Ferroelectric polarization tantalum nitride-based photo-assisted water photovoltaic power generation device and preparation method of ferroelectric polarization tantalum nitride-based photo-assisted water photovoltaic power generation device

Abstract

The invention belongs to the technical field of photo-assisted hydroelectric power generation, and particularly relates to a photo-assisted hydroelectric power generation device based on ferroelectric polarization tantalum nitride and a preparation method of the photo-assisted hydroelectric power generation device. The device comprises visible-light-responsive tantalum nitride and a ferroelectric material ultrathin layer on the surface of the visible-light-responsive tantalum nitride, wherein the ultrathin layer is subjected to annealing and polarization reversal treatment. The preparation method comprises the following steps: preparing a tantalum oxide nanowire array and a tantalum oxide nanotube array; preparing visible light response tantalum nitride; and preparing a ferroelectric material, dispensing the ferroelectric material on a substrate of the visible-light-responsive tantalum nitride nano material to form an ultrathin layer, and performing polarization reversal treatment after annealing. According to the ferroelectric polarization tantalum nitride-based water photovoltaic power generation device, the tantalum nitride material with the one-dimensional nano structure provides excellent photoelectric, evaporation power generation and directional rapid water vapor transmission performance, and the top and the polarizable ferroelectric polymer form a unique asymmetric heterojunction structure; through a polarization electric field generated by an ordered dipole in the ferroelectric material, stable and adjustable electric output is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of photo-assisted hydrovoltaic power generation, and in particular relates to a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride and a preparation method thereof. Background Art

[0002] At present, the world is facing energy shortage and environmental pollution problems. Traditional fossil fuels such as oil and natural gas are becoming increasingly depleted. The large amount of harmful substances and greenhouse gases emitted during their combustion process have seriously restricted social development and ecological civilization construction. In order to cope with the huge demand for energy consumption and achieve the goals of carbon peak and carbon neutrality, the development and utilization of new clean and renewable energy is imperative. Water covers more than 70% of the earth's surface and contains huge energy. Hydrovoltaic power generation has received great attention as an emerging power generation method. When water molecules interact with surface charged materials, the double electric layer boundary movement at the interface induces ion movement, which can generate electric potential and current, thereby converting water energy into electrical energy. Hydrovoltaic power generation includes wave power generation, droplet power generation, wet gas power generation and evaporation power generation. Among them, water evaporation power generation technology uses the evaporation of water in nature as a driving force. Compared with other water energy collection technologies, it has unique advantages such as strong spontaneity and low cost, and has broad development prospects. Carbon materials, semiconductor materials and biomass materials have all been proven to be used for water evaporation power generation. Semiconductor materials have unique light absorption properties. The electron-hole pairs generated by light excitation can increase the carrier concentration inside the material. At the same time, light can increase the evaporation rate and the flow rate of water molecules. Therefore, the coupling of the photovoltaic effect can improve the power generation effect of the device under uniform humidity and light-free conditions, and realize the efficient and coordinated collection of water energy and solar energy. At present, semiconductor materials such as titanium dioxide, tungsten disulfide, zinc oxide and cadmium sulfide have been used in the research of water evaporation power generation or sensor devices.

[0003] Traditional photovoltaic hydroelectric power generation devices have the following problems: first, the intrinsic carrier concentration of the photovoltaic material is low and the number of surface charges is small; second, the thermal diffusion effect generated by light induces hydrated ions to move in the direction opposite to the flow potential, making it difficult to achieve directional transport of charge carriers, resulting in a decrease in the potential of the hydroelectric power generation device; third, photovoltaic hydroelectric power generation devices are not easy to integrate and amplify, making it difficult to achieve large-scale production of high-output devices. Summary of the invention

[0004] The present invention discloses a photo-assisted hydrovoltaic power generation device based on ferroelectrically polarized tantalum nitride and a preparation method thereof. The present invention designs a ferroelectrically polarized tantalum nitride-based hydrovoltaic power generation device. The tantalum nitride material with a one-dimensional nanostructure provides excellent photoelectric, evaporative power generation and directional rapid transmission of water vapor performance. A unique asymmetric heterojunction structure is formed with a polarizable ferroelectric polymer on the top, and a stable and adjustable electrical output is achieved through the polarization electric field generated by the ordered dipoles inside the ferroelectric material.

[0005] To achieve the above purpose, the technical solution of the present invention is:

[0006] A photo-assisted hydrovoltaic power generation device based on ferroelectrically polarized tantalum nitride comprises tantalum nitride responsive to visible light and an ultra-thin layer of ferroelectric material dripped on its substrate, wherein the ultra-thin layer is subjected to annealing and polarization inversion treatment.

[0007] A method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride comprises the following steps:

[0008] (1) Preparation of tantalum oxide nanowire arrays and tantalum oxide nanotube arrays;

[0009] (2) Tantalum oxide nanowire arrays and tantalum oxide nanotube arrays are directly prepared in an ammonia atmosphere by controlling the reaction temperature, ammonia flow rate, and reaction time to produce visible light responsive tantalum nitride;

[0010] (3) A ferroelectric material is prepared and drop-coated on a substrate of a visible light-responsive tantalum nitride nanomaterial to form an ultra-thin layer, which is then annealed at 145°C for 30 minutes to perform a polarization reversal treatment.

[0011] Preferably, the step (1) comprises the following specific steps:

[0012] (11) Preparation of tantalum oxide nanowire arrays by template method: by using a coating process, an aluminum film of a certain thickness is evaporated on a tantalum substrate, and anodized for a certain period of time at a constant voltage of 60V in a 0.3M oxalic acid solution to prepare porous aluminum oxide AAO, and the AAO barrier layer is removed by an in-situ through-hole process to expose the metal tantalum surface corresponding to the bottom of the AAO template hole; the electrolyte is replaced with a concentrated sulfuric acid solution containing a certain amount of hydrofluoric acid, and the oxide nanowire array is grown in situ under the AAO confined template by anodization method, and finally the AAO template is dissolved by phosphoric acid to obtain the tantalum oxide nanowire array;

[0013] (12) Preparation of tantalum oxide nanotube arrays by anodization: the electrolyte is a concentrated sulfuric acid solution containing a certain amount of hydrofluoric acid. To reduce surface defects, the tantalum sheet is first pre-oxidized and then ultrasonically shaken in deionized water for 30 to 60 minutes to remove the tantalum oxide tubes. The tantalum sheet is then rinsed with deionized water and dried, followed by secondary oxidation to obtain a tantalum oxide nanotube array.

[0014] Preferably, in step (11), the thickness of the aluminum film is 200 nanometers to 20 micrometers.

[0015] Preferably, in the step (11), when the oxide nanowire array is in situ grown under the AAO confinement template by anodization, the AAO oxidation time is 5 min to 10 h.

[0016] Preferably, in step (11) and step (12), the concentration of the hydrofluoric acid is 0.5 vol% to 10 vol%.

[0017] Preferably, in step (11), the selection range of the constant voltage is 10V to 90V.

[0018] Preferably, in step (11) and step (12), the oxidation temperature of tantalum oxide is -0.5°C to 40°C.

[0019] Preferably, in step (11) and step (12), the oxidation time of tantalum oxide is 3 min to 120 min.

[0020] Preferably, in step (2), the reaction temperature is 850°C to 1200°C.

[0021] Preferably, in step (2), the reaction time is 5 to 15 hours.

[0022] Preferably, in step (2), the ammonia flow rate is 20 sccm to 50 sccm.

[0023] Preferably, in step (3), the ferroelectric material is at least one of PVDF, PTFE and P(VDF-TrFE).

[0024] Preferably, in step (3), the concentration of the ferroelectric material is 0.05-1 mg / mL.

[0025] Preferably, in step (3), the polarization reversal voltage is ±5V to ±10V.

[0026] The beneficial effects of the photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride and the preparation method of the present invention are:

[0027] 1. Tantalum nitride used in evaporation power generation devices has a photosensitivity effect, a wide light absorption range (can respond to visible light), a high intrinsic carrier concentration and a high surface charge.

[0028] 2. The evaporation power generation device has a one-dimensional ordered nanowire / nanotube structure, which can provide a directional vertical and controllable liquid transmission channel.

[0029] 3. Adding ferroelectric material between the nanostructured tantalum nitride and the top electrode can generate an additional electric field that promotes the selective separation and directional transmission of carriers by adjusting the polarization direction of the ferroelectric domain, further improving the output power.

[0030] 4. The prepared photo-assisted hydrovoltaic power generation device not only has excellent hydrovoltaic power generation performance, but also can realize the coordinated utilization of light energy and water energy.

[0031] 5. The photo-assisted hydrovoltaic power generation device proposed in the present invention has broad application prospects in the fields of self-power supply and sensing. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 , scanning electron microscope image of the tantalum oxide nanotube array of the present invention. DETAILED DESCRIPTION

[0033] The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

[0034] The following embodiments may be understood as individually expressing a part of a local structure or method of the present invention, or may be understood as a combination of the embodiments to explain the connotation of a larger structure or method of the present invention.

[0035] Example 1

[0036] A photo-assisted hydrovoltaic power generation device based on ferroelectrically polarized tantalum nitride comprises tantalum nitride responsive to visible light and an ultra-thin layer of ferroelectric material dripped on its substrate, wherein the ultra-thin layer is subjected to annealing and polarization inversion treatment.

[0037] Example 2

[0038] A method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride comprises the following steps:

[0039] (1) Preparation of tantalum oxide nanowire arrays and tantalum oxide nanotube arrays;

[0040] (2) Tantalum oxide nanowire arrays and tantalum oxide nanotube arrays are directly prepared in an ammonia atmosphere by controlling the reaction temperature, ammonia flow rate, and reaction time to produce visible light responsive tantalum nitride;

[0041] (3) A ferroelectric material is prepared and drop-coated on a substrate of a visible light-responsive tantalum nitride nanomaterial to form an ultra-thin layer, which is then annealed at 145°C for 30 minutes to perform a polarization reversal treatment.

[0042] Example 3

[0043] Based on Example 2, this embodiment discloses:

[0044] The step (1) comprises the following specific steps:

[0045] (11) Preparation of tantalum oxide nanowire arrays by template method: by using a coating process, a certain thickness of aluminum film is evaporated on a tantalum substrate, and anodized for a certain period of time at a constant voltage of 60V in a 0.3M oxalic acid solution to prepare porous aluminum oxide AAO, and the AAO barrier layer is removed by an in-situ through-hole process to expose the metal tantalum surface corresponding to the bottom of the AAO template hole; the electrolyte is replaced with a concentrated sulfuric acid solution containing hydrofluoric acid, and the oxide nanowire array is grown in situ under the AAO confined template by anodization method, and finally the AAO template is dissolved by phosphoric acid to obtain the tantalum oxide nanowire array;

[0046] (12) Tantalum oxide nanotube arrays were prepared by anodization: the electrolyte was a concentrated sulfuric acid solution containing hydrofluoric acid. To reduce surface defects, the tantalum sheet was pre-oxidized and then ultrasonically shaken in deionized water for 30 min to remove the tantalum oxide tubes. The tantalum sheet was rinsed with deionized water and dried, followed by secondary oxidation to obtain a tantalum oxide nanotube array.

[0047] In the step (11), the thickness of the aluminum film is 200 nanometers.

[0048] In the step (11), when the oxide nanowire array is in-situ grown under the AAO confinement template by anodization, the AAO oxidation time is 5 minutes.

[0049] In step (11) and step (12), the concentration of the hydrofluoric acid is 0.5 vol%.

[0050] In the step (11), the constant voltage is selected to be 10V.

[0051] In the steps (11) and (12), the oxidation temperature of tantalum oxide is 0.5°C.

[0052] In the steps (11) and (12), the oxidation time of tantalum oxide is 3 minutes.

[0053] Example 4

[0054] Based on Example 2, this embodiment discloses:

[0055] The step (1) comprises the following specific steps:

[0056] (11) Preparation of tantalum oxide nanowire arrays by template method: by using a coating process, a certain thickness of aluminum film is evaporated on a tantalum substrate, and anodized for a certain period of time at a constant voltage of 60V in a 0.3M oxalic acid solution to prepare porous aluminum oxide AAO, and the AAO barrier layer is removed by an in-situ through-hole process to expose the metal tantalum surface corresponding to the bottom of the AAO template hole; the electrolyte is replaced with a concentrated sulfuric acid solution containing hydrofluoric acid, and the oxide nanowire array is grown in situ under the AAO confined template by anodization method, and finally the AAO template is dissolved by phosphoric acid to obtain the tantalum oxide nanowire array;

[0057] (12) Tantalum oxide nanotube arrays were prepared by anodization: the electrolyte was a concentrated sulfuric acid solution containing hydrofluoric acid. To reduce surface defects, the tantalum sheet was pre-oxidized and then ultrasonically shaken in deionized water for 60 min to remove the tantalum oxide tubes. The tantalum sheet was rinsed with deionized water and dried, followed by secondary oxidation to obtain a tantalum oxide nanotube array.

[0058] In the step (11), the thickness of the aluminum film is 20 microns.

[0059] In the step (11), when the oxide nanowire array is in-situ grown under the AAO confinement template by anodization, the AAO oxidation time is 10 hours.

[0060] In step (11) and step (12), the concentration of the hydrofluoric acid is 10 vol%.

[0061] In the step (11), the constant voltage is selected to be 90V.

[0062] In the steps (11) and (12), the oxidation temperature of tantalum oxide is 40°C.

[0063] In the steps (11) and (12), the oxidation time of tantalum oxide is 120 minutes.

[0064] Example 5

[0065] Based on Examples 1-4, this embodiment discloses:

[0066] In the step (2), the reaction temperature is 850°C.

[0067] In the step (2), the reaction time is up to 5 hours.

[0068] In the step (2), the ammonia flow rate is 20 sccm.

[0069] Example 6

[0070] Based on Examples 1-4, this embodiment discloses:

[0071] In the step (2), the reaction temperature is 1200°C.

[0072] In the step (2), the reaction time is up to 15 hours.

[0073] In the step (2), the ammonia flow rate is 50 sccm.

[0074] Example 7

[0075] Based on Examples 1-6, this embodiment discloses:

[0076] In the step (3), the ferroelectric material is PVDF.

[0077] In the step (3), the concentration of the ferroelectric material is 0.05 mg / mL.

[0078] In the step (3), the polarization reversal voltage is -5V to 5V.

[0079] Example 8

[0080] Based on Examples 1-6, this embodiment discloses:

[0081] In the step (3), the ferroelectric material is PTFE.

[0082] In the step (3), the concentration of the ferroelectric material is 1 mg / mL.

[0083] In the step (3), the polarization reversal voltage is -10V to 10V.

[0084] Example 9

[0085] Based on Examples 1-6, this embodiment discloses:

[0086] In the step (3), the ferroelectric material is P(VDF-TrFE).

[0087] Example 10

[0088] Tantalum sheets of a certain size were cut, ultrasonically cleaned with acetone and ethanol for 30 minutes respectively, and placed in an oxidation constant temperature electrolytic cell. Graphite sheets were selected as cathodes, and the electrolyte was a concentrated sulfuric acid solution containing hydrofluoric acid (volume fraction of 1 vol%). The pre-oxidation voltage was 40V, the time was 30 minutes, and the experimental temperature was 15°C. After the reaction was completed, the oxide film was removed by ultrasonic treatment for 30 minutes, and the tantalum substrate was used as the secondary oxidation; the secondary oxidation voltage was 60V, the time was 30 minutes, and the reaction temperature was 10°C. The prepared samples were washed with deionized water and dried with N2 for later use. Finally, the prepared samples were heat treated at 450°C in an air atmosphere for 2 hours to obtain a crystallized tantalum oxide nanotube array. The scanning electron microscopy of the tantalum oxide nanotube array is as follows: Figure 1As shown. The nitridation temperature is 950℃, the time is 11h, and the ammonia flow rate is 40sccm. The ferroelectric material applied is 0.1mg / mL P(VDF-TrFE), and the polarization reversal voltage is -5V~5V.

[0089] Embodiment 11

[0090] Tantalum sheets of a certain size were cut and ultrasonically cleaned with acetone and ethanol for 30 minutes respectively, and then placed in an oxidation constant temperature electrolytic cell. Graphite sheets were selected as cathodes and the electrolyte was a concentrated sulfuric acid solution containing hydrofluoric acid (volume fraction of 5 vol%). The pre-oxidation voltage was 40V, the time was 30 minutes, and the experimental temperature was 15°C. After the reaction was completed, the oxide film was removed by ultrasonic for 30 minutes and used as a secondary oxidation tantalum substrate; the secondary oxidation voltage was 70V, the time was 60 minutes, and the reaction temperature was 20°C. The prepared samples were washed with deionized water and dried with N2 for use. Finally, the prepared samples were heat treated at 450°C in an air atmosphere for 2 hours to obtain a crystallized tantalum oxide nanotube array. The nitridation temperature was 1150°C, the time was 12 hours, and the ammonia flow rate was 50 sccm. The ferroelectric material applied by drop coating was 0.5 mg / mL P(VDF-TrFE), and the polarization reversal voltage was -7V to 7V.

[0091] Example 12

[0092] An aluminum film with a thickness of 3 microns was prepared on a tantalum substrate by ion sputtering technology, and then porous AAO was prepared by anodization method, and the oxidation time was 30 minutes. After through-hole treatment, it was placed in an oxidation constant temperature electrolytic cell, and a graphite sheet was selected as the cathode, and the electrolyte was a concentrated sulfuric acid solution containing hydrofluoric acid (volume fraction was 5 vol%). The pre-oxidation voltage was 40V, the time was 30 minutes, and the experimental temperature was 15°C. After the reaction was completed, the oxide film was removed by ultrasound for 30 minutes, and it was used as a secondary oxidation tantalum substrate; the secondary oxidation voltage was 90V, the time was 100 minutes, and the reaction temperature was 30°C. The prepared sample was washed with deionized water and dried with N2 for standby use. Finally, the prepared sample was heat treated at 450°C in an air atmosphere for 2 hours to obtain a crystallized tantalum oxide nanotube array. The nitridation temperature was 1200°C, the time was 14 hours, and the ammonia flow rate was 40 sccm. The ferroelectric material applied by drop coating is 1 mg / mL of P(VDF-TrFE), and the polarization reversal voltage is -10V to 10V.

[0093] Working principle of the present invention:

[0094] The tantalum nitride used in the evaporation power generation device of the present invention has a photosensitive effect, a wide light absorption range (can respond to visible light), a high intrinsic carrier concentration and a high surface charge. In addition, the one-dimensional ordered nanowire / nanotube structure can provide a directional vertical and controllable liquid transmission channel. By adding a ferroelectric material between the nanostructured tantalum nitride and the top electrode, an additional electric field that promotes the selective separation and directional transmission of carriers can be generated by adjusting the polarization direction of the ferroelectric domain, thereby further improving the output power. The prepared photo-assisted hydrovoltaic power generation device not only has excellent hydrovoltaic power generation performance, but also can realize the coordinated utilization of light energy and water energy.

Claims

1. A photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride, characterized by: The invention comprises tantalum nitride responsive to visible light and an ultra-thin layer of ferroelectric material drop-coated on a substrate, wherein the ultra-thin layer is subjected to annealing and polarization inversion treatment.

2. The method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride according to claim 1, characterized in that: The steps include: (1) Preparation of tantalum oxide nanowire arrays and tantalum oxide nanotube arrays; (2) Tantalum oxide nanowire arrays and tantalum oxide nanotube arrays are directly prepared in an ammonia atmosphere by controlling the reaction temperature, ammonia flow rate, and reaction time to produce visible light responsive tantalum nitride; (3) A ferroelectric material is prepared and drop-coated on a substrate of a visible light-responsive tantalum nitride nanomaterial to form an ultra-thin layer, which is then annealed at 145°C for 30 minutes to perform a polarization reversal treatment.

3. The method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride according to claim 2, characterized in that: The step (1) comprises the following specific steps: (11) Preparation of tantalum oxide nanowire arrays by template method: by using a coating process, an aluminum film of a certain thickness is evaporated on a tantalum substrate, and anodized for a certain period of time at a constant voltage of 60V in a 0.3M oxalic acid solution to prepare porous aluminum oxide AAO, and the AAO barrier layer is removed by an in-situ through-hole process to expose the metal tantalum surface corresponding to the bottom of the AAO template hole; the electrolyte is replaced with a concentrated sulfuric acid solution containing a certain amount of hydrofluoric acid, and the oxide nanowire array is grown in situ under the AAO confined template by anodization method, and finally the AAO template is dissolved by phosphoric acid to obtain the tantalum oxide nanowire array; (12) Preparation of tantalum oxide nanotube arrays by anodization: the electrolyte is a concentrated sulfuric acid solution containing a certain amount of hydrofluoric acid. To reduce surface defects, the tantalum sheet is first pre-oxidized and then ultrasonically shaken in deionized water for 30 to 60 minutes to remove the tantalum oxide tubes. The tantalum sheet is then rinsed with deionized water and dried, followed by secondary oxidation to obtain a tantalum oxide nanotube array.

4. The method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride as claimed in claim 3, characterized in that: In the step (1), the thickness of the aluminum film is 200 nanometers to 20 micrometers; when the oxide nanowire array is in situ grown under the AAO confined template by anodization, the AAO oxidation time is 5 minutes to 10 hours; the concentration of the hydrofluoric acid is 0.5 vol% to 10 vol%; the selection range of the constant voltage is 10V to 90V; the oxidation temperature of tantalum oxide is -0.5°C to 40°C; and the oxidation time of tantalum oxide is 3 minutes to 120 minutes.

5. The method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride according to claim 1, characterized in that: In the step (2), the reaction temperature is 850° C. to 1200° C.; the reaction time is 5 h to 15 h; and the ammonia flow rate is 20 sccm to 50 sccm.

6. The method for preparing a photo-assisted hydrovoltaic power generation device based on ferroelectric polarized tantalum nitride according to claim 1, characterized in that: In the step (3), the ferroelectric material is at least one of PVDF, PTFE and P(VDF-TrFE); the concentration of the ferroelectric material is 0.05 to 1 mg / mL; and the polarization reversal voltage is ±5V to ±10V.

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