CN111825083A - Preparation device and preparation method of highly-oriented two-dimensional nano material macroscopic body - Google Patents
Preparation device and preparation method of highly-oriented two-dimensional nano material macroscopic body Download PDFInfo
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- CN111825083A CN111825083A CN202010752073.1A CN202010752073A CN111825083A CN 111825083 A CN111825083 A CN 111825083A CN 202010752073 A CN202010752073 A CN 202010752073A CN 111825083 A CN111825083 A CN 111825083A
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Abstract
A preparation device and a preparation method of a highly oriented two-dimensional nano material macroscopic body belong to the technical field of preparation of nano material macroscopic bodies, and the specific scheme comprises the following steps: the utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body, refrigerator, freezer, temperature control system and solution tank, the solution tank communicates with the entrance point of the pump body, the exit end of the pump body and the front end intercommunication of freezer, the low slope setting in high back before the freezer, the rear end and the solution tank intercommunication of freezer, the refrigerator sets up the bottom surface that is close to or contacts the freezer in the below of freezer, temperature control system is connected with the refrigerator electricity. The invention can prepare two-dimensional nano material macroscopic bodies with different orientation degrees by controlling the temperature and the inclination angle of the freezing chamber, and regulate the size of the highly oriented two-dimensional nano material macroscopic body by regulating the size of the freezing chamber.
Description
Technical Field
The invention belongs to the technical field of preparation of nano material macroscopic bodies, and particularly relates to a preparation device and a preparation method of a highly oriented two-dimensional nano material macroscopic body.
Background
With the attention of people to light high-performance materials, in particular to aerospace and 5G fluxThe requirements of the fields of communication, wearable equipment and the like on multifunctional materials further demand the realization of the controllability of the microstructure of the light macroscopic body. Graphene is used as a two-dimensional material, has natural advantages for building a macroscopic body, has a unique hexagonal crystal structure as a novel two-dimensional nano carbon material, has high charge mobility, and moves at a speed close to light, so that the graphene becomes the current material with the maximum room-temperature conductivity. In addition to the electrical properties, each carbon atom in the graphene is combined with three surrounding carbon atoms through a strong sigma bond, so that the Young modulus is as high as 1.0TPa, and the strength is 100 times higher than that of a common steel material. In terms of thermal aspects, the thermal conductivity of graphene is mainly determined by phonon transmission, and the room temperature thermal conductivity of graphene is (4.84 +/-0.44) multiplied by 103～(5.30±0.48)×103W.m-1.K-1Theoretical thermal conductivity can reach 6000W.m-1.K-1The above. How to utilize the excellent performance of graphene becomes the key point of research of scientists, one of the strategies is to assemble graphene into a macroscopic material, so that the macroscopic material can give full play to multiple performances of the nanoscopic scale of graphene, and the preparation of a graphene macroscopic body is an effective method for realizing the practical application of graphene. Because graphene has excellent electrical, mechanical and thermal properties along a two-dimensional plane direction (in-plane), the advantages of graphene can be fully exerted only by arranging the graphene along a certain direction in a directional manner in the process of assembling the graphene into a macroscopic material.
The existing preparation methods of graphene macroscopic bodies comprise a CVD growth synthesis method, a porous polymer template method, a chemical reduction method, a hydrothermal reduction self-assembly method, a high-temperature high-pressure self-assembly method and the like. The graphene sheets can be promoted to be arranged in an oriented manner by inducing with a gradient temperature field (i.e. an ice template method), and some existing researches can regulate and control the microstructure of a graphene macroscopic body in one direction (such as a Z-axis direction) but disordered in the other two directions (XY directions).
Disclosure of Invention
The invention provides a preparation device of a highly oriented two-dimensional nanomaterial macroscopic body, aiming at realizing highly oriented arrangement of two-dimensional nanomaterials.
The second purpose of the invention is to provide a preparation method of the highly oriented two-dimensional nano material macroscopic body.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body, refrigerator, freezer, temperature control system and solution tank, the solution tank communicates with the entrance point of the pump body, the exit end of the pump body and the front end intercommunication of freezer, the low slope setting of high back before the freezer, the rear end and the solution tank intercommunication of freezer, the refrigerator sets up the bottom surface that is close to or contacts the freezer in the below of freezer, temperature control system is connected with the refrigerator electricity.
Furthermore, the inclination angle of the bottom surface of the freezing chamber is 5-80 degrees.
Furthermore, a heat conduction layer is attached to the bottom surfaces of the refrigerator and the freezing chamber.
Further, the temperature control system comprises a thermocouple and a temperature controller, the thermocouple is integrated in the heat conduction layer, and the thermocouple is electrically connected with the temperature controller.
Further, the device also comprises a cooler, and the cooler is arranged beside the refrigerator.
Further, the pump body is a peristaltic pump.
A method for preparing highly oriented two-dimensional nanomaterial macroscopic body by using the preparation device comprises the following steps:
the method comprises the following steps: preparing a two-dimensional nano material dispersion liquid;
step two: the pump body continuously conveys the two-dimensional nano material dispersion liquid in the solution tank into the freezing chamber, the two-dimensional nano material dispersion liquid flows from the front end to the rear end of the freezing chamber, the freezing chamber is continuously cooled by the refrigerator, one part of the two-dimensional nano material dispersion liquid grows a frozen mixture of two-dimensional nano materials and water which are directionally distributed on the bottom surface of the freezing chamber, and the other part of the two-dimensional nano material dispersion liquid flows to the solution tank;
step three: and (3) freeze-drying the frozen mixture of the two-dimensional nano material and water to obtain a two-dimensional nano material macroscopic body.
Further, in the first step, the prepared two-dimensional nano-material dispersion liquid is placed in an environment of 0-20 ℃ for heat balance.
Further, in the second step, the flow rate of the two-dimensional nano material dispersion liquid flowing through the freezing chamber is 0.2-3L/min.
Further, in the second step, the initial temperature of the freezing chamber is-2 to-20 ℃, and after the rate of the two-dimensional nano-material dispersion liquid flowing through the freezing chamber is stable, the refrigerator cools at the rate of 0.2-5 ℃/min.
Further, in the third step, the conditions of freeze drying are as follows: under the vacuum condition, the temperature is uniformly raised from minus 20 ℃ to minus 10 ℃ within 36 to 48 hours, then the temperature is uniformly raised from minus 10 ℃ to minus 2 ℃ within 90 to 150 hours, then the temperature is uniformly raised from minus 2 ℃ to 30 ℃ within 24 to 48 hours, and the drying is carried out for 48 to 100 hours at the temperature of 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed any more.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation device of the highly oriented two-dimensional nanomaterial macroscopic body is suitable for ordered assembly of any two-dimensional nanomaterial macroscopic body, and has a wide application range.
2. The invention can prepare two-dimensional nanomaterial macrostructures with different orientation degrees by controlling the temperature and the inclination angle of the freezing chamber.
3. The invention can regulate the size of the highly oriented two-dimensional nano material macroscopic body by regulating the size of the freezing chamber.
4. The invention prepares the two-dimensional nanometer material macroscopic body by the preparation device of the highly oriented two-dimensional nanometer material macroscopic body, and the refrigerator provides an upward temperature gradient (static temperature field) for the freezing chamber to realize the oriented arrangement in the Z-axis direction; the liquid flow provides a shearing driving force, the temperature of flowing liquid is relatively high when the flowing liquid just contacts the freezing chamber, the flowing liquid gradually flows downwards, the contact time with the freezing chamber is increased, the temperature is gradually reduced, a dynamic temperature gradient is formed in the flowing direction of the liquid, and under the combined action of the dynamic temperature gradient and hydromechanics, the two-dimensional nano material sheets are directionally arranged along the flowing direction of the liquid (XY direction), so that two-dimensional nano material macroscopic bodies which are directionally arranged in three directions are creatively prepared, and the excellent two-dimensional performance of the two-dimensional nano material can be furthest exerted.
On the basis of an ice template method, based on the idea of hydrodynamics, a flow shearing force is introduced in the direction vertical to the temperature gradient, and the two-dimensional nano material can be directionally arranged in three directions of XYZ under the synergistic action of hydrodynamics and a bidirectional temperature field, and a two-dimensional nano material macroscopic body can be expanded in a larger axial (Z-axis direction) size.
Drawings
FIG. 1 is a schematic structural diagram of a device for preparing a highly oriented two-dimensional nanomaterial macroscopic body;
FIG. 2 is a schematic view showing the construction of the manufacturing apparatus in which the inclination angle of the freezing chamber is 80 °;
FIG. 3 is a schematic view showing the construction of the manufacturing apparatus in which the inclination angle of the freezing chamber is 30 °;
in fig. 4, a) is a temperature distribution diagram of a macroscopic body of graphene grown in a freezing chamber; b) is a temperature gradient plot in the direction of L1 perpendicular to the surface of the graphene macroscopic body; c) is a flow temperature gradient plot in the direction L2 parallel to the surface of the graphene macroscopic body;
FIG. 5 is a schematic diagram of the principle of assembly of highly oriented two-dimensional nanomaterial macros;
FIG. 6 is a schematic diagram of an ice mixture of graphene oxide and water prepared in example 1;
FIG. 7 is SEM images of graphene macros prepared in examples 1-3, and a1-a3) are SEM images of graphene macros obtained in example 1; b1-b3) is a SEM image of a graphene macroscopic body obtained in example 2; c1-c3) are SEM images of the graphene macrostructures obtained in example 3.
In the figure: 1. the pump body, 2, the refrigerator, 3, the freezer, 4, temperature control system, 5, solution tank, 6, pipeline I, 7, pipeline II, 8, heat-conducting layer, 9, cooler.
Detailed Description
The technical scheme of the invention is explained in detail with reference to the accompanying drawings 1-7 and the embodiment.
Detailed description of the invention
The utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body 1, refrigerator 2, freezer 3, temperature control system 4 and solution tank 5, solution tank 5 passes through pipeline I6 and the entrance point intercommunication of the pump body 1, the exit end of the pump body 1 passes through pipeline II 7 and the front end intercommunication of freezer 3, 3 high back low slopes before the freezer set up, the rear end setting of freezer 3 is in the top of solution tank 5 and with solution tank 5 intercommunication, refrigerator 2 sets up the bottom surface that is close to or contacts freezer 3 in the below of freezer 3, temperature control system 4 is connected with 2 electricity of refrigerator. The refrigerator 2 is a semiconductor refrigeration sheet or a liquid nitrogen refrigeration device. Preferably, the semiconductor refrigeration piece is two double-layer semiconductor refrigeration pieces connected in parallel. The cross-sectional shape of the freezing chamber 3 is square or round, the freezing chamber 3 is made of acrylic materials, plastic materials or the thermal conductivity of 0.01-1Wm-1K-1The low thermal conductivity material of (2).
Further, the inclination angle of the bottom surface of the freezing chamber 3 is 5-80 degrees. Namely, the included angle between the bottom surface of the freezing chamber 3 and the horizontal plane is 5-80 degrees.
Further, a heat conduction layer 8 is arranged between the refrigerator 2 and the bottom surface of the freezing chamber 3 through heat conduction silicone grease, and the heat conduction layer 8 is an aluminum plate, a copper plate or a heat conduction layer with the heat conductivity between 10 and 500W m-1K-1Any other sheet of high thermal conductivity material.
Further, the temperature control system 4 includes a thermocouple and a temperature controller, the thermocouple is integrated inside the heat conduction layer 8, the thermocouple is electrically connected with the temperature controller, and the thermocouple is used for measuring the temperature of the heat conduction layer 8 in real time and controlling the voltage of the refrigerator through the temperature controller so as to control the refrigeration power thereof.
Further, the device also comprises a cooler 9, wherein the cooler 9 is arranged beside the refrigerator 2, heat generated by the refrigerator 2 is taken away through the cooler 9, and preferably, the cooler 9 is a water cooling bar.
Further, the pump body 1 is a peristaltic pump or any other device capable of providing power to the liquid to make the liquid flow, and the peristaltic pump conveys the liquid in the solution tank 5 to the freezing chamber.
Detailed description of the invention
A method for preparing highly oriented two-dimensional nanomaterial macroscopic body by using the preparation device of the first embodiment comprises the following steps:
the method comprises the following steps: preparing a two-dimensional nano material dispersion liquid, and placing the prepared two-dimensional nano material dispersion liquid in an environment of 0-20 ℃ for heat balance;
step two: under the temperature environment for carrying out solution heat balance, the pump body 1 continuously conveys the two-dimensional nano material dispersion liquid in the solution tank 5 into the freezing chamber 3, the two-dimensional nano material dispersion liquid flows from the front end to the rear end of the freezing chamber 3, the refrigerator 2 continuously cools the freezing chamber 3, a gradient temperature field (the temperature is gradually reduced from top to bottom) provided by the refrigerator 2 realizes the stable growth of ice crystals, the directional arrangement of two-dimensional nano material sheets is realized under the action of fluid shearing force, one part of the two-dimensional nano material dispersion liquid grows on the bottom surface of the freezing chamber 3 and has a certain thickness of a frozen mixture of two-dimensional nano materials and water which are directionally arranged, the other part flows to the solution tank 5, and the two-dimensional nano material dispersion liquid is continuously conveyed into the freezing chamber 3 through the pump body 1 to; the flow rate of the two-dimensional nano material dispersion liquid flowing through the freezing chamber 3 is 0.2-3L/min, the initial temperature of the freezing chamber 3 is-2 to-20 ℃, and after the flow rate of the two-dimensional nano material dispersion liquid flowing through the freezing chamber 3 is stable, the refrigerator 2 is cooled at the rate of 0.2-5 ℃/min.
Step three: freeze-drying the frozen mixture of the two-dimensional nano material and water to obtain a two-dimensional nano material macroscopic body; the conditions for freeze-drying were: under the vacuum condition, the temperature is uniformly increased from minus 20 ℃ to minus 10 ℃ within 36 to 48 hours, then the temperature is uniformly increased from minus 10 ℃ to minus 2 ℃ within 90 to 150 hours, then the temperature is uniformly increased from minus 2 ℃ to 30 ℃ within 24 to 48 hours, and the drying is carried out for 48 to 100 hours at the temperature of 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed (indicating complete drying).
Further, the two-dimensional nano material is graphene oxide, graphene, boron nitride, transition metal sulfide, layered metal oxide or layered double hydroxide.
In order to realize the height-oriented arrangement of the two-dimensional nano material sheets, the invention introduces the shearing driving force of solution flow on the basis of unidirectional freezing of the bottom surface of the freezing chamber 3 from top to bottom, and under the synergistic action of the shearing driving force and a bidirectional temperature field, the two-dimensional nano material can realize the height-oriented arrangement of three directions of an X-Y-Z axis, and the invention adjusts the orientation degree of a macroscopic body of the two-dimensional nano material by adjusting the initial temperature of the refrigerator 2, the cooling rate of the refrigerator 2, the inclination angle of the freezing chamber 3, the peristaltic rate of a peristaltic pump, the concentration of a two-dimensional nano material dispersion liquid and the like.
Detailed description of the invention
A method for preparing a graphene macroscopic body by using the apparatus according to the first embodiment of the present invention includes steps of firstly, preparing a graphene oxide dispersion solution and performing thermal equilibrium, then, performing ordered assembly on the graphene oxide macroscopic body by using the apparatus for preparing a highly oriented two-dimensional nanomaterial macroscopic body, then, freeze-drying, and finally, performing chemical vapor reduction to obtain a highly oriented graphene macroscopic body, which specifically includes the following steps:
the method comprises the following steps: preparing a graphene oxide dispersion liquid and carrying out thermal balance: dispersing a graphene oxide solution with the lamella size of 5-10 microns and the concentration of 10-20mg/ml in deionized water to prepare a graphene oxide dispersion liquid with the thickness of 5-15mg/ml, carrying out ultrasonic treatment on the graphene oxide dispersion liquid at the frequency of 10 KHz-100 KHz for 30-60 min, and then placing the graphene oxide dispersion liquid in an environment with the temperature of 0-20 ℃ for thermal equilibrium;
step two: under the temperature environment for heat balance of dispersion liquid, the pump body 1 conveys graphene oxide dispersion liquid in the solution tank 5 into the freezing chamber 3, the graphene oxide dispersion liquid flows from the front end to the rear end of the freezing chamber 3, the freezing chamber 3 is continuously cooled by the refrigerator 2, a gradient temperature field (the temperature is gradually reduced from top to bottom) provided by the refrigerator 2 realizes stable growth of ice crystals, directional arrangement of graphene oxide sheet layers is realized under the action of fluid shearing force, a part of the graphene oxide dispersion liquid grows on the bottom surface of the freezing chamber 3 and has a certain thickness of a frozen mixture of the graphene oxide and water which are directionally arranged, the other part of the graphene oxide dispersion liquid flows to the solution tank 5, and the flow rate of the graphene oxide dispersion liquid flowing through the freezing chamber 3 is 0.2-3L/min; the initial temperature of the freezing chamber 3 is-2 to-20 ℃, and after the speed of the graphene oxide dispersion liquid flowing through the freezing chamber 3 is stable, the refrigerator 2 is cooled at the speed of 0.2-5 ℃/min;
step three: freezing and drying the frozen mixture of the graphene oxide and water to obtain a graphene oxide macroscopic body; the conditions for freeze-drying were: uniformly heating from-20 ℃ to-10 ℃ within 36-48h under a vacuum condition, then uniformly heating from-10 ℃ to-2 ℃ within 90-150h, then uniformly heating from-2 ℃ to 30 ℃ within 24-48h, drying for 48-100h at 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed, and obtaining a graphene oxide macroscopic body after complete drying;
step four: reducing the graphene oxide macroscopic body to obtain a graphene macroscopic body: and (2) putting the freeze-dried graphene oxide macroscopic body into a closed container filled with hydrazine hydrate, putting the graphene oxide macroscopic body on a net rack with holes above the hydrazine hydrate, heating for 24 hours at the temperature of 90-100 ℃ without contacting the hydrazine hydrate, and removing oxygen-containing functional groups of the graphene oxide to obtain the graphene oxide macroscopic body.
Further, the graphene oxide dispersion liquid in the first step is prepared by a chemical method, and the preparation method specifically comprises the following steps: weighing 4g of flake graphite, placing the flake graphite in a beaker, pouring 400-500 ml of concentrated sulfuric acid and 40-50 ml of phosphoric acid into the beaker to prepare a mixed solution I, and stirring for 30-60 min at room temperature; placing the beaker in a water bath for heating in the water bath, adding 16-20 g of potassium permanganate into the mixed solution I respectively for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 60-70 ℃, taking out the mixed solution II after 10-20 hours, and cooling at room temperature; after cooling to room temperature, slowly pouring the mixed solution II into 600-700 ml of hydrogen peroxide mixed ice water, standing for 20-30 h, filtering out the supernatant, taking the lower layer solution, carrying out centrifugal washing on the lower layer solution for 2-3 times by using hydrochloric acid (HCl) with the mass fraction of 5%, then carrying out centrifugal washing on the lower layer solution for 2-3 times by using an ethanol solution, and finally washing by using deionized water to obtain a high-concentration graphene oxide solution; and finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion solution with the concentration of (5-15) mg/mL for later use. The preparation method of 600-700 ml of hydrogen peroxide mixed ice water comprises the steps of dissolving 6-7 ml of 30% hydrogen peroxide in water to form 600-700 ml of mixed solution III, and freezing the mixed solution III in a refrigerator in a subzero environment to obtain the hydrogen peroxide mixed ice water.
Example 1
The utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body 1, refrigerator 2, freezer 3, temperature control system 4 and solution tank 5, solution tank 5 passes through the entrance point intercommunication of pipeline I6 and pump body 4, the exit end of pump body 4 passes through the front end intercommunication of pipeline II 7 with freezer 3, 3 high back low slopes before the freezer set up, the rear end and the solution tank 5 intercommunication of freezer 3, refrigerator 2 sets up the bottom surface that is close to or contacts freezer 3 in the below of freezer 3, temperature control system 4 is connected with 2 electricity of refrigerator. The refrigerator 2 is a semiconductor refrigerating piece which is a rectangular 6cm by 12cm double-layer semiconductor refrigerating piece formed by two parallel 60W double-layer semiconductor refrigerating pieces 6cm by 6 cm. The freezing chamber 3 is an acrylic square tube, the size of the inner section of the freezing chamber is 3.5cm multiplied by 5cm, and the wall thickness is 0.5 mm.
Further, the bottom surface of the freezing chamber 3 is inclined at an angle of 5 °.
Further, be provided with heat-conducting layer 8 through the laminating of heat conduction silicone grease between the bottom surface of refrigerator 2 and freezer 3, heat-conducting layer 8 is 2 mm's aluminum plate for thickness.
Further, the temperature control system 4 comprises a PT100 thermocouple and a temperature controller, the PT100 thermocouple is integrated inside the heat conducting layer, the PT100 thermocouple is electrically connected with the temperature controller, and the PT100 thermocouple is used for measuring the temperature of the heat conducting layer 8 in real time and controlling the voltage of the refrigerator 2 through the temperature controller so as to control the refrigerating power of the refrigerator.
Further, the device also comprises a cooler 9, wherein the cooler 9 is arranged beside the refrigerator 2, heat generated by the refrigerator 2 is taken away through the cooler 9, and preferably, the cooler 9 is a water cooling bar.
Further, the pump body 1 is a peristaltic pump, and the peristaltic pump conveys the liquid in the solution tank 5 to the freezing chamber 3.
The method for preparing the highly-oriented graphene macroscopic body by using the preparation device of the highly-oriented two-dimensional nanomaterial macroscopic body comprises the following steps:
step one, preparing graphene oxide dispersion liquid and carrying out thermal equilibrium:
preparing a graphene oxide dispersion liquid by a chemical method: weighing 4g of flake graphite, placing the flake graphite in a beaker, pouring 450ml of concentrated sulfuric acid and 50ml of phosphoric acid into the beaker to prepare a mixed solution I, and stirring the mixed solution I at room temperature for 40 min. And (3) placing the beaker in a water bath for heating in the water bath, adding 18g of potassium permanganate into the mixed solution I respectively for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out the mixed solution II after 16 hours, and cooling the mixed solution at room temperature. And after cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24h, filtering out the supernatant, and taking the lower layer solution for centrifugal washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion solution with the concentration of 5mg/mL for later use. And (3) placing the prepared graphene oxide dispersion liquid in an environment of 1 ℃ for heat balance. The preparation method of 700ml of hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment to be frozen to obtain the hydrogen peroxide mixed ice water.
Step two, orderly assembling of graphene oxide:
in an environment of 1 ℃, pouring the graphene oxide dispersion liquid with uniform temperature after thermal equilibrium into a solution tank 5, setting the bottom surface of a freezing chamber 3 and a horizontal plane to form an included angle of 5 degrees, adjusting a peristaltic pump to convey the graphene oxide dispersion liquid to an acrylic square tube above a refrigerator 2 through the peristaltic pump with adjustable speed for freezing, wherein a part of the graphene oxide dispersion liquid grows on the bottom surface of the acrylic square tube to form a frozen mixture of graphene oxide and water which are directionally arranged at a certain thickness, as shown in fig. 4, the rest of the dispersion liquid flows back to the solution tank 5 to continue to circulate through the peristaltic pump, and the flow rate of the graphene oxide dispersion liquid through the freezing chamber 3 is controlled to be 3L/min. The initial temperature of the refrigerator 2 is-2 ℃, and after the flow velocity of the graphene oxide dispersion liquid is stable in the acrylic square tube, the refrigerator 2 is cooled at the speed of 0.2 ℃/min, so that ice crystals stably grow, and finally the frozen mixture of the graphene oxide and water is obtained.
Step three, freeze drying: putting the frozen mixture of the graphene oxide and water into a freeze dryer, wherein the freeze drying conditions are as follows: uniformly heating from-20 ℃ to-10 ℃ within 36h under a vacuum condition, then uniformly heating from-10 ℃ to-2 ℃ within 90h, uniformly heating from-2 ℃ to 30 ℃ within 36h, drying for 48h at 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed (indicating complete drying), and obtaining a graphene oxide macroscopic body after complete drying;
step four, chemical steam reduction: and (2) putting the freeze-dried graphene oxide macroscopic body into a closed container filled with hydrazine hydrate, putting the graphene oxide macroscopic body on a net rack with holes above the hydrazine hydrate (similar to steamed bread), heating for 24 hours at the temperature of 100 ℃ without contacting with the hydrazine hydrate, and removing oxygen-containing functional groups of the graphene oxide to obtain the highly oriented graphene macroscopic body.
Fig. 7a1-a3 are scanning electron micrographs of microstructures of the graphene macrosome obtained in this example, and it can be seen that, under the combined action of the refrigerator 2 and the solution flowing shear force, the samples are highly oriented in three directions.
The samples were tested for mechanical compression and thermal conductivity. In the X, Y and Z directions, the compression strength is 2.9KPa, 1.9KPa and 0.85KPa when the deformation is 30%, the compression strength is 3.5KPa, 2.2KPa and 1.2KPa when the deformation is 50%, the compression strength is 6.3KPa, 5.4KPa and 2.9KPa when the deformation is 70%, and the thermal conductivity is 0.019W m-1K-1,0.018W m-1K-1And 0.012W m-1K-1The method embodies that the highly oriented graphene macroscopic body has anisotropy, and fully embodies the high orientation of the material.
Example 2
The utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body 1, refrigerator 2, freezer 3, temperature control system 4 and solution tank 5, solution tank 5 passes through pipeline I6 and the entrance point intercommunication of the pump body 1, the exit end of the pump body 1 passes through pipeline II 7 and the front end intercommunication of freezer 3, 3 high back low slopes before the freezer set up, the rear end and the solution tank 5 intercommunication of freezer 3, refrigerator 2 sets up the bottom surface that is close to or contacts freezer 3 in the below of freezer 3, temperature control system 4 is connected with 2 electricity of refrigerator. The refrigerator 2 is a semiconductor refrigerating piece which is a rectangular 6cm by 12cm double-layer semiconductor refrigerating piece formed by two parallel 60W double-layer semiconductor refrigerating pieces 6cm by 6 cm. The freezing chamber 3 is an acrylic square tube, the size of the inner section of the freezing chamber is 3.5cm multiplied by 5cm, and the wall thickness is 0.5 mm.
Further, the inclination angle of the freezing chamber 3 is 80 °.
Further, be provided with heat-conducting layer 8 through the laminating of heat conduction silicone grease between the bottom surface of refrigerator 2 and freezer 3, heat-conducting layer 8 is 2 mm's aluminum plate for thickness.
Further, the temperature control system 4 comprises a PT100 thermocouple and a temperature controller, the PT100 thermocouple is integrated inside the heat conducting layer 8, the PT100 thermocouple is electrically connected with the temperature controller, and the PT100 thermocouple is used for measuring the temperature of the heat conducting layer 8 in real time and controlling the voltage of the refrigerator 2 through the temperature controller so as to control the refrigerating power of the refrigerator.
Further, the device also comprises a cooler 9, wherein the cooler 9 is arranged beside the refrigerator 2, heat generated by the refrigerator 2 is taken away through the cooler 9, and preferably, the cooler 9 is a water cooling bar.
Further, the pump body 1 is a peristaltic pump, and the peristaltic pump conveys the liquid in the solution tank 5 to the freezing chamber 3.
The method for preparing the highly-oriented graphene macroscopic body by using the preparation device of the highly-oriented two-dimensional nanomaterial macroscopic body comprises the following steps:
step one, preparing graphene oxide dispersion liquid and carrying out thermal equilibrium:
preparing a graphene oxide dispersion liquid by a chemical method: weighing 4g of flake graphite, placing the flake graphite in a beaker, pouring 450ml of concentrated sulfuric acid and 50ml of phosphoric acid into the beaker to prepare a mixed solution I, and stirring the mixed solution I at room temperature for 40 min. And (3) placing the beaker in a water bath for heating in the water bath, adding 18g of potassium permanganate into the mixed solution I respectively for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out the mixed solution II after 16 hours, and cooling the mixed solution at room temperature. And after cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24 hours, filtering out the supernatant, and taking the lower layer solution for centrifugal washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide in deionized water to obtain graphene oxide dispersion liquid with the concentration of 8mg/mL for later use. And (3) placing the prepared graphene oxide dispersion liquid in an environment of 1 ℃ for heat balance. The preparation method of 700ml of hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment to be frozen to obtain the hydrogen peroxide mixed ice water.
Step two, orderly assembling of graphene oxide:
and pouring the graphene oxide dispersion liquid with uniform temperature after thermal equilibrium into the solution tank 5 in an environment of 1 ℃. The included angle of the freezing chamber 3 and the horizontal plane is set to be 80 degrees, the peristaltic pump is adjusted, graphene oxide dispersion liquid is conveyed to an acrylic square tube above the refrigerator 2 through the peristaltic pump with adjustable speed to be frozen, a frozen mixture of graphene oxide and water which are directionally arranged in a certain thickness is grown on the bottom surface of the acrylic square tube by a part of the graphene oxide dispersion liquid, the rest of the dispersion liquid flows back to the solution tank 5 to continue to circulate through the peristaltic pump, and the flow rate of the graphene oxide dispersion liquid flowing through the freezing chamber 3 is controlled to be 0.2L/min. The initial temperature of the refrigerator is-20 ℃, and after the flow velocity of the graphene oxide dispersion liquid is stabilized in the acrylic square tube, the refrigerator 2 is cooled at the speed of 5 ℃/min, so that ice crystals grow stably, and finally the frozen mixture of the graphene oxide and water is obtained.
Step three, freeze drying: putting the frozen mixture of the graphene oxide and water into a freeze dryer, wherein the freeze drying conditions are as follows: under the vacuum condition, uniformly heating from-20 ℃ to-10 ℃ within 48h, then uniformly heating from-10 ℃ to-2 ℃ within 150h, uniformly heating from-2 ℃ to 30 ℃ within 24h, drying for 100h at 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed (indicating complete drying), and obtaining a graphene oxide macroscopic body after complete drying;
step four, chemical steam reduction: and (2) putting the freeze-dried graphene oxide macroscopic body into a closed container filled with hydrazine hydrate, putting the graphene oxide macroscopic body on a net rack with holes above the hydrazine hydrate (similar to steamed bread), heating for 24 hours at 90 ℃ without contacting with the hydrazine hydrate, and removing oxygen-containing functional groups of the graphene oxide to obtain the highly oriented graphene macroscopic body.
Fig. 7b1-b3 are scanning electron micrographs of microstructures of the graphene macrosome obtained in this example, and it can be seen that the samples are highly oriented in three directions under the combined action of the refrigerator and the solution flowing shear force.
The samples were tested for mechanical compression and thermal conductivity. In the X, Y and Z directions, the compressive strength is 5.3KPa, 2.2KPa and 1.9KPa when the deformation is 30%, the compressive strength is 7.1KPa, 5.2KPa and 3.5KPa when the deformation is 50%, the compressive strength is 16.9KPa when the deformation is 70%, and the thermal conductivity is 0.021W m when the deformation is 14.3KPa and 6.8KPa-1K-1,0.019W m-1K-1And 0.015W m-1K-1The method embodies that the highly oriented graphene macroscopic body has anisotropy, and fully embodies the high orientation of the material.
Example 3
The utility model provides a preparation facilities of high directional two dimension nano-material macroscopic body, includes the pump body 1, refrigerator 2, freezer 3, temperature control system 4 and solution tank 5, solution tank 5 passes through pipeline I6 and the entrance point intercommunication of the pump body 1, the exit end of the pump body 1 passes through pipeline II 7 and the front end intercommunication of freezer 3, 3 high back low slopes before the freezer set up, the rear end and the solution tank 5 intercommunication of freezer 3, refrigerator 2 sets up the bottom surface that is close to or contacts freezer 3 in the below of freezer 3, temperature control system 4 is connected with 2 electricity of refrigerator. The refrigerator 2 is a semiconductor refrigerating piece which is a rectangular 6cm by 12cm double-layer semiconductor refrigerating piece formed by two parallel 60W double-layer semiconductor refrigerating pieces 6cm by 6 cm. The freezing chamber 3 is an acrylic square tube, the size of the inner section of the freezing chamber is 3.5cm multiplied by 5cm, and the wall thickness is 0.5 mm.
Further, the bottom surface of the freezing chamber 3 is inclined at an angle of 30 °.
Further, be provided with heat-conducting layer 8 through the laminating of heat conduction silicone grease between the bottom surface of refrigerator 2 and freezer 3, heat-conducting layer 8 is 2 mm's aluminum plate for thickness.
Further, the temperature control system 4 comprises a PT100 thermocouple and a temperature controller, the PT100 thermocouple is integrated inside the heat conducting layer, the PT100 thermocouple is electrically connected with the temperature controller, and the PT100 thermocouple is used for measuring the temperature of the heat conducting layer 8 in real time and controlling the voltage of the refrigerator 2 through the temperature controller so as to control the refrigerating power of the refrigerator.
Further, the device also comprises a cooler 9, wherein the cooler 9 is arranged beside the refrigerator 2, heat generated by the refrigerator 2 is taken away through the cooler 9, and preferably, the cooler 9 is a water cooling bar.
Further, the pump body 1 is a peristaltic pump, and the peristaltic pump conveys the liquid in the solution tank 5 to the freezing chamber 3.
The method for preparing the highly-oriented graphene macroscopic body by using the preparation device of the highly-oriented two-dimensional nanomaterial macroscopic body comprises the following steps:
step one, preparing graphene oxide dispersion liquid and carrying out thermal equilibrium:
preparing a graphene oxide dispersion liquid by a chemical method: weighing 4g of flake graphite, placing the flake graphite in a beaker, pouring 450ml of concentrated sulfuric acid and 50ml of phosphoric acid into the beaker to prepare a mixed solution I, and stirring the mixed solution I at room temperature for 40 min. And (3) placing the beaker in a water bath for heating in the water bath, adding 18g of potassium permanganate into the mixed solution I respectively for 8 times to obtain a mixed solution II, heating the mixed solution II at a constant temperature of 70 ℃, taking out the mixed solution II after 16 hours, and cooling the mixed solution at room temperature. And after cooling to room temperature, slowly pouring the mixed solution II into 700ml of hydrogen peroxide mixed ice water, standing for 24h, filtering out the supernatant, and taking the lower layer solution for centrifugal washing to obtain the high-concentration graphene oxide solution. And finally dispersing the washed high-concentration graphene oxide solution in deionized water to obtain a graphene oxide dispersion liquid with the concentration of 15mg/mL for later use, and placing the prepared graphene oxide dispersion liquid in an environment at 1 ℃ for thermal equilibrium. The preparation method of 700ml of hydrogen peroxide mixed ice water comprises the steps of dissolving 6ml of hydrogen peroxide solution with the mass fraction of 30% in water to form 700ml of mixed solution III, and placing the mixed solution III in a refrigerator in a subzero environment for freezing to obtain the hydrogen peroxide mixed ice water.
Step two, orderly assembling of graphene oxide:
in the environment of 1 ℃, the graphene oxide dispersion liquid with uniform temperature after thermal balance is poured into a solution tank 5, an included angle of 30 degrees is formed between a freezing chamber 3 and the horizontal plane, a peristaltic pump is adjusted, the graphene oxide dispersion liquid is conveyed to an acrylic square tube above a refrigerator 2 through the peristaltic pump with adjustable speed for freezing, wherein a part of the graphene oxide dispersion liquid grows on the bottom surface of the acrylic square tube to form a frozen mixture of graphene oxide and water which are directionally arranged at a certain thickness, the rest of the dispersion liquid flows back to the solution tank 5 to continue to circulate through the peristaltic pump, and the flow rate of the graphene oxide dispersion liquid flowing through the freezing chamber 3 is controlled to be 0.5L/min. The initial temperature of the refrigerator 2 is-5 ℃, and after the flow velocity of the graphene oxide dispersion liquid is stabilized in the acrylic square tube, the refrigerator 2 is cooled at the speed of 1 ℃/min to ensure that ice crystals stably grow, and finally the frozen mixture of the graphene oxide and water is obtained.
Step three, freeze drying: putting the frozen mixture of the graphene oxide and water into a freeze dryer, wherein the freeze drying conditions are as follows: under the vacuum condition, the temperature is uniformly increased from minus 20 ℃ to minus 10 ℃ within 42h, then the temperature is uniformly increased from minus 10 ℃ to minus 2 ℃ within 120h, the temperature is uniformly increased from minus 2 ℃ to 30 ℃ within 36h, and the drying is carried out for 60h at the temperature of 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed (indicating complete drying). Completely drying to obtain a graphene oxide macroscopic body;
step four, chemical steam reduction: and (2) putting the freeze-dried graphene oxide macroscopic body into a closed container filled with hydrazine hydrate, putting the graphene oxide macroscopic body on a net rack with holes above the hydrazine hydrate (similar to steamed bread), heating for 24 hours at the temperature of 95 ℃ without contacting with the hydrazine hydrate, and removing oxygen-containing functional groups of the graphene oxide to obtain the highly oriented graphene macroscopic body.
Fig. 7c1-c3 are scanning electron micrographs of microstructures of the graphene macrosome obtained in this example, and it can be seen that, under the combined action of the refrigerator 2 and the solution flowing shear force, the samples are highly oriented in three directions.
The samples were tested for mechanical compression and thermal conductivity. In X, Y and Z directions, the compressive strength is 15.1KPa, 9.8KPa and 5.1KPa when the deformation is 30%, the compressive strength is 18.1 KPa, 13.2KPa and 6.9KPa when the deformation is 50%, the compressive strength is 29.1KPa when the deformation is 70%, the thermal conductivity is 0.025W m when the deformation is 28.3KPa and 11.2KPa-1K-1,0.023W m-1K-1And 0.018W m-1K-1The method embodies that the highly oriented graphene macrostructure has anisotropy, and fully embodies the high orientation of the material.
The above-described embodiments are merely illustrative of the present invention and do not limit the scope thereof, and those skilled in the art may make partial changes therein without departing from the spirit of the invention and it is intended to cover all equivalent modifications of the invention within the scope thereof.
Claims (11)
1. A preparation device of a highly oriented two-dimensional nano material macroscopic body is characterized in that: including the pump body (1), refrigerator (2), freezer (3), temperature control system (4) and solution tank (5), solution tank (5) and the entrance point intercommunication of the pump body (1), the exit end of the pump body (1) and the front end intercommunication of freezer (3), the low slope setting in high back before freezer (3), the rear end and the solution tank (5) intercommunication of freezer (3), refrigerator (2) set up the bottom surface that is close to or contacts freezer (3) in the below of freezer (3), temperature control system (4) are connected with refrigerator (2) electricity.
2. The apparatus for preparing highly oriented two-dimensional nano material macroscopic body as recited in claim 1, wherein: the inclination angle of the bottom surface of the freezing chamber (3) is 5-80 degrees.
3. The apparatus for preparing highly oriented two-dimensional nano material macroscopic body as recited in claim 1, wherein: and a heat conduction layer (8) is attached between the bottom surfaces of the refrigerator (2) and the freezing chamber (3).
4. The apparatus for preparing highly oriented two-dimensional nano material macroscopic body as recited in claim 3, wherein: the temperature control system (4) comprises a thermocouple and a temperature controller, the thermocouple is integrated in the heat conduction layer (8), and the thermocouple is electrically connected with the temperature controller.
5. The apparatus for preparing highly oriented two-dimensional nano material macroscopic body as recited in claim 1, wherein: the device also comprises a cooler (9), and the cooler (9) is arranged beside the refrigerator (2).
6. The apparatus for preparing highly oriented two-dimensional nano material macroscopic body as recited in claim 1, wherein: the pump body (1) is a peristaltic pump.
7. A method for preparing highly oriented two-dimensional nanomaterial macroscopic body by using the preparation apparatus of any one of claims 1 to 6, characterized in that: the method comprises the following steps:
the method comprises the following steps: preparing a two-dimensional nano material dispersion liquid;
step two: the pump body (1) continuously conveys the two-dimensional nano material dispersion liquid in the solution tank (5) into the freezing chamber (3) and flows from the front end to the rear end of the freezing chamber (3), the refrigerator (2) continuously cools the freezing chamber (3), a part of the two-dimensional nano material dispersion liquid grows a frozen mixture of two-dimensional nano materials and water which are directionally arranged on the bottom surface of the freezing chamber (3), and the other part of the two-dimensional nano material dispersion liquid flows to the solution tank (5);
step three: and (3) freeze-drying the frozen mixture of the two-dimensional nano material and water to obtain a two-dimensional nano material macroscopic body.
8. The method of claim 7, wherein: in the first step, the prepared two-dimensional nano material dispersion liquid is placed in an environment of 0-20 ℃ for heat balance.
9. The method of claim 7, wherein: in the second step, the flow speed of the two-dimensional nano material dispersion liquid flowing through the freezing chamber (3) is 0.2-3L/min.
10. The method of claim 7, wherein: in the second step, the initial temperature of the freezing chamber (3) is-2 to-20 ℃, and after the two-dimensional nano material dispersion liquid flows through the freezing chamber (3) at a stable speed, the refrigerator (2) is cooled at a speed of 0.2-5 ℃/min.
11. The method of claim 7, wherein: in the third step, the freeze-drying conditions are as follows: under the vacuum condition, the temperature is uniformly raised from minus 20 ℃ to minus 10 ℃ within 36 to 48 hours, then the temperature is uniformly raised from minus 10 ℃ to minus 2 ℃ within 90 to 150 hours, then the temperature is uniformly raised from minus 2 ℃ to 30 ℃ within 24 to 48 hours, and the drying is carried out for 48 to 100 hours at the temperature of 30 ℃ until the vacuum degree in the cavity of the freeze dryer is not changed any more.
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