CN112480717B - Method for preparing core-shell structure nano composite particles by aerogel method - Google Patents
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Abstract
A method for preparing core-shell structure nano composite particles by an aerogel method, belonging to the field of preparation of core-shell structure nano composite particles. The invention aims to solve the problem of easy communication of a two-dimensional nano material in a dielectric composite material and the problem of dispersibility of a second-phase filler in a ferroelectric polymer substrate. The method comprises the following steps: firstly, preparing barium titanate nano particles and graphene oxide into dispersion liquid; and then placing the core-shell structure nano composite particles in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops, then entering a high-temperature area of a tubular furnace under the drive of carrier gas, quickly drying the small liquid drops at the temperature of 500-800 ℃, carrying out suction filtration on the small liquid drops to a receiving film of a receiver, and taking down the particles to obtain the core-shell structure nano composite particles. The invention can be used in the field of dielectric energy storage.
Description
Technical Field
The invention belongs to the field of preparation of core-shell structure nano composite particles; in particular to a method for preparing core-shell structure nano composite particles by an aerogel method.
Background
With the development of science and technology, non-renewable energy sources such as fossil fuels are increasingly exhausted, and in order to realize effective utilization of new energy sources, more efficient, more stable and cheaper energy storage technologies need to be developed; the dielectric capacitor is concerned about due to high energy density and millisecond-level charge-discharge time, and has wide application prospects in the fields of vehicle acceleration, power grid frequency modulation and the like; however, the low energy density of the dielectric capacitor limits the further development of the dielectric capacitor, and in the research of improving the energy storage density, the multiphase composite ferroelectric polymer composite material becomes the most commonly used material system, but when the second phase particles are two-dimensional nano materials, the two-dimensional nano materials are easy to communicate, and the second phase particles can cause the increase of film defects and the increase of loss.
Disclosure of Invention
The invention aims to solve the problem of easy communication of a two-dimensional nano material in a dielectric composite material and the problem of dispersibility of a second-phase filler in a ferroelectric polymer substrate; and provides a method for preparing the core-shell structure nano composite particles by an aerogel method.
In order to solve the technical problems, the method for preparing the core-shell structure nano composite particles by the aerogel method comprises the following steps:
mixing barium titanate nanoparticles with deionized water, performing ultrasonic dispersion at 0-5 ℃ for 30-90 min, adding graphene oxide, and performing ultrasonic dispersion at 0-5 ℃ for 15-30 min to obtain a dispersion liquid;
and step two, placing the dispersion liquid obtained in the step one in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops, then entering a high-temperature area of a tubular furnace under the drive of carrier gas, quickly drying at 500-800 ℃, then carrying out suction filtration on the small liquid drops to a receiving film of a receiver, and taking down the particles to obtain the core-shell structure nano composite particles.
Further limiting, in the first step, the mass ratio of the graphene oxide to the barium titanate nanoparticles is (0.5-4): 1; further limited, the total mass fraction of the graphene oxide and the barium titanate nanoparticles in the dispersion liquid is 0.05-0.2%.
Further limited, in the first step, the lateral dimension of the graphene oxide is 2-20 μm, and the thickness is 1-50 nm.
Further, the particle size of the barium titanate nanoparticles in the first step is 10nm to 500 nm.
Further limiting, the ultrasonic power in the step one is 450W-900W.
The method can adopt nano particles of magnesium oxide, silicon oxide, titanium oxide, hafnium oxide, nickel oxide, aluminum oxide, nano gold, nano silver or barium strontium titanate to replace the barium titanate nano particles in the step one.
According to the invention, graphene or MXene can be adopted to replace the graphene oxide nanosheet in the first step.
Further limit, the particle diameter of the small liquid drops in the step two is 5-20 μm.
Further limiting, in the step two, the carrier gas is high-purity nitrogen (nitrogen with the mass purity of more than or equal to 99.999%) or high-purity argon (argon with the mass purity of more than or equal to 99.999%), and the speed of the carrier gas is 0.5L/min-2L/min.
Further, the receiving film in the second step is one of a silicon wafer, ITO glass, copper foil, an alumina filter membrane, foamed nickel, carbon cloth, porous polycarbonate and a PTFE film.
And further limiting, the material of the atomizing cup in the second step is organic glass, quartz glass or common glass.
The graphene oxide used in the invention can be prepared by the following steps:
firstly, preparing 60-98% concentrated sulfuric acid by mass percent, adding graphite, and uniformly stirring; adding potassium persulfate and phosphorus pentoxide into the mixed solution, uniformly stirring, standing, reacting at 60-90 ℃ for 1-2 h, and carrying out heat insulation cooling on the obtained dark green mixture to room temperature; then adding deionized water, uniformly stirring, and standing for 12-36 h to obtain standing liquid;
the volume ratio of the mass of the potassium persulfate to the volume of the concentrated sulfuric acid is 1g (1-10) mL; the mass ratio of the potassium persulfate to the phosphorus pentoxide is 1 (0.5-1.5); the mass ratio of the potassium persulfate to the graphite is 1 (1-3); the volume ratio of the mass of the graphite to the volume of the deionized water is 1g (100-1000) mL;
pouring out the supernatant of the standing liquid, taking out the precipitate, adding deionized water, stirring uniformly, filtering water by using a suction filter, adding deionized water again for washing, filtering, and repeating the above operations until the filtered water is neutral; then drying the obtained product at 60-80 ℃ to obtain pre-oxidized graphite;
thirdly, under the stirring condition, adding pre-oxidized graphite into 60-98 mass percent concentrated sulfuric acid precooled to minus 10-0 ℃, slowly adding potassium permanganate after uniform dispersion, heating to 30-40 ℃, stirring and reacting for 1-3 h, adding deionized water and 10-30 mass percent hydrogen peroxide into reaction liquid after reaction is finished, stirring until the solution is bright yellow, and centrifuging at low speed for 30-90 min to obtain a crude product;
the volume ratio of the mass of the pre-oxidized graphite to the concentrated sulfuric acid is 1g (20-30) mL; the mass ratio of the pre-oxidized graphite to the potassium permanganate is 1 (2-5); the volume ratio of the mass of the pre-oxidized graphite to the deionized water is 1g (100-150) mL; the volume ratio of the pre-oxidized graphite to hydrogen peroxide with the mass percent of 10-30% is 1g (1-10) mL; the low-speed centrifugation speed is 1000 r/min-3000 r/min;
adding the crude product into a hydrochloric acid solution with the mass fraction of 5% -15% for cleaning, centrifuging at low speed to obtain a precipitate, cleaning twice with hydrochloric acid, cleaning with deionized water until the supernatant obtained by centrifuging is neutral, and finally putting the cleaned product into a dialysis bag for dialysis for 10-45 days to obtain a graphene oxide solution;
the volume ratio of the mass of the crude product to the hydrochloric acid is 1g (50-100) mL; the volume ratio of the mass of the crude product to the deionized water is 1g (50-100) mL.
The second step of the invention is carried out in the following aerogel device:
bending a pipe:
the bent pipe consists of two parts of quartz glass pipes, and the main pipe is communicated with the side pipe;
the outer diameter of the main pipe is 20 mm-100 mm, and the length of the main pipe is 600 mm-1500 mm; the wall thickness of the main pipe is 1 mm-5 mm; the outer diameter of the side pipe is 10 mm-50 mm; the length of the side pipe is 30 mm-200 mm; the wall thickness of the side pipe is 1 mm-5 mm;
② atomizing cup:
the atomizing cup is made of organic glass, quartz glass or common glass; the atomizing cup is cylindrical and comprises two parts, namely a cup top and a cup body; the middle of the top of the atomizing cup is provided with a hole and is connected with a hollow bent pipe; a small hole is formed in the position, close to the middle, of the top of the atomizing cup; the atomizing cup has no cup bottom, the side surface of the cup body is provided with an opening and is connected with an outer spiral hollow tube, and the outer spiral hollow tube is connected with an air pipe; the two-phase dispersion liquid is filled in the atomizing cup, and the cup bottom is supported by a polymer film; the polymer film at the bottom of the atomizing cup is fixed by a flange; the bottom flange of the atomizing cup is in a ring shape;
the diameter of the atomizing cup body is 30 mm-100 mm, and the wall thickness is 2 mm-5 mm; the diameter of an opening in the middle of the cup cover of the atomizing cup is 5-25 mm; the hollow bent pipe is made of organic glass, quartz glass or common glass; the outer diameter of a hollow elbow connected with the cup cover of the atomizing cup is 5-25 mm; the wall thickness of a hollow elbow connected with the cup cover of the atomizing cup is 1-5 mm; the diameter of a small hole formed in any position of the cup cover of the atomizing cup is 2-15 mm; the height of the atomizing cup body is 50 mm-200 mm; the height of the opening on the side surface of the atomizing cup body is 25-150 mm away from the cup cover; the diameter of the opening on the side surface of the atomizing cup body is 5-10 mm; the inner diameter of a flange ring at the bottom of the atomizing cup is 26-96 mm; the outer diameter of the flange ring at the bottom of the atomizing cup is 40-110 mm; the diameter of a flange screw hole at the bottom of the atomizing cup is 4-8 mm;
③ receiver:
the receiver is made of stainless steel or quartz glass; the receiver is of a disc shape; the bottom of the disc is provided with a hole and is connected with hollow pipes made of the same material; the disc and the hollow pipe are connected in a welding mode; the tail end of the hollow pipe is provided with an external thread; the external thread is connected with a straight-through pneumatic joint; the pneumatic joint is connected with a hose;
the inner diameter of the receiver disc is 11-51 mm; the outer diameter of the hollow pipe of the receiver is 2 mm-15 mm; the specification of the external thread is 1/8-1/2; the type of the pneumatic connector is PC- (4-12) - (1/8-1/2); the outer diameter of the hose is 4 mm-12 mm;
fourthly, the aerogel device:
the aerogel device consists of five parts, namely an ultrasonic atomizer, an atomizing cup, a flange, a quartz tube and a receiver; the top elbow of the atomizing cup is connected with the tube furnace through a flange; the quartz tube side tube is connected with the receiver; the receiver was connected to a hose connected to a vacuum filter to vent the tail gas as shown in figure 4.
According to the invention, graphene oxide is used as an insulating layer to be coated on the surface of the nano barium titanate particles to form the nano composite particles with the core-shell structure, and the graphene oxide has good insulating property, can effectively hinder charge transfer, and prevents the formation of a leakage current channel, thereby reducing dielectric loss; the prepared nano particles with the core-shell structure are introduced into a high polymer, so that the composite material has excellent energy storage performance and high energy storage efficiency under the condition of low filling amount, and a simple, universal and effective technology is provided for obtaining a capacitor with high energy storage efficiency.
The preparation method can realize the curling of the graphene oxide and the preparation of the graphene oxide coated nano particles by an aerogel method, can obviously distinguish the formation of the graphene oxide shrinkage globules by scanning electron microscope pictures, and can distinguish the existence of the nano particles in the shell layer by transmission. The method for preparing the core-shell structure particles by the aerogel method is simple, the structure is controllable, the expandability is realized, and the application prospect is good; provides a simple and effective method for preparing the core-shell structure nano-particles.
According to the invention, by adding a trace amount of graphene oxide @ barium titanate core-shell structure (0.05 wt% -0.8 wt%), the dielectric constant of the graphene oxide @ barium titanate/polyvinylidene fluoride composite film is obviously improved, the dielectric property of the composite film is increased more along with the increase of the filler content, but the dielectric loss of the graphene oxide @ barium titanate/polyvinylidene fluoride composite film is obviously reduced compared with that of an uncoated material.
The core-shell structure nano-particles have high structural stability and good dispersibility, and the graphene oxide shell layer with good insulativity is introduced, so that charge transfer can be effectively hindered, the formation of an electric leakage current channel is prevented, and the dielectric loss is reduced; under the condition of lower filling amount, the dielectric loss of the composite material is as low as 0.066-0.079, the dielectric constant is improved to 8.1-9.2 (the pure PVDF film is 8.1), and the energy storage efficiency can be more than 83%. Has great application prospect in dielectric energy storage.
Drawings
FIG. 1 is an SEM image of a core-shell structure of graphene oxide-coated nanoparticles;
FIG. 2 is a TEM image of a core-shell structure of graphene oxide-coated nanoparticles;
FIG. 3 is a graph of the trend of dielectric constant and dielectric loss with filler content;
FIG. 4 is a schematic structural diagram of an aerogel device, 1-ultrasonic atomizer, 2-atomizing cup, 3-flange, 4-tube furnace, 5-quartz tube, 6-receiver, 7-elbow, 701-main tube, 702-side tube, with the direction of the arrow indicating the flow direction of the carrier gas.
Detailed Description
Example 1: in this embodiment, a method for preparing core-shell structured nanocomposite particles by an aerogel method is performed according to the following steps:
mixing barium titanate nanoparticles with the average particle size of 80nm with deionized water, performing ultrasonic dispersion for 90min at the temperature of 0 ℃ and the ultrasonic power of 450W, adding graphene oxide with the transverse size of 2 mu m and the thickness of 3nm, and performing ultrasonic dispersion for 30min at the temperature of 0 ℃ and the ultrasonic power of 450W to obtain a dispersion liquid;
wherein the mass ratio of the graphene oxide to the barium titanate nanoparticles is 1:1, and the total mass fraction of the graphene oxide to the barium titanate nanoparticles in the dispersion liquid is 0.05%;
and step two, placing the dispersion liquid obtained in the step one in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops with the average particle size of 10 microns, then entering a high-temperature area of a tubular furnace under the drive of carrier gas high-purity nitrogen, rapidly drying at 800 ℃, drying the small liquid drops in the rapid drying process, curling the lamellar nano material, wrapping the spherical nano particles, performing suction filtration on a PTFE film of a receiver, and taking down the particles to obtain the core-shell structure nano composite particles, wherein the core-shell structure nano composite particles are shown in the figure 1 and the figure 2.
The dielectric loss and dielectric constant of the core-shell structured nanocomposite particles of the present example at different low loadings are shown in table 1.
TABLE 1
| Amount of filling | Dielectric constant | Dielectric loss |
| 0 | 8.1 | 0.072 |
| 0.05 | 8.1 | 0.073 |
| 0.2 | 8.4 | 0.075 |
| 0.4 | 8.9 | 0.066 |
| 0.8 | 9.2 | 0.079 |
As can be seen from table 1, under the condition of low filling amount, the dielectric loss of the core-shell structure nanocomposite particle of the embodiment is as low as 0.066-0.079, the dielectric constant is increased to 8.1-9.2 (8.1 for pure PVDF film), and the energy storage efficiency can be greater than 83%.
Example 2: in this embodiment, a method for preparing core-shell structured nanocomposite particles by an aerogel method is performed according to the following steps:
mixing titanium oxide nanoparticles with the average particle size of 20nm with deionized water, performing ultrasonic dispersion for 30min at the temperature of 5 ℃ and the ultrasonic power of 900W, adding graphene oxide with the transverse size of 5 microns and the thickness of 15nm, and performing ultrasonic dispersion for 15min at the temperature of 2 ℃ and the ultrasonic power of 900W to obtain a dispersion liquid;
wherein the mass ratio of the graphene to the titanium oxide nanoparticles is 4:1, and the total mass fraction of the graphene and the barium titanate nanoparticles in the dispersion liquid is 0.2%;
and step two, placing the dispersion liquid obtained in the step one in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops with the average particle size of 5 microns, then entering a high-temperature area of a tubular furnace under the drive of carrier gas high-purity nitrogen, rapidly drying the carrier gas at the temperature of 700 ℃, drying the small liquid drops in the rapid drying process, curling the lamellar nano material, wrapping the spherical nano particles, performing suction filtration on carbon cloth of a receiver, and taking down the particles to obtain the core-shell structure nano composite particles.
Example 3: in this embodiment, a method for preparing core-shell structured nanocomposite particles by an aerogel method is performed according to the following steps:
mixing silicon oxide nanoparticles with the particle size of 500nm with deionized water, performing ultrasonic dispersion for 60min at the temperature of 0 ℃ and the ultrasonic power of 600W, adding graphene with the transverse size of 20 mu m and the thickness of 50nm, and performing ultrasonic dispersion for 20min at the temperature of 0 ℃ and the ultrasonic power of 600W to obtain a dispersion liquid;
wherein the mass ratio of the graphene to the silicon oxide nanoparticles is 2:1, and the total mass fraction of the graphene and the barium titanate nanoparticles in the dispersion liquid is 0.1%;
and step two, placing the dispersion liquid obtained in the step one in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops with the average particle size of 20 microns, then entering a high-temperature area of a tubular furnace under the drive of carrier gas high-purity nitrogen, rapidly drying the small liquid drops at the temperature of 500 ℃ at the speed of 0.5L/min, drying the small liquid drops in the rapid drying process, curling the lamellar nano material, wrapping spherical nano particles, performing suction filtration on ITO glass of a receiver, and taking down the particles to obtain the core-shell structure nano composite particles.
The graphene oxide used in this example can be prepared by the following steps:
firstly, preparing concentrated sulfuric acid with the mass percent of 98%, adding graphite, and uniformly stirring; adding potassium persulfate and phosphorus pentoxide into the mixed solution, uniformly stirring, standing, reacting at 35 ℃ for 2 hours, and carrying out heat insulation cooling on the obtained dark green mixture to room temperature; then adding deionized water, uniformly stirring, and standing for 24 hours to obtain standing liquid;
the volume ratio of the mass of the potassium persulfate to the volume of the concentrated sulfuric acid is 1g (10) mL; the mass ratio of the potassium persulfate to the phosphorus pentoxide is 1 (1); the mass ratio of the potassium persulfate to the graphite is 1 (1); the volume ratio of the mass of the graphite to the deionized water is 1g (500) mL;
pouring out the supernatant of the standing liquid, taking out the precipitate, adding deionized water, stirring uniformly, filtering water by using a suction filter, adding deionized water again for washing, filtering, and repeating the above operations until the filtered water is neutral; then drying the obtained product at 60 ℃ to obtain pre-oxidized graphite;
thirdly, under the stirring condition, adding pre-oxidized graphite into concentrated sulfuric acid with the mass percent of 98% and the temperature of 0 ℃, slowly adding potassium permanganate after uniform dispersion, heating to 35 ℃, stirring for reaction for 2 hours, adding deionized water and hydrogen peroxide with the mass percent of 30% into a reaction solution after the reaction is finished, stirring until the solution is bright yellow, and centrifuging at low speed for 60min to obtain a crude product;
the volume ratio of the mass of the pre-oxidized graphite to the concentrated sulfuric acid is 1g (20) mL; the mass ratio of the pre-oxidized graphite to the potassium permanganate is 1 (2); the volume ratio of the mass of the pre-oxidized graphite to the deionized water is 1g (100) mL; the volume ratio of the pre-oxidized graphite to the hydrogen peroxide with the mass percent of 30% is 1g (10) mL; the low-speed centrifugation speed is 3000 r/min;
adding the crude product into a hydrochloric acid solution with the mass fraction of 10% for cleaning, centrifuging at a low speed to obtain a precipitate, cleaning twice with hydrochloric acid, then using deionized water until the supernatant obtained by centrifuging is neutral, and finally putting the washed product into a dialysis bag for dialysis for 30 days to obtain a graphene oxide solution;
the volume ratio of the mass of the crude product to the hydrochloric acid is 1g (50) mL; the ratio of the mass of the crude product to the volume of the deionized water is 1g (50) mL.
The aerogel device used in the second step of the embodiment mainly comprises an ultrasonic atomizer, an atomizing cup, a flange, a quartz tube and a receiver; the top elbow of the atomizing cup is connected with the tube furnace through a flange; the quartz tube side tube is connected with the receiver; the receiver was connected to a hose connected to a vacuum filter to vent the tail gas as shown in figure 4.
Wherein the bent pipe consists of two parts of quartz glass pipes, and the main pipe is communicated with the side pipe;
the outer diameter of the main pipe is 50mm, and the length of the main pipe is 60 mm; the wall thickness of the main pipe is 2 mm; the outer diameter of the side pipe is 25 mm; the length of the side pipe is 80 mm; the wall thickness of the side pipe is 2 mm;
the atomizing cup is made of organic glass; the atomizing cup is cylindrical and comprises two parts, namely a cup top and a cup body; the middle of the top of the atomizing cup is provided with a hole and is connected with a hollow bent pipe; a small hole is formed in the position, close to the middle, of the top of the atomizing cup; the atomizing cup has no cup bottom, the side surface of the cup body is provided with an opening and is connected with an outer spiral hollow tube, and the outer spiral hollow tube is connected with an air pipe; the two-phase dispersion liquid is filled in the atomizing cup, and the cup bottom is supported by a polymer film; the polymer film at the bottom of the atomizing cup is fixed by a flange; the bottom flange of the atomizing cup is in a ring shape;
the diameter of the atomizing cup body is 60mm, and the wall thickness is 3 mm; the diameter of an opening in the middle of the cup cover of the atomizing cup is 10 mm; the diameter of a small hole formed in any position of the cup cover of the atomizing cup is 2 mm; the height of the atomizing cup body is 100 mm; the height of the opening on the side surface of the atomizing cup body is 50mm from the cup cover; the diameter of an opening on the side surface of the atomizing cup body is 10 mm; the inner diameter of a flange ring at the bottom of the atomizing cup is 60 mm; the outer diameter of a flange ring at the bottom of the atomizing cup is 80 mm; the diameter of a flange screw hole at the bottom of the atomizing cup is 2 mm;
③ receiver:
the receiver is made of stainless steel; the receiver is of a disc shape; the bottom of the disc is provided with a hole and is connected with hollow pipes made of the same material; the disc and the hollow pipe are connected in a welding mode; the tail end of the hollow pipe is provided with an external thread; the external thread is connected with a straight-through pneumatic joint; the pneumatic joint is connected with a hose;
the inner diameter of the receiver disc is 27 mm; the outer diameter of the hollow pipe of the receiver is 10 mm; the specification of the external thread is 1/4; the type of the pneumatic connector is PC- (6) -1/8); the outer diameter of the hose is 6 mm.
Claims (4)
1. A method for preparing core-shell structure nano composite particles by an aerogel method is characterized by comprising the following steps:
mixing barium titanate nanoparticles with deionized water, performing ultrasonic dispersion at 0-5 ℃ for 30-90 min, adding graphene oxide, and performing ultrasonic dispersion at 0-5 ℃ for 15-30 min to obtain a dispersion liquid;
placing the dispersion liquid obtained in the step one in an atomizing cup of an ultrasonic atomizer, controlling the water temperature of the ultrasonic atomizer to be 0-20 ℃, ultrasonically oscillating the dispersion liquid into small liquid drops, then entering a high-temperature area of a tubular furnace under the drive of carrier gas, quickly drying at 500-800 ℃, then carrying out suction filtration on a receiving film of a receiver, and taking down particles to obtain core-shell structure nano composite particles;
wherein the mass ratio of the graphene oxide to the barium titanate nanoparticles in the first step is (0.5-4) to 1;
the total mass fraction of the graphene oxide and barium titanate nanoparticles in the dispersion liquid is 0.05-0.2%;
in the first step, the transverse size of the graphene oxide is 2-20 mu m, and the thickness of the graphene oxide is 1-50 nm; the particle size of the barium titanate nano-particles is 10 nm-500 nm; the particle size of the small and medium liquid drops in the second step is 5-20 microns; the carrier gas is high-purity nitrogen or high-purity argon, and the speed of the carrier gas is 0.5L/min-2L/min.
2. The method for preparing the core-shell structure nanocomposite particles by the aerogel method according to claim 1, wherein the ultrasonic power in the step one is 450W-900W.
3. The method for preparing core-shell structure nanocomposite particles according to claim 1, wherein the receiving film in the second step is one of a silicon wafer, ITO glass, copper foil, an alumina filter membrane, nickel foam, carbon cloth, porous polycarbonate, and a PTFE film.
4. The method for preparing core-shell structure nanocomposite particles according to claim 1, wherein the material of the atomizing cup in the second step is organic glass, quartz glass or common glass.
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