNO was slowly added 2 Dispersing the aqueous solution to obtain a diazonium salt solution;
(b) Slowly dropwise adding the diazonium salt solution into an aqueous solution of 3, 5-dimethoxy aniline, regulating the pH value of the system by using alkali after the dropwise adding is completed, and stirring for reaction to obtain a crude product of trifluoromethyl azobenzene;
(c) The crude product is purified to obtain the trifluoromethyl azobenzene.
10. The production method according to any one of claims 6 to 7, wherein in the step (2), the reduced graphene oxide is added in the form of an aqueous reduced graphene oxide solution;
and/or in the step (2), the volume ratio of the reduced graphene oxide aqueous solution to the dilute sulfuric acid aqueous solution in the step (1) is (1-7): 1;
and/or, in the step (2), stirring the reaction under an inert atmosphere;
and/or, the stirred reaction comprises two stages: a low temperature reaction stage and a room temperature reaction stage.
11. The method of claim 10, wherein the concentration of the reduced graphene oxide aqueous solution is 0.5-2mg/mL.
12. The method of claim 10, wherein the stirring reaction comprises two stages: firstly, carrying out a low-temperature reaction stage, and stirring for 3-7 hours under the ice water bath condition; and then the room temperature reaction stage is carried out, and the stirring reaction is continued for 20 to 30 hours under the room temperature condition.
13. The method according to claim 6, wherein in the step (2), the preparation process of the reduced graphene oxide comprises: and adopting sodium borohydride to perform reduction treatment on the graphene oxide, and washing to obtain the reduced graphene oxide.
14. The method according to claim 13, wherein sodium borohydride is added to an aqueous solution of graphene oxide having a pH of 8 to 10, and the reduction treatment is performed under an inert atmosphere;
the mass ratio of the graphene oxide to the sodium borohydride is 1 (5-20);
the temperature of the reduction treatment is 80-100 ℃, and the time of the reduction treatment is 1-5 hours.
15. Use of the graphene synergistic photo-thermal energy storage composite material of any one of claims 1-5 in a solar energy storage device.
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