CN114023566A - Au @ CNT/PVDF pyroelectric composite material and application thereof - Google Patents
Au @ CNT/PVDF pyroelectric composite material and application thereof Download PDFInfo
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- CN114023566A CN114023566A CN202111330629.9A CN202111330629A CN114023566A CN 114023566 A CN114023566 A CN 114023566A CN 202111330629 A CN202111330629 A CN 202111330629A CN 114023566 A CN114023566 A CN 114023566A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2095—Light-sensitive devices comprising a flexible sustrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Abstract
The invention discloses an Au @ CNT/PVDF pyroelectric composite material and application thereof. The Au @ CNT/PVDF pyroelectric composite material can effectively capture solar energy, and the open-circuit voltage and the short-circuit current density of the Au @ CNT/PVDF pyroelectric composite material can respectively reach 96V and 303 muA/m2. The blade type pyroelectric power generation device is obtained by skillfully connecting the high-performance pyroelectric material with the windmill blade, the functional device can reasonably utilize the rotation of the windmill blade to manufacture temperature fluctuation, light-heat-electricity conversion is realized without an external light intensity adjusting device, and the maximum output power of the device is as high as 29.2 mW/m2And can be used for the instant effective charging of the capacitor. In addition, the device can also collect the energy of air flow, rain wash and the like at different temperatures in the environment.
Description
Technical Field
The invention belongs to the technical field of flexible device application, and particularly relates to an Au @ CNT/PVDF pyroelectric composite material and application thereof.
Background
As is well known, sunlight is a clean, green, efficient and rich energy source, so that the temperature change caused by sunlight irradiation is used as a heat source, and a photo-thermal type pyroelectric nano-generator (S-PENG) prepared based on a flexible high-molecular polymer polyvinylidene fluoride (PVDF) film is expected to be put into practical application. This S-pen is a non-contact energy harvesting technique. The solar heat-electricity generation device can realize conversion from fluctuating photothermal to pyroelectric by using temperature change caused by sunlight irradiation as a heat source. However, temperature fluctuations upon continuous irradiation of outdoor sunlight are generally small, and therefore, it is difficult to obtain a high-efficiency pyroelectric output by relying only on sunlight. In order to improve the pyroelectric output, the current research mostly needs a mechanical device to shield sunlight to obtain a large temperature oscillation rate, which causes additional energy waste, and because the output power is low, the device is complex and the cost is too high, it is difficult to put the device into practical use on a large scale.
Disclosure of Invention
In order to overcome the defects of low performance, inconvenient actual operation conditions and the like of the existing S-PENG, the invention provides an Au @ CNT/PVDF pyroelectric composite material and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an Au @ CNT/PVDF pyroelectric composite material is composed of an Au nano particle in-situ composite carbon nano tube photothermal material layer and a polarized PVDF layer.
Further, the Au nano particle in-situ composite carbon nano tube photo-thermal material is prepared from CNT and HAuCl4·4H2O is prepared by oxidation-reduction reaction.
Further, the Au nanoparticle in-situ composite carbon nanotube photothermal material layer is prepared by the following method:
(1) mixing CNT with HAuCl4·4H2Performing oxidation-reduction reaction on the O to prepare an Au @ CNT photo-thermal material;
(2) and dispersing the Au @ CNT photo-thermal material into an ethanol solution, forming an Au @ CNT layer on the filter paper in a suction filtration mode, and drying at normal temperature to obtain the Au @ CNT photo-thermal material layer.
Further, the aperture of the filter paper is 0.45 μm, and formed Au @ CNThe surface density of the T photo-thermal material layer is 1.5 mg/cm2。
Further, the polarized PVDF surface is plated with an aluminum electrode.
Au @ CNT is a material prepared by the redox reaction of multi-walled carbon nanotubes with a solution of tetrachloroauric acid. Among them, since the CNT has an oxygen-containing functional group such as O = C, C-O, Au3+The gold nanoparticles can be successfully introduced by spontaneous reduction on the surface of the CNT through current displacement and redox reaction. The gold nanoparticles are used as a plasma metal, have a surface plasma resonance effect, can generate strong heat under solar radiation, and can generate a synergistic effect with the photothermal effect of the carbon-based material CNT due to the introduction of the nanoparticles, so that the photothermal absorption performance of the Au @ CNT layer is promoted. When the Au @ CNT photo-thermal material disclosed by the invention is irradiated for 30s in the sun, the photo-thermal temperature can reach 79.6 ℃, and is respectively 20.2 ℃ higher and 9.5 ℃ higher than that of reduced graphene oxide and CNT.
The pyroelectric layer is a polarized PVDF film. The high molecular polymer has higher pyroelectric coefficient (p = 25 mu C m)-2 K-1) And, the film surface is aluminized the electrode, it has better stability than surface silvering electrode PVDF film. In addition, the surface resistance is low (2 Ω), and the conductivity is excellent.
The Au @ CNT photo-thermal material and the polarized PVDF are compounded to form the pyroelectric power generation material capable of effectively capturing solar energy, and the open-circuit voltage and the short-circuit current density of the pyroelectric power generation material can respectively reach 96V and 303 mu A/m211V and 6V higher than open circuit voltage based on reduced graphene oxide and CNT, and 75 μ A/m higher short circuit current density2And 30. mu.A/m2。
As another aspect of the present invention, the Au @ CNT/PVDF pyroelectric composite material of the present invention can be used in a pyroelectric generator, particularly a photothermal type pyroelectric generator.
The invention relates to a blade type pyroelectric power generation device, which is characterized in that an Au @ CNT/PVDF pyroelectric composite material is fixed with a windmill blade to obtain the Au @ CNT/PVDF blade type pyroelectric power generation device, wherein the Au @ CNT is used as a key material for photothermal conversion, and polarized PVDF is used as a core material for converting photothermal into pyroelectric.
The blade type pyroelectric power generation device is obtained by skillfully connecting the high-performance pyroelectric material with the windmill blade, the functional device can reasonably utilize the rotation of the windmill blade to manufacture temperature fluctuation (about 14 ℃), light-heat-electricity conversion is realized without an external light intensity adjusting device, and the maximum output power of the device is as high as 29.2 mW/m2And can be used for the instant effective charging of the capacitor. In addition, the device can also collect the energy of air flow, rain wash and the like at different temperatures in the environment.
Compared with the prior art, the invention has the advantages that:
1. the Au @ CNT/PVDF pyroelectric composite material can effectively capture solar energy, and the open-circuit voltage and the short-circuit current density of the Au @ CNT/PVDF pyroelectric composite material can respectively reach 96V and 303 muA/m211V and 6V higher than open circuit voltage based on reduced graphene oxide and CNT, and 75 μ A/m higher short circuit current density2And 30. mu.A/m2。
2. The blade type pyroelectric power generation device prepared by the pyroelectric composite material can reasonably utilize the rotation of windmill blades to manufacture temperature fluctuation, realizes light-heat-electricity conversion without an external light intensity adjusting device, and has the maximum output power as high as 29.2 mW/m2The materials required by the invention are all flexible, so that the obtained Au @ CNT/PVDF pyroelectric material can be fixed on a windmill to prepare a blade type pyroelectric power generation device, and the power generation device can obtain a fluctuating temperature through the rotation of the windmill in work without an additional mechanical device for regulating and controlling the temperature, and can be applied to daily life in a large scale.
3. The preparation method is simple in preparation process, controllable in process, environment-friendly, low in cost and capable of being put into practical application in a large scale.
Drawings
FIG. 1 is a schematic diagram of an Au @ CNT/PVDF blade type pyroelectric power generation device prepared by the invention and a power generation performance display thereof;
FIG. 2 is a test case where a device prepared according to the present invention can be used for the immediate and efficient charging of a capacitor;
fig. 3 shows that the device prepared by the invention is used for collecting the energy of air flow and rain wash at different temperatures in the environment.
Detailed Description
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were all commercially available unless otherwise specified.
The invention will be further described with reference to the accompanying drawings in which:
example 1 preparation of Au @ CNT/PVDF pyroelectric composite
The Au @ CNT/PVDF pyroelectric composite material is composed of an Au nanoparticle in-situ composite carbon nanotube photothermal material layer and a polarized PVDF layer.
(1) Weighing 6 mg of CNT powder, ultrasonically dispersing the CNT powder in 10 mL of deionized water, adding 125 muL of gold tetrachloroate solution, stirring and reacting for 24 hours under a dark condition, centrifugally washing the reacted solution for 3-4 times, and freeze-drying to obtain the Au @ CNT photothermal material.
(2) 6 mgAu @ CNT was dispersed in 6 mL of ethanol solution and dropped uniformly to 4 cm2And carrying out suction filtration on the surface of the filter paper, and drying at room temperature for 3 h to obtain the Au @ CNT photothermal material layer. In this example, the aperture of the filter paper is 0.45 μm, and the surface density of the formed Au @ CNT photothermal material layer is controlled to be 1.5 mg/cm2。
(3) And transferring the Au @ CNT photothermal material layer from the filter paper to the surface of the polarized PVDF film for fixation, and plating an aluminum electrode on the surface of the PVDF film to obtain the Au @ CNT/PVDF pyroelectric composite material.
The prepared Au @ CNT/PVDF pyroelectric composite material is exposed to illumination (0.1W/cm) with different switching frequencies of 200, 100, 50 and 33.4mHz- 2) In the experiment, a Keithley 2450 type digital source meter is adopted to monitor the open-circuit voltage and short-circuit current output of the high-performance pyroelectric material, and the specific method is that a power generation device is connected with the digital source meter by a lead, and the digital source meter is connected with a computer through a USB interface. Under the illumination switching frequency of 50 mHz, the performance output is stable, and the open-circuit voltage and the short-circuit current density can respectively reach 96V and 303 muA/m2Based on reduced oxideOpen circuit voltage of graphene and CNT is high at 11V and 6V, and short circuit current density is high at 75 μ A/m2And 30. mu.A/m2。
Example 2 preparation of a vane-type pyroelectric Power Generation device
The Au @ CNT/PVDF pyroelectric composite material is fixed with a windmill blade to obtain an Au @ CNT/PVDF blade type pyroelectric power generation device.
The blade type pyroelectric power generation device prepared by the Au @ CNT/PVDF pyroelectric composite material can reasonably utilize the rotation of the windmill blade to manufacture temperature fluctuation, and realizes light-heat-electricity conversion without an external light intensity adjusting device. In the experiment, a Keithley 2450 type digital source meter is adopted to monitor the open-circuit voltage and short-circuit current output of the high-performance pyroelectric material, and the specific method is that a power generation device is connected with the digital source meter by a lead, and the digital source meter is connected with a computer through a USB interface. When the ambient temperature is 30 ℃ and the wind speed is 3.6m/s, the rotation of the windmill blade can generate 29.2 mW/m2The output power of (1).
Application example 1
The Au @ CNT/PVDF blade type pyroelectric power generation device is placed outdoors, when sunlight irradiates, light-heat-electricity conversion can be realized without an external light intensity adjusting device by means of temperature fluctuation generated when a windmill rotates, and a capacitor can be effectively charged in real time by rectifying alternating current generated by the power generation device by using a rectifier. A schematic view thereof is shown in fig. 2 (a). The charging process is monitored by a Keithley 2450 type digital source meter, and the specific method is that a power generation device is connected with the digital source meter by a lead, and the digital source meter is connected with a computer through a USB interface. And (5) drawing a conclusion that: the capacitor with a capacity of 4.7 muF can be charged to 5V in 5 min, as shown in FIG. 2 (b), and the stored electric energy can be used to power the LED bulb.
Application example 2
The Au @ CNT/PVDF blade type pyroelectric power generation device is placed outdoors, and in special weather such as blowing and raining, wind and rain bring away heat on the surface of a windmill blade, and the pyroelectric conversion can be realized through temperature fluctuation caused by the wind and rain. In an outdoor environment with an ambient temperature of 24 ℃ and a wind speed of 3.2 m/s, as shown in fig. 3(a), when the wind temperature fluctuates between 32 ℃ and 38 ℃, the open-circuit voltage output of the power generation device is monitored by using a Keithley 2450 type digital source meter, and the specific method is that the power generation device is connected with the digital source meter by using a lead, the digital source meter is connected with a computer through a USB interface, the real-time open-circuit voltage output of 100 s is collected, and the conclusion is obtained: when the temperature of the wind reaches 38 ℃, the open-circuit voltage can reach 43V at most, and the obtained result is shown in figure 3 (b); similarly, when the ambient temperature is 24 ℃, the volume of rainwater flowing through the surface of the blade is 2 mL, and the temperature of the rainwater fluctuates between 28 and 35 ℃, the Keithley 2450 type digital source meter is adopted to monitor the open-circuit voltage of the blade type pyroelectric power generation device, the specific method is that the power generation device is connected with the digital source meter by a lead, the digital source meter is connected with a computer through a USB interface, the real-time open-circuit voltage output of 100 s is collected, and the conclusion is obtained: when the temperature of rainwater reached 35 ℃, the open circuit voltage thereof reached up to 18V, and the obtained result is shown in fig. 3 (d). The result shows that the Au @ CNT/PVDF blade type pyroelectric power generation device has stable and higher output and is expected to be put into large-scale practical application.
Claims (7)
1. An Au @ CNT/PVDF pyroelectric composite material is characterized by being composed of an Au nano particle in-situ composite carbon nano tube photothermal material layer and a polarized PVDF layer.
2. The Au @ CNT/PVDF pyroelectric composite material as claimed in claim 1, wherein the Au nanoparticle in-situ composite carbon nanotube photothermal material is prepared from CNT and HAuCl4·4H2O is prepared by oxidation-reduction reaction.
3. The Au @ CNT/PVDF pyroelectric composite material of claim 1, wherein the Au nanoparticle in-situ composite carbon nanotube photothermal material layer is prepared by the following method:
(1) mixing CNT with HAuCl4·4H2Performing oxidation-reduction reaction on the O to prepare an Au @ CNT photo-thermal material;
(2) and dispersing the Au @ CNT photo-thermal material into an ethanol solution, forming an Au @ CNT layer on the filter paper in a suction filtration mode, and drying at normal temperature to obtain the Au @ CNT photo-thermal material layer.
4. The Au @ CNT/PVDF pyroelectric composite material of claim 3, wherein the pore size of the filter paper is 0.45 μm, and the areal density of the Au @ CNT photothermal material layer is 1.5 mg/cm2。
5. The Au @ CNT/PVDF pyroelectric composite of claim 1, wherein the polarized PVDF surface is aluminized with electrodes.
6. Use of the Au @ CNT/PVDF pyroelectric composite material as claimed in any one of claims 1-5 in a photothermal type pyroelectric generator.
7. A vane type pyroelectric power generation device, which comprises a windmill vane, and is characterized in that the Au @ CNT/PVDF pyroelectric composite material as claimed in any one of claims 1-5 is fixed on the windmill vane.
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