CN113173864A - 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 PDF

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CN113173864A
CN113173864A CN202011193448.1A CN202011193448A CN113173864A CN 113173864 A CN113173864 A CN 113173864A CN 202011193448 A CN202011193448 A CN 202011193448A CN 113173864 A CN113173864 A CN 113173864A
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graphene oxide
aqueous solution
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azobenzene
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赵建国
杨翔宇
李世杰
刘锐
邢宝岩
张进
潘启亮
陕多亮
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Shanxi Datong University
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Abstract

The invention discloses a graphene synergistic photothermal energy storage composite material and a preparation method and application thereof. The composite material comprises trifluoromethylated azobenzene and reduced graphene oxide, wherein the trifluoromethylated azobenzene is grafted on the surface of a sheet layer of the reduced graphene oxide in a covalent coupling mode. The graphene synergistic photothermal energy storage composite material at least has low-temperature heat release performance and excellent energy storage density, is greatly improved in low-temperature heat release and energy density compared with the traditional trifluoromethylated azobenzene molecules, and has wide application prospects in the fields of solar energy utilization and photothermal conversion in the future.

Description

Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof
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 abundant content, and has the outstanding advantages of low price, safety, environmental protection, inexhaustibility and the like. With the continuous advance of modernization, the demand of various industries on energy sources is continuously increased, the traditional series of fossil fuels cannot adapt to the huge problem of the current energy source demand, and a series of problems such as climate change, environmental deterioration and the like caused by the fossil fuels also enable countries in the world to reduce the dependence on the fossil fuels step by step, so that various clean and renewable energy sources are vigorously developed. Among a series of clean energy sources, the development and utilization of solar energy have recently been receiving increased research and attention from people around the world. Under the background, the development and utilization of solar energy are increased, which is one of the key subjects of the current research in China, and particularly, the intensive research on the aspects of conversion and storage between solar energy and heat energy has important practical application value.
The Jeffrey C.Grossman topic group of the Massachusetts institute of technology elaborates the Mechanism of dihydroazene-vinyl heptene (DHA-VHF) as a photoisomerizable responsive material and its potential for use in photothermal storage (Kanai, Y., Srinivasan, V., Meier, S.K., Vollhardt, K.P.C.and Grossman, J.C. (2010), Mechanism of Thermal recovery of the (Fulvalene) tetrachloro titanium photosynthesis: heated Molecular solvent-Thermal Energy storage, Angewandte chemical International Edition,49: 8926-8929). However, the energy density of the material is low, and the practical application cost is high. In addition, CN110305635A discloses a shaped heat storage material and a method for preparing the same, which has the advantages of a wide range of heat storage applications, but the material uses graphene as an auxiliary material, and does not use the excellent heat conductivity of graphene.
Azobenzene is one of photosensitive dyes and photoresponse materials which are widely researched, and in recent years, researchers have attracted more and more research and attention in the field of solar heat storage. Azobenzene has both cis and trans isomers. The isomerization conversion phenomenon that the trans-configuration is changed into the cis-configuration can occur under the illumination of specific wavelength; then, under the action of external stimuli (such as light irradiation and heating), the isomerization reversion phenomenon of changing from cis configuration to trans configuration can occur. The difference of certain energy exists between two different isomers of azobenzene, and certain energy can be stored in a chemical energy mode in the process of transition from a trans configuration to a cis configuration, and conversely, the stored energy can be released in the form of heat in the process of transition from the cis configuration to the trans configuration.
In the prior art, azobenzene grafted graphene composite energy storage materials are available, but the heat release temperature of the energy storage material is as high as 80 ℃, so that the heat release of the material under a low external temperature condition is greatly limited. Therefore, it is an urgent technical problem to provide an azobenzene grafted graphene composite material having at least low-temperature heat release performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a graphene synergistic photothermal energy storage composite material, which comprises trifluoromethylated azobenzene and reduced graphene oxide, wherein the trifluoromethylated azobenzene is grafted on the surface of a reduced graphene oxide sheet in a covalent coupling mode.
According to an embodiment of the present invention, the sheet surface of the reduced graphene oxide is grafted with one trifluoromethylazobenzene molecule per 20 to 40 carbon atoms on average; for example, on average, one trifluoromethylazobenzene molecule per 25 to 35 carbon atoms; also for example, on average, one trifluoromethylazobenzene molecule is grafted per 27 to 32 carbon atoms. Illustratively, on average, one trifluoromethylazobenzene molecule is grafted per 20, 22, 24, 25, 26, 28, 30, 31, 32, 33, 34, 35, 37, 39, or 40 carbon atoms.
According to an embodiment of the present invention, the trifluoromethylated azobenzenes are covalently coupled and grafted on the surface of the reduced graphene oxide sheet in an array form.
According to an embodiment of the present invention, the trifluoromethylazobenzene has a structure as shown in formula (I):
Figure BDA0002753378930000031
according to an embodiment of the invention, the graphene synergistic photothermal energy storage composite material has a structure substantially as shown in the following:
Figure BDA0002753378930000032
according to the embodiment of the invention, the energy density of the graphene synergistic photothermal energy storage composite material is not lower than 100 kJ-kg-1For example, an energy density of 110--1Exemplary 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 the embodiment of the invention, the heat release temperature span range (referring to the temperature difference range from the beginning of heat release to the end of heat release) of the graphene synergistic photo-thermal energy storage composite material is 40-60 ℃, for example 42-58 ℃, exemplary 45 ℃, 50 ℃ and 55 ℃.
According to an embodiment of the invention, the initial heat release temperature of the graphene synergistic photothermal energy storage composite material is 30-40 ℃, such as 32-38 ℃, and exemplary is 30 ℃, 32 ℃, 34 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃.
According to an embodiment of the invention, the graphene synergistic photothermal energy storage composite material has an exothermic termination temperature of 80-90 ℃, such as 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) preparation of azobenzene diazonium salt solution: uniformly dispersing trifluoromethylazobenzene in dilute sulfuric acid aqueous solution, and adding NaNO into the dilute sulfuric acid aqueous solution at low temperature2Dispersing to obtain azobenzene diazonium salt solution;
(2) and dispersing the azobenzene diazonium salt solution into 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 NaNO2The molar ratio of (A) to (B) is 1 (0.8-1.2), preferably 1: 1. Preferably, the trifluoromethylazobenzene is used in an amount of 3 to 15 parts by mole, for example 4 to 12 parts by mole, illustratively 3 parts by mole, 5 parts by mole, 6 parts by mole, 8 parts by mole, 10 parts by mole.
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 to 3mol/L, such as 1 to 2 mol/L.
According to an embodiment of the invention, in step (1), the NaNO is2Added in the form of an aqueous solution thereof, preferably, NaNO2The aqueous solution was added in a slowly dropwise fashion. For example, NaNO2NaNO in aqueous solution2Is 50-100mg/mL, such as 60-90mg/mL, exemplary 60mg/mL, 70mg/mL, 80mg/mL, 90 mg/mL.
According to an embodiment of the present invention, in step (1), the trifluoromethylated azobenzene and H2SO4In a molar ratio of 1 (2.5-5), such as 1 (3-4), illustratively 1:2.5, 1: 3.5.
According to an embodiment of the invention, in step (1), the cryogenic conditions are provided by an ice bath.
According to an embodiment of the invention, in step (1), the time of said dispersing is between 0.5 and 2 hours, for example 1 hour. Preferably, the dispersion is a stirring dispersion so that the trifluoromethylated azobenzene is uniformly dispersed in the dilute sulfuric acid aqueous solution.
According to an embodiment of the present invention, the preparation process of the trifluoromethylated azobenzene comprises the steps of:
(a) 3-amino-5- (trifluoromethyl) benzoic acid was mixed with dilute aqueous sulfuric acid solution, to which NaNO was slowly added2Dispersing the aqueous solution to obtain a diazonium salt solution;
(b) slowly dripping the diazonium salt solution into the aqueous solution of the 3, 5-dimethoxyaniline, adjusting the pH of the system by using alkali after finishing dripping, and stirring for reaction to obtain a crude product of the trifluoromethylated azobenzene;
(c) and purifying the crude product to obtain the trifluoromethylated azobenzene.
Preferably, in step (a), the molar ratio of 3-amino-5- (trifluoromethyl) benzoic acid to sodium nitrite is 1 (0.9-2), e.g. 1 (1-1.5); for example, 3-amino-5- (trifluoromethyl) benzoic acid is used in an amount of 3 to 25 molar parts, such as 5 to 20 molar parts, illustratively 5 molar parts, 7 molar parts, 10 molar parts;
preferably, in step (a), H is added to a mixture of 3-amino-5- (trifluoromethyl) benzoic acid and dilute aqueous sulfuric acid2SO4And 3-amino-5- (trifluoromethyl) benzoic acid in a molar ratio of 1 (5-10), preferably 1 (2-8), e.g. 1:5, 1:6, 1:7, 1: 8;
preferably, H in said dilute aqueous sulfuric acid solution2SO4Is in the range of 0.3 to 1mol/L, for example 0.5 mol/L.
Preferably, in step (a), the time of dispersion is 0.5 to 2 hours, for example 1 hour.
Preferably, in step (a), the NaNO is2The addition of the aqueous solution and the dispersion to give the diazonium salt solution are carried out at low temperatures, preferably at low temperatures provided by an ice bathUnder the condition of the reaction.
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 and the like, preferably sodium hydroxide; preferably, the base is added as a basic solution; preferably, the concentration of the alkali is 0.5-1 mol/L;
preferably, in step (b), the pH of the system is adjusted to 4-6;
preferably, in the 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 diazonium salt solution is slowly added dropwise to the aqueous solution of 3, 5-dimethoxyaniline and the reaction is stirred at a low temperature, preferably 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 employ purification methods known in the art, such as column chromatography separation.
The preparation route of trifluoromethylazobenzene is as follows:
Figure BDA0002753378930000061
according to an embodiment of the present invention, in the step (2), the reduced graphene oxide is added in the form of an aqueous solution of reduced graphene oxide. Preferably, the concentration of the reduced graphene oxide aqueous solution is 0.5-2mg/mL, such as 1 mg/mL.
According to an embodiment of the present invention, in the step (2), the stirring reaction is performed 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, a low temperature reaction stage is performed, and the mixture is stirred for 3 to 7 hours, such as 5 hours, under the ice-water bath condition; the reaction is then continued at room temperature with stirring for 20-30 hours, for example 25 hours, at room temperature.
According to an embodiment of the present invention, in the step (2), the preparation process of the reduced graphene oxide includes: and (3) reducing the graphene oxide by using sodium borohydride, 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 the graphene oxide to the sodium borohydride is 1 (5-20), such as 1 (7-15), exemplarily 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 "mole fraction" may refer to 1mmol or 1 mol.
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 photothermal energy storage composite material is prepared by grafting trifluoromethylated azobenzene to the surface of reduced graphene oxide in a covalent coupling mode. Observing the structure of the material by a scanning electron microscope to find that the trifluoromethylated azobenzene molecules are successfully grafted on the surface of the reduced graphene oxide. The graphene synergistic photothermal energy storage composite material at least has low-temperature heat release performance and excellent energy storage density, is greatly improved in low-temperature heat release and energy density compared with the traditional trifluoromethylated azobenzene molecules, and has wide application prospects in the fields of solar energy utilization and photothermal 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 micrograph of the graphene synergistic photothermal energy storage composite material prepared by the invention.
FIG. 3 is a nuclear magnetic characterization map of the trifluoromethylated azobenzene compound prepared by the present invention.
FIG. 4 is an infrared characterization map of the graphene synergistic photothermal energy storage composite material prepared by the invention.
Fig. 5 is a differential scanning calorimetry thermogram of the graphene synergistic photothermal energy storage composite material prepared by the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the synthesis process of the trifluoromethylated azobenzene, the equivalent and 2 equivalents are respectively one time and 2 times of the molar weight of the 3-amino-5- (trifluoromethyl) benzoic acid based on the molar weight of the 3-amino-5- (trifluoromethyl) benzoic acid.
Energy density test 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 with a 365nm LED light source for energy storage. After the energy storage was complete, the test was performed by DSC. The DSC was first set to 10 ℃ and stabilized for 15 minutes, after which the entire energy density testing process was completed by heating to 140 ℃ at a ramp rate of 10 ℃/min.
Example 1
1) 5mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and uniformly dispersed in 10ml of deionized water, and 50ml of 0.5 mol.L is added-1H of (A) to (B)2SO4The solution was stirred well in an ice bath, and 5mL of 70mg/mL solution was slowly added-1NaNO of (2)2Dissolving in waterThe solution is stirred for 1 hour under ice bath condition to obtain diazonium salt solution. The diazonium salt solution was then slowly added dropwise to an aqueous solution of 0.765g of 3, 5-dimethoxyaniline, followed by 0.5 mol. L-1Adjusting the pH value of the system to 4 by using NaOH aqueous solution, continuously stirring in an ice bath for 1 hour under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate to obtain a crude trifluoromethylated azobenzene product. And (4) performing column chromatography separation on the crude product to obtain a final trifluoromethylated azobenzene product.
2) Preparing reduced graphene oxide: with saturated NaHCO3300mL of 1mg/mL aqueous solution-1Adjusting the pH value of the uniformly dispersed graphene oxide aqueous solution to 9, performing ultrasonic treatment for 2 hours to uniformly disperse the uniformly dispersed graphene oxide aqueous solution, adding 2.7g of sodium borohydride, reacting for 2 hours under the argon atmosphere and at 85 ℃, washing the product for 3 times respectively by using deionized water ionized water and absolute ethyl alcohol to obtain a 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) Preparing a graphene synergistic photo-thermal energy storage composite material: 3mmol of trifluoromethylazobenzene was uniformly dispersed in 10ml of deionized water, and 7.5ml of 1 mol. L was added-1H of (A) to (B)2SO4After stirring uniformly under ice bath condition, 3mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution is stirred for 1 hour under the ice bath condition to obtain azobenzene diazonium salt solution. Then slowly dropwise adding azobenzene diazonium salt solution into uniformly dispersed 75mL of 1mg/mL-1In the reduced graphene oxide aqueous solution, continuously stirring in an ice bath for 1 hour under the argon atmosphere, then continuously reacting for 5 hours at 25 ℃, finally grafting the trifluoromethylazobenzene to the surface of the reduced graphene oxide in a covalent coupling mode, and grafting one trifluoromethylazobenzene molecule on average per 37 carbon atoms. And (3) respectively washing the product for multiple times by deionized water and acetone after centrifugation, and then carrying out vacuum drying to obtain the graphene synergistic photothermal energy storage composite material. The energy density is 129.3 kJ.kg-1。
Example 2
1) Weighing 10mmol of 3-amino-5- (trifluoromethyl) benzoic acid, uniformly dispersing in20ml of deionized water and 60ml of 0.5 mol.L-1H of (A) to (B)2SO4The solution was stirred well in an ice bath, and 12mL of 70mg/mL solution was slowly added-1NaNO of (2)2Aqueous solution, and stirring for 1 hour under ice bath conditions to obtain a diazonium salt solution. The diazonium salt solution was then slowly added dropwise to an aqueous solution of 1.53g of 3, 5-dimethoxyaniline, followed by 0.6 mol. L-1Adjusting the pH value of the system to 4.5 by using NaOH aqueous solution, continuously stirring in an ice bath for 2 hours in an argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate to obtain a crude trifluoromethylazobenzene product. And (4) performing column chromatography separation on the crude product to obtain a final trifluoromethylated azobenzene product.
2) Preparing reduced graphene oxide: with saturated NaHCO3450mL of the aqueous solution was mixed at 1mg/mL-1Adjusting the pH value of the uniformly dispersed graphene oxide aqueous solution to 9, performing ultrasonic treatment for 2 hours to uniformly disperse the uniformly dispersed graphene oxide aqueous solution, adding 3.15g of sodium borohydride, reacting for 3 hours under the argon atmosphere and at 90 ℃, washing the product for 3 times respectively by deionized water ionized water and absolute ethyl alcohol to obtain a 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) Preparing a graphene synergistic photo-thermal energy storage composite material: 6mmol of trifluoromethylazobenzene is uniformly dispersed in 20ml of deionized water and 18ml of 1 mol.L is added-1H of (A) to (B)2SO4After stirring uniformly under ice bath condition, 6mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution is stirred for 1 hour under the ice bath condition to obtain azobenzene diazonium salt solution. Then slowly dropwise adding the azobenzene diazonium salt solution into the uniformly dispersed 150mL of 1mg/mL-1In the reduced graphene oxide aqueous solution, continuously stirring in an ice bath for 2 hours under the argon atmosphere, then continuously reacting for 10 hours at 25 ℃, finally grafting trifluoromethylazobenzene to the surface of the reduced graphene oxide in a coupling mode, grafting one trifluoromethylazobenzene molecular product to each 28 carbon atoms on average, washing the product for multiple times by deionized water and acetone after centrifugation, and then carrying out vacuum drying to obtain the graphene synergistic photothermal energy storage composite material. Energy ofDensity 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, 105ml of 0.5 mol.L are added-1H of (A) to (B)2SO4The solution was stirred well in an ice bath, and then 21mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution was stirred under ice bath conditions for 1 hour to obtain a diazonium salt solution. The diazonium salt solution was then slowly added dropwise to 2.295g of an aqueous solution of 3, 5-dimethoxyaniline, followed by 0.7 mol.L-1Adjusting the pH value of the system to 5 by using NaOH aqueous solution, continuously stirring in an ice bath for 3 hours in an argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate to obtain a crude trifluoromethylated azobenzene product. And (4) performing column chromatography separation on the crude product to obtain a final trifluoromethylated azobenzene product.
2) Preparing reduced graphene oxide: with saturated NaHCO3450mL of the aqueous solution was mixed at 1mg/mL-1Adjusting the pH value of the uniformly dispersed graphene oxide aqueous solution to 9, performing ultrasonic treatment for 2 hours to uniformly disperse the uniformly dispersed graphene oxide aqueous solution, adding 3.15g of sodium borohydride, reacting for 3 hours under the argon atmosphere and at 90 ℃, washing the product for 3 times respectively by deionized water ionized water and absolute ethyl alcohol to obtain a 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) Preparing a graphene synergistic photo-thermal energy storage composite material: dispersing 9mmol of trifluoromethylazobenzene in 30ml of deionized water uniformly, and adding 31.5ml of 1 mol.L-1H of (A) to (B)2SO4After stirring the mixture evenly in an ice bath, 9mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution is stirred for 1 hour under the ice bath condition to obtain azobenzene diazonium salt solution. Then slowly dropwise adding azobenzene diazonium salt solution into uniformly dispersed 225mL of 1mg/mL-1In the reduced graphene oxide aqueous solution, continuously stirring in an ice bath for 3 hours under the argon atmosphere, continuously reacting for 15 hours at 25 ℃, and finally grafting trifluoromethylazobenzene to the surface of the reduced graphene oxide in a coupling mode, wherein average grafting is carried out on every 22 carbon atomsOne trifluoromethylated azobenzene molecule. And (3) respectively washing the product for multiple times by deionized water and acetone after centrifugation, and then carrying out vacuum drying to obtain the graphene synergistic photothermal energy storage composite material. The energy density is 334.5kJ kg-1。
Example 4
1) 20mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and uniformly dispersed in 40ml of deionized water, 160ml of 0.5 mol.L are added-1H of (A) to (B)2SO4The solution was stirred uniformly in an ice bath, and 36mL of 70mg/mL solution was slowly added-1NaNO of (2)2Aqueous solution, and stirring for 1 hour under ice bath conditions to obtain a diazonium salt solution. The diazonium salt solution was then slowly added dropwise to an aqueous solution of 3.06g of 3, 5-dimethoxyaniline, followed by 0.8 mol.L-1Adjusting the pH value of the system to 5.5 by using NaOH aqueous solution, continuously stirring in an ice bath for 4 hours under the argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate to obtain a crude trifluoromethylazobenzene product. And (4) performing column chromatography separation on the crude product to obtain a final trifluoromethylated azobenzene product.
2) Preparing reduced graphene oxide: with saturated NaHCO3600mL of the aqueous solution was mixed and adjusted to 1mg/mL-1Adjusting the pH value of the uniformly dispersed graphene oxide aqueous solution to 9, performing ultrasonic treatment for 2 hours to uniformly disperse the uniformly dispersed graphene oxide aqueous solution, adding 5.4g of sodium borohydride, reacting for 4 hours under the argon atmosphere and at 95 ℃, washing the product for 3 times respectively by using deionized water ionized water and absolute ethyl alcohol to obtain a 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) Preparing a graphene synergistic photo-thermal energy storage composite material: uniformly dispersing 12mmol of trifluoromethylazobenzene in 40ml of deionized water, and adding 48ml of 1 mol.L-1H of (A) to (B)2SO4After stirring uniformly under ice bath condition, 12mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution is stirred for 1 hour under the ice bath condition to obtain azobenzene diazonium salt solution. Then slowly dropwise adding azobenzene diazonium salt solution into uniformly dispersed 300mL of 1mg/mL-1In the reduced graphene oxide aqueous solution of (a), under an argon atmosphereAnd (2) continuously carrying out ice bath and stirring for 4 hours, then continuously reacting for 20 hours at 25 ℃, finally grafting the trifluoromethylazobenzene to the surface of the reduced graphene oxide in a coupling mode, centrifuging and washing with deionized water and acetone for multiple times after grafting one trifluoromethylazobenzene molecular product to every 31 carbon atoms on average, and then carrying out vacuum drying to obtain the graphene synergistic photo-thermal energy storage composite material. The energy density is 221.5kJ kg-1。
Example 5
1) 25mmol of 3-amino-5- (trifluoromethyl) benzoic acid are weighed out and uniformly dispersed in 50ml of deionized water, and 250ml of 0.5 mol.L is added-1H of (A) to (B)2SO4The solution was stirred well in an ice bath, and 50mL of 70mg/mL solution was slowly added-1NaNO of (2)2Aqueous solution, and stirring for 1 hour under ice bath conditions to obtain a diazonium salt solution. The diazonium salt solution was then slowly added dropwise to an aqueous solution of 3.825g of 3, 5-dimethoxyaniline, followed by 1 mol. L-1Adjusting the pH value of the system to 6 by using NaOH aqueous solution, continuously stirring in an ice bath for 5 hours in an argon atmosphere, standing after the reaction is finished, and performing vacuum filtration to obtain a precipitate to obtain a crude trifluoromethylated azobenzene product. And (4) performing column chromatography separation on the crude product to obtain a final trifluoromethylated azobenzene product.
2) Preparing reduced graphene oxide: with saturated NaHCO3The aqueous solution was mixed with 750mL of 1mg/mL-1Adjusting the pH value of the uniformly dispersed graphene oxide aqueous solution to 9, performing ultrasonic treatment for 2 hours to uniformly disperse the uniformly dispersed graphene oxide aqueous solution, adding 7.5g of sodium borohydride, reacting for 5 hours under the condition of argon atmosphere and 100 ℃, washing the product for 3 times respectively by deionized water ionized water and absolute ethyl alcohol to obtain a 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) Preparing a graphene synergistic photo-thermal energy storage composite material: uniformly dispersing 15mmol of trifluoromethylazobenzene in 50ml of deionized water, and adding 75ml of 1 mol.L-1H of (A) to (B)2SO4After stirring uniformly under ice bath condition, 15mL of 70mg/mL solution was slowly added-1NaNO of (2)2The aqueous solution was stirred under ice-bath conditions for 1 hourTo obtain azobenzene diazonium salt solution. Then slowly dropping azobenzene diazonium salt solution into 375mL of evenly dispersed 1mg/mL-1In the reduced graphene oxide aqueous solution, continuously stirring in an ice bath for 5 hours under the argon atmosphere, then continuously reacting for 25 hours at 25 ℃, finally grafting the trifluoromethylazobenzene to the surface of the reduced graphene oxide in a coupling mode, and grafting one trifluoromethylazobenzene molecule on average per 33 carbon atoms. And (3) respectively washing the product for multiple times by deionized water and acetone after centrifugation, and then carrying out vacuum drying to obtain the graphene synergistic photothermal energy storage composite material. The energy density is 179.2 kJ.kg-1。
FIG. 3 is a nuclear magnetic spectrum of a trifluoromethylated azobenzene product prepared in any of the above examples. As can be seen from the figures, it is,1H NMR(400MHz,DMSO-d6) Delta 12.95(s,1H),8.43(s,1H),8.17(s,1H),7.99(s,1H),6.23(s,2H) and 3.93(s,6H), wherein the number and the type of hydrogen atoms in the molecule are consistent, and the nuclear magnetic results prove that the trifluoromethylazobenzene compound has the structure shown in the formula (I).
The graphene synergistic photothermal energy storage composite material prepared in example 3 is characterized. Fig. 4 is an infrared spectrum of the graphene synergistic photothermal energy storage composite material prepared in any of the above embodiments. The target graphene synergistic photothermal energy storage composite material is successfully prepared from the following characteristic peaks: 3142cm-1The absorption peak at (b) is the characteristic absorption peak of-OH in-COOH at 1708cm-1The absorption peak at position (D) is a characteristic absorption peak of carbonyl in-COOH of 1399cm-1The absorption peak at (A) is a characteristic absorption peak of-N-1148 cm-1The absorption peak is the characteristic absorption peak of-C-F.
In addition, as shown in fig. 2, it can be clearly seen that the graphene synergistic photothermal energy storage composite material prepared in example 3 has clear wrinkles, and the surface thereof shows a significant rough structure; the surface of the reduced graphene oxide shown in fig. 1 is smooth, 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 trifluoromethylated azobenzene, that is, the trifluoromethylated 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 calorimetry thermogram of the graphene synergistic photothermal energy storage composite material in example 3, and it can be seen from the thermogram that the material starts to release heat at 35 ℃ and finishes releasing heat at 85 ℃, the total release of stored energy can be started at a lower external temperature, and the obtained 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.
The preparation of the trifluoromethylated azobenzene/graphene composite material can be realized by adjusting the process parameters recorded in the content of the invention, and the trifluoromethylated azobenzene/graphene composite material shows basically consistent energy storage and release performances.
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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The graphene synergistic photothermal energy storage composite material is characterized by comprising trifluoromethylated azobenzene and reduced graphene oxide, wherein the trifluoromethylated azobenzene is grafted on the surface of a reduced graphene oxide sheet in a covalent coupling mode.
2. The composite material according to claim 1, wherein the sheet surface of the reduced graphene oxide is grafted with one trifluoromethylazobenzene molecule per 20 to 40 carbon atoms on average.
Preferably, the trifluoromethylazobenzene is covalently coupled and grafted on the surface of the reduced graphene oxide sheet in an array form.
Preferably, the trifluoromethylazobenzene has a structure as shown in formula (I):
Figure FDA0002753378920000011
3. the composite material of claim 1 or 2, wherein the graphene enhanced photothermal energy storage composite material has a structure substantially as shown in the following:
Figure FDA0002753378920000012
4. the composite material of any one of claims 1-3, wherein the graphene enhanced photothermal energy storage composite material has an energy density of not less than 100 kJ-kg-1For example, an energy density of 110--1。
Preferably, the heat release temperature span range of the graphene synergistic photothermal energy storage composite material is 40-60 ℃.
Preferably, the initial heat release temperature of the graphene synergistic photo-thermal energy storage composite material is 30-40 ℃.
Preferably, the terminating exothermic temperature of the graphene synergistic photo-thermal energy storage composite material is 80-90 ℃.
5. The preparation method of the graphene synergistic photothermal composite energy storage material as described in any one of claims 1 to 4, wherein the preparation method comprises the following steps:
(1) preparation of azobenzene diazonium salt solution: uniformly dispersing trifluoromethylazobenzene in dilute sulfuric acid aqueous solution, and adding NaNO into the dilute sulfuric acid aqueous solution at low temperature2Dispersing to obtain azobenzene diazonium salt solution;
(2) and dispersing the azobenzene diazonium salt solution into a reduced graphene oxide aqueous solution, and stirring for reaction to obtain the graphene synergistic photo-thermal composite energy storage material.
6. The method according to claim 5, wherein the reaction mixture is heated to a temperature in the reaction mixtureIn the step (1), the trifluoromethylated azobenzene and NaNO2The molar ratio of (1) to (0.8-1.2).
Preferably, in the step (1), the concentration of the sulfuric acid in the dilute sulfuric acid aqueous solution is 0.5-3 mol/L.
Preferably, in step (1), the NaNO is2Added in the form of an aqueous solution thereof, preferably, NaNO2The aqueous solution was added in a slowly dropwise fashion.
Preferably, in step (1), the trifluoromethylated azobenzene and H2SO4The molar ratio of (1) to (2.5-5).
Preferably, in step (1), the cryogenic conditions are provided by an ice bath.
Preferably, in step (1), the dispersion time is 0.5 to 2 hours.
7. The method according to claim 5 or 6, wherein the trifluoromethylated azobenzene is prepared by a process comprising the steps of:
(a) 3-amino-5- (trifluoromethyl) benzoic acid was mixed with dilute aqueous sulfuric acid solution, to which NaNO was slowly added2Dispersing the aqueous solution to obtain a diazonium salt solution;
(b) slowly dripping the diazonium salt solution into the aqueous solution of the 3, 5-dimethoxyaniline, adjusting the pH of the system by using alkali after finishing dripping, and stirring for reaction to obtain a crude product of the trifluoromethylated azobenzene;
(c) and purifying the crude product to obtain the trifluoromethylated azobenzene.
8. The production method according to any one of claims 5 to 7, wherein in the step (2), the reduced graphene oxide is added in the form of an aqueous solution of the reduced graphene oxide. Preferably, the concentration of the reduced graphene oxide aqueous solution is 0.5-2 mg/mL.
Preferably, 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.
Preferably, 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, a low-temperature reaction stage is firstly carried out, and the mixture is stirred for 3 to 7 hours under the condition of ice-water bath; then the reaction is carried out at room temperature, and the reaction is continued to be stirred for 20 to 30 hours at room temperature.
9. The method according to any one of claims 5 to 8, wherein in the step (2), the process for preparing the reduced graphene oxide comprises: and (3) reducing the graphene oxide by using sodium borohydride, and washing to obtain the reduced graphene oxide.
Preferably, sodium borohydride is added to the aqueous solution of graphene oxide with the pH of 8-10, and reduction treatment is carried out under an inert atmosphere.
Preferably, the mass ratio of the graphene oxide to the sodium borohydride is 1 (5-20).
Preferably, the temperature of the reduction treatment is 80 to 100 ℃ and the time of the reduction treatment is 1 to 5 hours.
10. Use of the graphene enhanced photo-thermal energy storage composite material according to any one of claims 1 to 4 in a solar energy storage device.
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