CN109326450B - Counter electrode material of dye-sensitized solar cell and preparation method thereof - Google Patents
Counter electrode material of dye-sensitized solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flexible carbon fiber-based dye-sensitized solar cell counter electrode material and a preparation method thereof, and solves the technical problem that the traditional flat-plate dye-sensitized solar cells (PDSSCs) based on a hard substrate are limited in portable application due to poor external force resistance and large space limitation. The material is applied to the counter electrode of the dye-sensitized solar cell, has extremely large specific surface area, extremely large porosity and good flexibility, breaks through the hard base of the traditional counter electrode material, and is an effective material for the counter electrode of the flexible dye-sensitized solar cell.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a flexible carbon fiber-based dye-sensitized solar cell counter electrode material and a preparation method thereof. In particular to a preparation method of a counter electrode material applicable to a dye-sensitized solar cell (DSSC).
Background
With the continuous development of world economy, the human society has more and more demands on energy, and the development and utilization of new energy become a hotspot of research in a plurality of fields. How to convert solar energy into electrical energy or other forms of energy at low cost and efficiently is a significant challenge facing scientists.
The main structure of the DSSC comprises a photo anode, a dye molecule, an electrolyte, a counter electrode and the like. The operation of the DSSC is essentially a continuous cycle of photoelectrochemical reactions. The chemical reaction of the battery mainly occurs in two regions: firstly, the interface surface of the photo-anode and the electrolyte is arranged; the other occurs at the contact interface of the counter electrode and the electrolyte. The rate of the electrochemical reaction is closely related to the nature of the electrocatalyst, which is typically composed of a conductive substrate and catalytic layer materials. The main function of the conductive substrate is to collect electrons from an external circuit; the catalytic layer material mainly has the functions of providing catalytic active sites for redox electron pairs in the electrolyte, promoting the cyclic regeneration of redox electrolytic pairs and further promoting the cyclic regeneration of dye molecules in the photoanode. At present, platinum is the most commonly used catalyst of the DSSC counter electrode, and other commonly used non-platinum catalytic materials comprise carbon materials, conductive polymers, carbides, sulfides, nitrides of transition metals and the like. Generally, the following three conditions are required as a counter electrode material: the electrolyte has good chemical stability and does not react with redox substances in the electrolyte; the conductive performance is excellent, and the rapid transmission of electrons is facilitated; and the catalyst has better catalytic reduction capability on the electrolyte. Although the photoelectric performance of DSSCs has been greatly improved over twenty years, there is some work in the process of practical implementation that requires further improvement. Traditional flat-plate dye-sensitized solar cells (PDSSCs) based on a hard substrate are limited in portable application due to poor external force resistance and large space limitation. The flexible fiber dye-sensitized solar cells (FDSSCs) can be woven into wearable flexible functional devices such as clothes and caps, and become a research hotspot in the photovoltaic field. Currently, commercial Pt wires are used as the typical counter electrodes of the FDSSCs, but the counter electrodes are too expensive to be manufactured, which is not favorable for commercialization of the FDSSCs.
Electrospinning is a spinning technology developed based on the principle that high-speed jet is generated by conductive fluid under a high-voltage electrostatic field, and is different from the conventional method, and the spun nanofiber has a thin diameter and a large specific surface area.
Disclosure of Invention
The invention aims to solve the technical problems that the traditional flat-plate dye-sensitized solar cells (PDSSCs) based on a hard substrate are limited in portable application due to poor external force resistance and large space limitation, and a typical FDSSCs counter electrode adopts commercial Pt filaments, but the manufacturing cost is too high, so that the commercialization of the FDSSCs is not facilitated, and provides a flexible carbon fiber-based dye-sensitized solar cell counter electrode material and a preparation method thereof. Performing electrostatic spinning by using a polyacrylonitrile and N-N dimethylformamide blended solution, taking a carbon filament as a core layer, wrapping a layer of oriented polyacrylonitrile nano fiber on the conductive carbon filament by using a conjugated electrostatic spinning technology, and then depositing a conductive polymer- - -polypyrrole in situ on the carbon filament/polyacrylonitrile nano fiber core-spun yarn to obtain the carbon filament/polyacrylonitrile/polypyrrole (CF/PAN/PPy) nano fiber core-spun yarn counter electrode material. The material fiber has extremely fine diameter and large specific surface area, and polypyrrole deposited by the core spun yarn improves the conductivity of the yarn, increases the porosity of the material, and can provide more catalytic active sites for the redox reaction of an electrolytic pair.
In order to solve the technical problems, the invention adopts the following technical scheme: the utility model provides a flexible carbon fiber base dye-sensitized solar cell counter electrode material, includes sandwich layer and the cortex of parcel in the sandwich layer outside, the sandwich layer be conductive carbon filament, the cortex is polyacrylonitrile nanofiber, the surface deposit of polyacrylonitrile nanofiber has the electrically conductive nano-particle of polypyrrole.
The polyacrylonitrile nano-fiber is wrapped on the conductive carbon filament through conjugate electrostatic spinning, and the diameter of the polyacrylonitrile nano-fiber is 100-500 nm. The porosity is 40-80%, and the pore size is 8-25 nm.
The polypyrrole conductive nanoparticles are chemically deposited on the surface of polyacrylonitrile nanofibers in situ, and the particle size of the polypyrrole conductive nanoparticles is 30-180 nm. The polypyrrole conductive nanoparticles have good conductivity and electrocatalytic activity, the particle size of the polypyrrole nanoparticles is 30-180 nm, the pore size is 8-25 nm, and the crystal structure is a ferroelectric phase.
The preparation method of the flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) drying polyacrylonitrile powder at 20-60 ℃ for 20-60 min, adding the dried polyacrylonitrile powder into a solvent by taking an N-N dimethylformamide solution as the solvent, and stirring at 30-70 ℃ for 3-8 h to obtain a spinning solution with the mass fraction of polyacrylonitrile being 10-15%;
(2) performing electrostatic spinning on the spinning solution obtained in the step (1), and twisting conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare carbon filament/polyacrylonitrile nanofiber core-spun yarns;
(3) placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 20-80 min; taking out the core-spun yarn after soaking, and adding the FeCl3•6H2Dropwise adding the O solution into the pyrrole monomer solution, uniformly stirring, putting the soaked core-spun yarn again, reacting for 2-7 h at the temperature of 0-5 ℃, taking out the core-spun yarn, fully cleaning, and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn;
(4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, and attaching a gel electrolyte to the plain mesh fabric to obtain the counter electrode material of the dye-sensitized solar cell.
The molecular weight of the polyacrylonitrile in the step (1) is 50000-150000.
The spinning voltage of the conjugated electrostatic spinning device in the step (2) is 10 kV to 25 kV, the spinning temperature is 20 ℃ to 25 ℃, the spinning humidity is 10 percent to 40 percent, the flow ratio of the solution of the positive spray head and the negative spray head is 3/5 to 3/2, the distance between the positive spray head and the negative spray head is 10cm to 20cm, the vertical distance between the spray heads and the edge of the bell mouth is 2cm to 8 cm, the inner diameter of the spray heads is 0.1mm to 0.5mm, the rotating speed of the bell mouth is 0r/min to 180 r/min, and the winding speed is 0 r/min.
FeCl described in step (3)3•6H25-15 percent of O, 0.3-1.8 percent of pyrrole monomer solution and FeCl3•6H2The mass ratio of the O solution to the pyrrole monomer solution is 1: 10-1: 20.
The invention utilizes a method combining electrostatic spinning technology and in-situ polymerization, takes conductive carbon filaments as a core layer, wraps polyacrylonitrile nanofibers on the carbon filaments by the conjugated electrostatic spinning technology, and then carries out in-situ polymerization and deposition on the core-spun yarns to prepare the oriented carbon filament/polyacrylonitrile/polypyrrole (CF/PAN/PPy) nanofiber core-spun yarns, which have good conductivity and electrocatalytic activity, are applied to the counter electrode of the dye-sensitized solar cell, have extremely large specific surface area, extremely large porosity and good flexibility, break through the hard base of the traditional counter electrode material, and are effective materials as the counter electrode of the flexible dye-sensitized solar cell.
Compared with the prior counter electrode material of the dye-sensitized solar cell and the preparation method thereof, the invention has the following advantages: (1) the oriented CF/PAN/PPy nanofiber core-spun yarn obtained by the invention has extremely small pore size, extremely large specific surface area and porosity, is beneficial to permeation of electrolyte and rapid transmission of electrons, can provide more catalytic active sites for redox reaction of an electrolytic pair, and further obtains higher photoelectric conversion efficiency. (2) The oriented CF/PAN/PPy nanofiber core-spun yarn prepared by the invention has good flexibility, can be used as an electrode material of FDSSCs, and has the advantages of being bendable, capable of being woven, wide in application range and the like compared with the traditional rigid PDSSCs electrode material. (3) The whole manufacturing process is simple and convenient, easy to operate, simple in process, low in cost and environment-friendly.
Drawings
Fig. 1 is a low-magnification electron micrograph of the prepared carbon filament/polyacrylonitrile nanofiber core-spun yarn.
Fig. 2 is a high-magnification electron microscope photograph of the prepared polypyrrole/carbon filament/polyacrylonitrile nanofiber covering yarn.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) drying polyacrylonitrile powder at 60 ℃ for 30min, taking N-N dimethylformamide solution as a solvent, wherein the mass ratio of N-N dimethylformamide to polyacrylonitrile is 9: 1. stirring the mixture for 5 hours at the temperature of 40 ℃ to prepare polyacrylonitrile spinning solution with the mass fraction of 10 percent. The molecular weight of polyacrylonitrile is 80000.
(2) And (2) performing electrostatic spinning on the polyacrylonitrile spinning solution obtained in the step (1), and twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn. Spinning voltage: 10 kV, spinning temperature: 20 ℃, spinning humidity: 15 percent, the flow ratio of the solution of the positive spray head and the negative spray head is 3/5, the distance between the positive spray head and the negative spray head is 10cm, the vertical distance between the spray heads and the edge of the bell mouth is 4cm, the inner diameter of the spray heads is 0.3mm, the rotating speed of the bell mouth is 150 r/min, and the winding speed is 30 r/min.
(3) Placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 50min, and adding FeCl3•6H2The mass ratio of O to deionized water is 2:25, the core-spun yarn is taken out after the soaking is finished, and the FeCl is added3•6H2And dropwise adding the O solution into the pyrrole monomer solution, wherein the mass ratio of the pyrrole monomer (Py) to the deionized water is 1:250, uniformly stirring, putting the soaked core-spun yarn again, sealing, placing in an environment at 0 ℃, reacting for 6 hours, taking out the yarn, fully cleaning with the deionized water, and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nanofiber core-spun yarn. FeCl3•6H2The mass fraction of the O solution is 8 percent, and the mass fraction of the pyrrole is 0.4 percent. The average diameter of the PAN nanofiber is 150 nm, the porosity is 80%, the particle size of the polypyrrole is 100nm, and the pore size is 10 nm.
(4) And (4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, attaching a gel electrolyte, and using the plain mesh fabric as a counter electrode material of a dye-sensitized solar cell.
Table 1 shows photovoltaic parameters of the dye-sensitized solar cell of the flexible carbon fiber-based counter electrode material of each example, SEM photographs of the surface morphology structure of the flexible carbon fiber-based counter electrode material are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that polyacrylonitrile nanofibers are wrapped on carbon filaments in an oriented manner, the fibers are uniform in thickness and good in formation, the average diameter is 300 nanometers, and it can be seen from fig. 2 that polypyrrole is uniformly deposited on the nanofibers.
Example 2
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) drying polyacrylonitrile powder at 50 ℃ for 40min, taking N-N dimethylformamide solution as a solvent, wherein the mass ratio of N-N dimethylformamide to polyacrylonitrile is 8: 1. stirring for 4h at 50 ℃ to prepare the polyacrylonitrile spinning solution with the mass fraction of 11%. The molecular weight of polyacrylonitrile is 70000.
(2) And (2) performing electrostatic spinning on the polyacrylonitrile spinning solution obtained in the step (1), and twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn. Spinning voltage: 12 kV, spinning temperature: 21 ℃, spinning humidity: 18 percent, the flow ratio of the solution of the positive spray head and the negative spray head is 3/4, the distance between the positive spray head and the negative spray head is 12cm, the vertical distance between the spray heads and the edge of the bell mouth is 5cm, the inner diameter of the spray heads is 0.4mm, the rotating speed of the bell mouth is 130 r/min, and the winding speed is 40 r/min.
(3) Placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 40min, and adding FeCl3•6H2The mass ratio of O to deionized water is 1:10, and the materials are taken after soakingTaking out the core-spun yarn, and mixing the FeCl3•6H2And dropwise adding the O solution into the pyrrole monomer solution, wherein the mass ratio of pyrrole (Py) to deionized water is 1:100, uniformly stirring, putting the soaked core-spun yarn again, sealing, placing in an environment at 1 ℃, reacting for 4 hours, taking out the yarn, fully cleaning with deionized water, and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nanofiber core-spun yarn. FeCl3•6H2The mass fraction of the O solution is 9 percent, and the mass fraction of the pyrrole is 1 percent. The average diameter of the PAN nanofiber is 200 nm, the porosity is 70%, the particle size of the polypyrrole is 80nm, and the pore size is 12 nm.
(4) And (4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, attaching a gel electrolyte, and using the plain mesh fabric as a counter electrode material of a dye-sensitized solar cell.
The photovoltaic parameters of the dye-sensitized solar cell based on the composite material counter electrode are shown in table 1.
Example 3
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) drying polyacrylonitrile powder at 40 ℃ for 50min, taking N-N dimethylformamide solution as a solvent, wherein the mass ratio of N-N dimethylformamide to polyacrylonitrile is 7: 1. stirring for 4h at 55 ℃ to prepare polyacrylonitrile spinning solution with the mass fraction of 12.5%. The molecular weight of polyacrylonitrile is 100000.
(2) And (2) performing electrostatic spinning on the polyacrylonitrile spinning solution obtained in the step (1), and twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn. Spinning voltage: 14 kV, spinning temperature: 22 ℃, spinning humidity: 20 percent, 1/1 flow ratio of the solution of the positive spray head and the negative spray head, 13cm distance between the positive spray head and the negative spray head, 6cm vertical distance between the spray heads and the edge of the bell mouth, 0.5mm inner diameter of the spray heads, 120 r/min rotation speed of the bell mouth and 35 r/min winding speed.
(3) Firstly, placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 30min, and adding FeCl3•6H2The mass ratio of O to deionized water is 1:9, the core-spun yarn is taken out after the soaking is finished, and the FeCl is added3•6H2And dropwise adding the O solution into the pyrrole monomer solution, wherein the mass ratio of pyrrole (Py) to deionized water is 3:200, uniformly stirring, putting the soaked core-spun yarn again, sealing, placing in an environment at 2 ℃, reacting for 3.5 hours, taking out the yarn, fully cleaning with deionized water, and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nanofiber core-spun yarn. FeCl3•6H2The mass fraction of the O solution is 10 percent, and the mass fraction of the pyrrole is 1.2 percent. The average diameter of the PAN nano-fiber is 100-500 nm, the porosity is 40% -80%, the particle size of the polypyrrole is 30-180 nm, and the pore size is 8-25 nm.
(4) And (4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, attaching a gel electrolyte, and using the plain mesh fabric as a counter electrode material of a dye-sensitized solar cell.
The photovoltaic parameters of the dye-sensitized solar cell based on the composite material counter electrode are shown in table 1.
Example 4
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) drying polyacrylonitrile powder at 30 ℃ for 60min, taking N-N dimethylformamide solution as a solvent, wherein the mass ratio of N-N dimethylformamide to polyacrylonitrile is 6: 1. stirring for 3h at 60 ℃ to prepare polyacrylonitrile spinning solution with the mass fraction of 14%. The molecular weight of polyacrylonitrile is 110000.
(2) And (2) performing electrostatic spinning on the polyacrylonitrile spinning solution obtained in the step (1), and twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn. Spinning voltage: 15 kV, spinning temperature: 24 ℃, spinning humidity: 23 percent, the flow ratio of the solution of the positive spray head and the negative spray head is 3/2, the distance between the positive spray head and the negative spray head is 14cm, the vertical distance between the spray heads and the edge of the bell mouth is 7cm, the inner diameter of the spray heads is 0.6mm, the rotating speed of the bell mouth is 110 r/min, and the winding speed is 30 r/min.
(3) Firstly, the carbon filament/polymer prepared in the step (2)The acrylonitrile nano-fiber core-spun yarn is arranged in FeCl3•6H2Soaking in O solution for 20min, and adding FeCl3•6H2The mass ratio of O to deionized water is 1:7, the core-spun yarn is taken out after the soaking is finished, and the FeCl is added3•6H2And dropwise adding the O solution into the pyrrole monomer solution, wherein the mass ratio of the pyrrole (Py) monomer to the deionized water is 1:50, uniformly stirring, putting the soaked core-spun yarn again, sealing and placing the core-spun yarn in an environment at 3 ℃, reacting for 3 hours, taking out the yarn, fully cleaning the yarn with the deionized water, and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nanofiber core-spun yarn. FeCl3•6H2The mass fraction of the O solution is 14 percent, and the mass fraction of the pyrrole is 1.5 percent. The average diameter of the PAN nano-fiber is 100-500 nm, the porosity is 40% -80%, the particle size of the polypyrrole is 30-180 nm, and the pore size is 8-25 nm.
(4) And (4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, attaching a gel electrolyte, and using the plain mesh fabric as a counter electrode material of a dye-sensitized solar cell.
Example 5
The utility model provides a flexible carbon fiber base dye-sensitized solar cell counter electrode material, includes sandwich layer and the cortex of parcel in the sandwich layer outside, the sandwich layer be conductive carbon filament, the cortex is polyacrylonitrile nanofiber, the surface deposit of polyacrylonitrile nanofiber has the electrically conductive nano-particle of polypyrrole. The polyacrylonitrile nano-fiber is wrapped on the conductive carbon filament through conjugate electrostatic spinning, and the diameter of the polyacrylonitrile nano-fiber is 100-500 nm. The polypyrrole conductive nanoparticles are chemically deposited on the surface of polyacrylonitrile nanofibers in situ, and the particle size of the polypyrrole conductive nanoparticles is 30-180 nm.
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) preparing a spinning solution: drying polyacrylonitrile powder at 20 ℃ for 20min, taking an N-N dimethylformamide solution as a solvent, adding the dried polyacrylonitrile powder into the solvent, and stirring at 30 ℃ for 3h to obtain a spinning solution with the mass fraction of polyacrylonitrile being 10%; the molecular weight of the polyacrylonitrile is 50000-150000;
(2) carrying out electrostatic spinning on the spinning solution obtained in the step (1): twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn; the spinning voltage of the conjugated electrostatic spinning device is 10 kV, the spinning temperature is 20 ℃, the spinning humidity is 10%, the solution flow ratio of the positive nozzle and the negative nozzle is 3/5, the distance between the positive nozzle and the negative nozzle is 10cm, the vertical distance between the nozzle and the edge of the bell mouth is 2cm, the inner diameter of the nozzle is 0.1mm, the rotating speed of the bell mouth is 180 r/min, and the winding speed is 50 r/min;
(3) depositing pyrrole conductive nanoparticles: placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 20 min; taking out the core-spun yarn after soaking, and adding the FeCl3•6H2Dropwise adding the O solution into the pyrrole monomer solution, uniformly stirring, putting the soaked core-spun yarn again, reacting for 7 hours at the temperature of 5 ℃, taking out the core-spun yarn, fully cleaning and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn; the FeCl3•6H2The mass fraction of the O solution is 5 percent, the mass fraction of the pyrrole monomer solution is 0.3 percent, and FeCl is added3•6H2The mass ratio of the O solution to the pyrrole monomer solution is 1: 10;
(4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, and attaching a gel electrolyte to the plain mesh fabric to obtain the counter electrode material of the dye-sensitized solar cell.
Example 6
The utility model provides a flexible carbon fiber base dye-sensitized solar cell counter electrode material, includes sandwich layer and the cortex of parcel in the sandwich layer outside, the sandwich layer be conductive carbon filament, the cortex is polyacrylonitrile nanofiber, the surface deposit of polyacrylonitrile nanofiber has the electrically conductive nano-particle of polypyrrole.
A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises the following steps: (1) preparing a spinning solution: drying polyacrylonitrile powder at 40 ℃ for 40min, taking an N-N dimethylformamide solution as a solvent, adding the dried polyacrylonitrile powder into the solvent, and stirring at 50 ℃ for 5h to obtain a spinning solution with the mass fraction of polyacrylonitrile being 15%; the molecular weight of the polyacrylonitrile is 50000-150000;
(2) carrying out electrostatic spinning on the spinning solution obtained in the step (1): twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn; the spinning voltage of the conjugated electrostatic spinning device is 25 kV, the spinning temperature is 22 ℃, the spinning humidity is 20%, the solution flow ratio of the positive nozzle and the negative nozzle is 3/4, the distance between the positive nozzle and the negative nozzle is 15 cm, the vertical distance between the nozzle and the edge of the bell mouth is 5cm, the inner diameter of the nozzle is 0.3mm, the rotating speed of the bell mouth is 90 r/min, and the winding speed is 25 r/min;
(3) depositing pyrrole conductive nanoparticles: placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 50 min; taking out the core-spun yarn after soaking, and adding the FeCl3•6H2Dropwise adding the O solution into the pyrrole monomer solution, uniformly stirring, putting the soaked core-spun yarn again, reacting for 2 hours at the temperature of 0 ℃, taking out the core-spun yarn, fully cleaning and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn; the FeCl3•6H2The mass fraction of the O solution is 15 percent, the mass fraction of the pyrrole monomer solution is 1.8 percent, and FeCl is added3•6H2The mass ratio of the O solution to the pyrrole monomer solution is 1: 10;
(4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, and attaching a gel electrolyte to the plain mesh fabric to obtain the counter electrode material of the dye-sensitized solar cell.
The photovoltaic parameters of the dye-sensitized solar cell based on the composite material counter electrode are shown in table 1.
Table 1 photovoltaic parameters of dye-sensitized solar cell of flexible carbon fiber-based counter electrode material of each example
Therefore, the flexible carbon fiber-based dye-sensitized solar cell counter electrode material obtained by the invention has the advantages that the nano fibers are wrapped on the carbon filaments in a certain orientation, the surface of the yarn is provided with a large number of pores, and the material has a large specific surface area and a very fine fiber diameter, so that the permeation of electrolyte and the transmission of electrons are facilitated. The polypyrrole deposited by in-situ polymerization has uniform particle size, improves the conductivity of the yarn, and can provide more catalytic active sites for the redox reaction of the electrolytic couple. The DSSC based on the composite material as the counter electrode achieves ideal photoelectric performance, and the composite material can be used as an effective counter electrode material of the DSSC. In addition, the carbon filament/polyacrylonitrile/polypyrrole nanofiber core-spun yarn prepared by the invention has certain flexibility and knittability, can be knitted into wearable flexible functional equipment such as clothes, hats and the like, and has a wide application range.
Claims (6)
1. A preparation method of a flexible carbon fiber-based dye-sensitized solar cell counter electrode material is characterized by comprising the following steps: (1) preparing a spinning solution: drying polyacrylonitrile powder at 20-60 ℃ for 20-60 min, adding the dried polyacrylonitrile powder into a solvent by taking an N-N dimethylformamide solution as the solvent, and stirring at 30-70 ℃ for 3-8 h to obtain a spinning solution with the mass fraction of polyacrylonitrile being 10-15%;
(2) carrying out electrostatic spinning on the spinning solution obtained in the step (1): twisting the conductive carbon filaments into fiber bundles as a core layer by using a conjugated electrostatic spinning device to prepare the carbon filament/polyacrylonitrile nanofiber core-spun yarn;
(3) depositing pyrrole conductive nanoparticles: placing the carbon filament/polyacrylonitrile nano-fiber core-spun yarn prepared in the step (2) in FeCl3•6H2Soaking in O solution for 20-80 min; taking out the core-spun yarn after soaking, and adding the FeCl3•6H2Adding the O solution into the pyrrole monomer solution drop by drop, stirring uniformly, and then putting into the solution again for soakingPlacing the soaked core-spun yarn in an environment of 0-5 ℃, reacting for 2-7 h, taking out the core-spun yarn, fully cleaning and drying to obtain the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn;
(4) weaving the carbon filament/polyacrylonitrile/polypyrrole nano-fiber core-spun yarn obtained in the step (3) into a plain mesh fabric, and attaching a gel electrolyte to the plain mesh fabric to obtain a counter electrode material of the dye-sensitized solar cell;
the flexible carbon fiber-based dye-sensitized solar cell counter electrode material comprises a core layer and a skin layer wrapped on the outer side of the core layer, wherein the core layer is conductive carbon filaments, the skin layer is polyacrylonitrile nanofibers, and polypyrrole conductive nanoparticles are deposited on the surface of the polyacrylonitrile nanofibers.
2. The method for preparing the flexible carbon fiber-based dye-sensitized solar cell counter electrode material according to claim 1, characterized in that: the polyacrylonitrile nano-fiber is wrapped on the conductive carbon filament through conjugate electrostatic spinning, and the diameter of the polyacrylonitrile nano-fiber is 100-500 nm.
3. The method for preparing the flexible carbon fiber-based dye-sensitized solar cell counter electrode material according to claim 1, characterized in that: the polypyrrole conductive nanoparticles are chemically deposited on the surface of polyacrylonitrile nanofibers in situ, and the particle size of the polypyrrole conductive nanoparticles is 30-180 nm.
4. The method for preparing the flexible carbon fiber-based dye-sensitized solar cell counter electrode material according to claim 1, characterized in that: the molecular weight of the polyacrylonitrile in the step (1) is 50000-150000.
5. The method for preparing the flexible carbon fiber-based dye-sensitized solar cell counter electrode material according to claim 1, characterized in that: the spinning voltage of the conjugated electrostatic spinning device in the step (2) is 10 kV to 25 kV, the spinning temperature is 20 ℃ to 25 ℃, the spinning humidity is 10 percent to 40 percent, the flow ratio of the solution of the positive spray head and the negative spray head is 3/5 to 3/2, the distance between the positive spray head and the negative spray head is 10cm to 20cm, the vertical distance between the spray heads and the edge of the bell mouth is 2cm to 8 cm, the inner diameter of the spray heads is 0.1mm to 0.5mm, the rotating speed of the bell mouth is 0r/min to 180 r/min, and the winding speed is 0 r/min.
6. The method for preparing the flexible carbon fiber-based dye-sensitized solar cell counter electrode material according to claim 1, characterized in that: FeCl described in step (3)3•6H25-15% of O solution, 0.3-1.8% of pyrrole monomer solution and FeCl3•6H2The mass ratio of the O solution to the pyrrole monomer solution is 1: 10-1: 20.
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