CN114023566B - 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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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 36
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000010248 power generation Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000006479 redox reaction Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010931 gold Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920009405 Polyvinylidenefluoride (PVDF) Film Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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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 composite material can respectively reach 96V and 303 muA/m 2 . 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, the 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/m 2 And can be used for the instant and 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 on the basis of 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 increase the pyroelectric output, the current research needs mechanical devices to shield sunlight to obtain a large temperature oscillation rate, which causes additional energy waste, and because the output power is low, the devices are complicated and the cost is too high, it is difficult to put the devices into practical use on a large scale.
Disclosure of Invention
In order to overcome the defects of low performance, inconvenient actual operating 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 problem 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 HAuCl 4 ·4H 2 O 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 HAuCl 4 ·4H 2 Performing oxidation-reduction reaction on O to prepare an Au @ CNT photo-thermal material;
(2) And dispersing the Au @ CNT photothermal material in an ethanol solution, then forming an Au @ CNT layer on the filter paper in a suction filtration mode, and drying at normal temperature to obtain the Au @ CNT photothermal material layer.
Furthermore, the aperture of the filter paper is 0.45 μm, and the density of the formed Au @ CNT photo-thermal material layer is 1.5 mg/cm 2 。
Further, the polarized PVDF surface is plated with an aluminum electrode.
Au @ CNT is a material prepared by redox reaction of multi-walled carbon nanotubes with a tetrachloroauric acid solution. Among them, since the CNT contains an oxygen-containing functional group such as O = C, C-O, au is present 3+ 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 by introducing the nanoparticles, so that the photothermal absorption performance of the Au @ CNT layer is promoted. When the Au @ CNT photo-thermal material is irradiated for 30s in the sun, the photo-thermal temperature can reach 79.6 ℃, and the specific reduction oxygen is generatedGraphene and CNT were 20.2 and 9.5 ℃ higher, respectively.
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 silvered electrode PVDF film. In addition, the surface resistance is low (2 Ω), and the conductivity is excellent.
The Au @ CNT photothermal 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/m 2 11V and 6V higher than open circuit voltage based on reduced graphene oxide and CNT, and 75 μ A/m higher short circuit current density 2 And 30. Mu.A/m 2 。
As another aspect of the invention, the Au @ CNT/PVDF pyroelectric composite material can be used for a pyroelectric generator, in particular a photo-thermal type pyroelectric generator.
The invention relates to a vane type pyroelectric power generation device, which is obtained by fixing an Au @ CNT/PVDF pyroelectric composite material with a windmill vane, wherein the Au @ CNT/PVDF vane type pyroelectric power generation device is prepared by taking the Au @ CNT as a key material for photothermal conversion and polarized PVDF 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 ℃), the 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/m 2 And 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 composite material can respectively reach 96V and 303 mu A/m 2 Is based onThe open circuit voltage of the original graphene oxide and the CNT is high, namely 11V and 6V, and the short circuit current density is high, namely 75 mu A/m 2 And 30. Mu.A/m 2 。
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/m 2 The 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 the power generation device 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 on 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 is a diagram of a device prepared according to the present invention for collecting energy from air flow and rain wash at different temperatures in an environment.
Detailed Description
The experimental procedures in the following examples are all conventional ones 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 Material
The 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.
(1) Weighing CNT powder of 6 mg, ultrasonically dispersing the CNT powder in 10 mL deionized water, adding 125 mu L of gold tetrachloro 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 ethanol solution and dropped uniformly to 4 cm 2 The surface of the filter paper of (2) was suction filtered, and 3 h was dried at room temperature to obtain an au @ cnt photothermal material layer. In this example, the aperture of the filter paper was 0.45 μm, and the layer density of the formed Au @ CNT photothermal material was controlled to be 1.5 mg/cm 2 。
(3) 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 placed in 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 to connect the power generation device with the digital source meter by using 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 reach 96V and 303 mu A/m respectively 2 11V and 6V higher than open circuit voltage based on reduced graphene oxide and CNT, and 75 μ A/m higher short circuit current density 2 And 30. Mu.A/m 2 。
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 the 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 windmill blades to produce 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 communicated with the digital source meterConnected with a computer through a USB interface. When the ambient temperature is 30 ℃ and the wind speed is 3.6m/s, the windmill blade rotates to generate 29.2 mW/m 2 The 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 to connect the power generating device with the digital source meter by using a lead, wherein the digital source meter is connected with a computer through a USB interface. The conclusion is drawn: a capacitor with a capacity of 4.7 μ F can be charged to 5V in 5 min, as shown in fig. 2 (b), and its stored electrical energy can subsequently power the LED light bulb.
Application example 2
The Au @ CNT/PVDF blade type pyroelectric power generation device is placed outdoors, and in special weather such as blowing rain, wind and rain take away heat on the surface of a windmill blade, and the temperature fluctuation caused by the wind and rain can realize pyroelectric conversion. In an outdoor environment with an environmental 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 ℃, a Keithley 2450 type digital source meter is used for monitoring the open circuit voltage output of the 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 the wind reaches 38 ℃, the open-circuit voltage can reach 43V at most, and the obtained result is shown in fig. 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 open-circuit voltage of the blade type pyroelectric power generation device is monitored by adopting a Keithley 2450 type digital source meter, 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 acquired, 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 high output and is expected to be put into large-scale practical application.
Claims (1)
1. A vane type pyroelectric power generation device comprises windmill vanes and is characterized in that Au @ CNT/PVDF pyroelectric composite materials are fixed on the windmill vanes; the Au @ CNT/PVDF pyroelectric composite material is formed by an Au nano particle in-situ composite carbon nano tube photothermal material layer and a polarized PVDF layer; the Au nano particle in-situ composite carbon nano tube photo-thermal material layer is prepared by the following method:
(1) Mixing CNT with HAuCl 4 ·4H 2 Performing oxidation-reduction reaction on O to prepare an Au @ CNT photothermal material;
(2) Dispersing the Au @ CNT photothermal material in an ethanol solution, forming an Au @ CNT layer on filter paper in a suction filtration mode, and drying at normal temperature to obtain the Au @ CNT photothermal material layer, wherein the aperture of the filter paper is 0.45 mu m, and the layer density of the formed Au @ CNT photothermal material layer is 1.5 mg/cm 2 ；
And plating an aluminum electrode on the surface of the polarized PVDF.
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| KR20170037261A (en) * | 2015-09-25 | 2017-04-04 | 주식회사 엘지화학 | New compound semiconductors and their application |
| JP2018049711A (en) * | 2016-09-20 | 2018-03-29 | 康博 青木 | Electrogenic composition, power-generating device using the same, power generator, and power storage-generator |
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| JP5808618B2 (en) * | 2011-09-05 | 2015-11-10 | 株式会社クレハ | Power generator with pyroelectric body |
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| KR20170037261A (en) * | 2015-09-25 | 2017-04-04 | 주식회사 엘지화학 | New compound semiconductors and their application |
| JP2018049711A (en) * | 2016-09-20 | 2018-03-29 | 康博 青木 | Electrogenic composition, power-generating device using the same, power generator, and power storage-generator |
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