CN114373637B - Quantum dot sensitized solar cell counter electrode and preparation method thereof - Google Patents
Quantum dot sensitized solar cell counter electrode and preparation method thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 79
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000003763 carbonization Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000001276 controlling effect Effects 0.000 description 15
- 230000001105 regulatory effect Effects 0.000 description 15
- 239000002390 adhesive tape Substances 0.000 description 14
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention provides a quantum dot sensitized solar cell counter electrode and a preparation method thereof, wherein the preparation method comprises the following steps: (a) preparing polyacrylonitrile carbon nanofibers; (b) Uniformly mixing sodium carboxymethyl cellulose, isopropanol and ethanol, and magnetically stirring for 10-14 h to obtain an adhesive; (c) Grinding the carbon nanofibers obtained in the step (a) into powder, dropwise adding the adhesive, and continuously grinding to prepare carbon paste; (d) Uniformly coating the carbon paste on a titanium mesh substrate, and placing the titanium mesh substrate in an oven for drying; (e) And (3) placing the dried titanium mesh in a nitrogen-protected tubular furnace, calcining at 500-700 ℃ for 20-40 min, and naturally cooling to obtain the counter electrode. Compared with the traditional counter electrode material, the material is cheaper and is easy to obtain, has better stability and can provide higher catalytic performance.
Description
Technical Field
The invention relates to the technical field of solar cell materials, in particular to a quantum dot sensitized solar cell counter electrode and a preparation method thereof.
Background
Energy plays a vital role in the sustainable development process of human beings, however, with the development of modern technology, the problem of environmental pollution and the energy crisis are more and more highlighted, and it is urgent to find efficient, easily available and low-cost renewable environmental cleaning products. Therefore, wind energy, water energy, solar energy, geothermal energy and the like are the focus of attention, wherein solar energy is the most widely distributed renewable energy source on the earth, and has great development potential. Solar cells are one of the important ways to develop and utilize solar energy, and are devices that can directly convert solar energy into electric energy.
The quantum dot sensitized solar cell is used as a third generation solar cell and is called pioneer's name of a novel green energy source in a photoelectric conversion device. The quantum dot sensitized solar cell has a main structure comprising: photo anode (TiO) 2 、SnO 2 ZnO and the like) A sensitizer (quantum dot, etc.), an electrolyte (S) n 2- /S 2- 、((CH 3 ) 4 N) 2 S/((CH 3 ) 4 N) 2 S n Etc.), the counter electrode. The counter electrode is an important component of the quantum dot sensitized solar cell and mainly plays a role in catalyzing the cyclic regeneration of the redox couple in the cell electrolyte, so that the function of reducing sensitizer holes into sensitizer molecules is ensured. Quantum dot sensitized solar cells are more powerful competitors for next generation solar cells by virtue of their high photoelectric conversion efficiency and low production cost.
At present, the counter electrode material of the quantum dot sensitized solar cell has the common problems of high cost, poor stability and non-ideal catalytic performance. Carbon fiber is a conductive material with excellent performance, and has the same conductive performance and stability as other carbon materials due to the unique tubular structure, but has larger specific surface area, so that more catalytic active sites can be provided, the catalytic performance is improved, and the transmission of electrons is facilitated. Therefore, research on the counter electrode of the quantum dot sensitized solar cell based on the carbon fiber has important significance for improving the cell efficiency and the application value.
Disclosure of Invention
The invention aims to provide a quantum dot sensitized solar cell counter electrode and a preparation method thereof, which are used for solving the problems of high price, non-ideal catalytic performance, limited application range and the like of the conventional common electrode.
The technical scheme of the invention is as follows: a quantum dot sensitized solar cell counter electrode, the counter electrode prepared by the method of:
(a) Taking polyacrylonitrile as a solute and dimethylformamide as a solvent, preparing a polyacrylonitrile solution with the mass concentration of 10-15%, stirring to be transparent and viscous, injecting into a high-voltage electrostatic spinning machine for spinning, and carbonizing a spun polyacrylonitrile precursor to obtain the polyacrylonitrile carbon nanofiber;
(b) Uniformly mixing sodium carboxymethyl cellulose, isopropanol and ethanol, and magnetically stirring for 10-14 h to obtain an adhesive;
(c) Grinding the carbon nanofibers obtained in the step (a) into powder, dropwise adding the adhesive, and continuously grinding to prepare carbon paste;
(d) Uniformly coating the carbon paste on a titanium mesh substrate, and placing the titanium mesh substrate in an oven for drying;
(e) And (3) placing the dried titanium mesh in a nitrogen-protected tubular furnace, calcining for 20-40 min at 500-700 ℃, and naturally cooling to obtain the quantum dot sensitized solar cell counter electrode.
In the step (a), the electrostatic spinning process comprises the following steps: the flow rate of the polyacrylonitrile solution is 20-30 uL/min, the total liquid supply rate is 1.2-1.8 mL/h, the voltage of the high-voltage electrostatic spinning machine is 8-12 kv, the needle length is 20-30 cm, and the diameter is 0.5-0.9 mm.
In the step (a), the carbonization process comprises the following steps: placing polyacrylonitrile precursor into a carbonization furnace, heating the inside of the carbonization furnace from room temperature to 280-320 ℃, and keeping the temperature to 0.5-1.5 h to pre-oxidize the polyacrylonitrile; then heating to 900-1100 ℃ under the protection of nitrogen, keeping 0.5-1 h, and cooling to room temperature.
In the step (b), the dosage ratio of sodium carboxymethyl cellulose, isopropanol and ethanol is 0.8g:3-5mL:6-10mL.
In the step (c), the dosage ratio of the carbon nano fiber to the binder is 0.3-3 g:3 mL.
In the step (d), the drying temperature is 50-70 ℃ and the time is 2-4 h; the mesh number of the titanium is 1500-2500 meshes, and the thickness is 0.1-0.3-mm. The carbon paste coating thickness is 0.4-0.9mm.
A preparation method of a quantum dot sensitized solar cell counter electrode comprises the following steps:
(a) Taking polyacrylonitrile as a solute and dimethylformamide as a solvent, preparing a polyacrylonitrile solution with the mass concentration of 10-15%, stirring to be transparent and viscous, injecting into a high-voltage electrostatic spinning machine for spinning, and carbonizing a spun polyacrylonitrile precursor to obtain the polyacrylonitrile carbon nanofiber;
(b) Uniformly mixing sodium carboxymethyl cellulose, isopropanol and ethanol, and magnetically stirring for 10-14 h to obtain an adhesive;
(c) Grinding the carbon nanofibers obtained in the step (a) into powder, dropwise adding the adhesive, and continuously grinding to prepare carbon paste;
(d) Uniformly coating the carbon paste on a titanium mesh substrate, and placing the titanium mesh substrate in an oven for drying;
(e) And (3) placing the dried titanium mesh in a nitrogen-protected tubular furnace, calcining at 500-700 ℃ for 20-40 min, and naturally cooling to obtain the counter electrode.
In the step (a), the electrostatic spinning process comprises the following steps: the flow rate of the polyacrylonitrile solution is 20-30 uL/min, the total liquid supply rate is 1.2-1.8 mL/h, the voltage of the high-voltage electrostatic spinning machine is 8-12 kv, the needle length is 20-30 cm, and the diameter is 0.5-0.9 mm;
the carbonization process comprises the following steps: placing polyacrylonitrile precursor into a carbonization furnace, heating the inside of the carbonization furnace from room temperature to 280-320 ℃, and keeping the temperature to 0.5-1.5 h to pre-oxidize the polyacrylonitrile; then heating to 900-1100 ℃ under the protection of nitrogen, keeping 0.5-1 h, and cooling to room temperature.
In the step (b), the dosage ratio of sodium carboxymethyl cellulose, isopropanol and ethanol is 0.8g:3-5mL:6-10mL. In the step (c), the dosage ratio of the carbon nano fiber to the binder is 0.3-3 g:3 mL; in the step (d), the drying temperature is 50-70 ℃ and the time is 2-4 h; the mesh number of the titanium is 1500-2500 meshes, and the thickness is 0.1-0.3-mm. The carbon paste coating thickness is 0.4-0.9mm.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional counter electrode material, the material of the quantum dot sensitized solar cell counter electrode is cheaper and is easy to obtain, so that the quantum dot sensitized solar cell counter electrode has better stability and can provide higher catalytic performance.
According to the invention, the polyacrylonitrile carbon nanofiber which is regular in shape, has a solid section and uniform in diameter distribution is prepared by an electrostatic spinning technology, and the carbon fiber is directly coated on a titanium mesh by adopting an organic solvent adhesive. The method is simple to operate, so that the carbon fiber and the titanium mesh are stably combined together, and the method has higher conversion efficiency. Compared with the traditional counter electrode, the titanium mesh is cheaper and more available, the mesh structure of the titanium mesh is more beneficial to the diffusion of electrolyte, the conductivity is stronger, the charge transfer dynamics is improved, and the efficient utilization is realized.
Drawings
FIG. 1 is an electron microscopic view of the polyacrylonitrile carbon nanofiber in example 1 of the present invention.
FIG. 2 is a graph showing the comparison of I-V curves of the carbon nanofiber/titanium mesh counter electrode prepared in example 1 of the present invention and a conventional Pt counter electrode in a dye-sensitized solar cell.
Detailed Description
The invention is further illustrated by the following examples, in which the processes and methods not described in detail are conventional and well known in the art, and in which the starting materials or reagents used are commercially available unless otherwise indicated.
Example 1:
firstly, polyacrylonitrile (PAN) is dissolved in 25 mL Dimethylformamide (DMF), wherein the mass percentage content of the PAN is 15%, the PAN is stirred at room temperature to be uniform, transparent and sticky, and then the PAN is transferred into a 10mL syringe, and a needle head with the length of about 25 cm and the diameter of about 0.7 mm is arranged at the front end of the syringe; starting a high-voltage static device, adjusting the voltage to be 10 kV, starting spinning, collecting uniformly distributed PAN filaments at a receiving plate, placing the spun PAN filaments in a tubular reaction furnace, regulating and controlling the heating speed in the carbonization furnace to be 1 ℃/min, heating the carbonization chamber to 300 ℃ from room temperature, and keeping for 1h to pre-oxidize polyacrylonitrile; pre-oxidized polyacrylonitrile is added in N 2 Under protection, the temperature rising speed is regulated to be 1 ℃/min, the temperature is raised to 1000 ℃, the polyacrylonitrile carbon nanofiber is cooled to room temperature, and the black fiber cloth is prepared, and the thickness of the black fiber cloth is measured to be 1.3 mu m.
0.8g sodium carboxymethyl cellulose, 8 mL ethanol and 4 mL isopropanol are weighed, uniformly mixed and continuously stirred for 12 h, so as to obtain the organic adhesive. Weighing 0.3. 0.3 g carbon fiber, grinding into powder, dropwise adding 3. 3 mL binder, and continuously grinding for 40min to obtain carbon paste. The method comprises the steps of taking a 2000-mesh titanium net with the specification of 1.5 cm multiplied by 2.5 cm, controlling the coating thickness through the number of adhesive tape layers, pasting 3 layers of 3M-1600 electric insulating adhesive tapes (specification: 18 mm multiplied by 20M multiplied by 0.15 mm), uniformly coating the surface of the titanium net with a glass rod, and drying the titanium net in an oven at 60 ℃ for 3 h.
Placing the dried titanium mesh electrode into a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 5 ℃/min, and adding the titanium mesh electrode into N 2 And (3) heating from room temperature to 600 ℃ under protection, preserving heat for 30 min, and naturally cooling to room temperature to obtain the carbon nanofiber/titanium mesh counter electrode material. The materials were characterized as shown in figure 1. The photoelectric conversion efficiency of the counter electrode prepared from the material is 8.07 percent according to the measurement.
Example 2:
firstly, polyacrylonitrile (PAN) is dissolved in 25 mL Dimethylformamide (DMF), wherein the mass percentage content of the PAN is 10 percent, the PAN is stirred at room temperature to be uniform, transparent and sticky, and then the PAN is transferred into a 10mL syringe, and a needle head with the length of about 25 cm and the diameter of about 0.7 mm is arranged at the front end of the syringe; starting a high-voltage static device, adjusting the voltage to be 10 kV, starting spinning, collecting uniformly distributed PAN filaments at a receiving plate, placing the spun PAN filaments in a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 1 ℃/min, heating the carbonization chamber to 280 ℃, and keeping the temperature to be 1.5 h, so that polyacrylonitrile is pre-oxidized; pre-oxidized polyacrylonitrile is added in N 2 Under protection, the temperature rising speed is regulated to be 1 ℃/min, the temperature is raised to 1100 ℃, the polyacrylonitrile carbon nanofiber is cooled to room temperature, and the black fiber cloth is prepared, and the thickness of the black fiber cloth is measured to be 1.2 mu m.
(2) 0.8g sodium carboxymethyl cellulose, 8 mL ethanol and 4 mL isopropanol are weighed and mixed uniformly, and then the mixture is continuously stirred for 12 h, so as to obtain the organic adhesive. Weighing 0.3. 0.3 g carbon fiber, grinding into powder, dropwise adding 3. 3 mL binder, and continuously grinding for 40min to obtain carbon paste. The method comprises the steps of taking a titanium mesh with a size of 2000 meshes and a size of 1.5 cm multiplied by 2.5 cm, controlling the coating thickness through the number of adhesive tape layers, pasting 4 layers of transparent adhesive tapes (the thickness of a single layer is 0.15 mm), uniformly coating the transparent adhesive tapes on the surface of the titanium mesh by using a glass rod, and drying the titanium mesh in a 60 ℃ oven for 3 h.
(3) Placing the dried titanium mesh electrode into a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 5 ℃/min, and adding the titanium mesh electrode into N 2 Heating from room temperature to 500 deg.c under protection, maintaining for 40min, and naturally cooling to room temperature to obtain the final productFiber/titanium mesh counter electrode material. The photoelectric conversion efficiency of the counter electrode made of the material is 7.68 percent according to measurement.
Example 3:
firstly, polyacrylonitrile (PAN) is dissolved in 25 mL Dimethylformamide (DMF), wherein the mass percentage content of the PAN is 15%, the PAN is stirred at room temperature to be uniform, transparent and sticky, and then the PAN is transferred into a 10mL syringe, and a needle head with the length of about 25 cm and the diameter of about 0.7 mm is arranged at the front end of the syringe; starting a high-voltage static device, adjusting the voltage to be 10 kV, starting spinning, collecting uniformly distributed PAN filaments at a receiving plate, placing the spun PAN filaments in a tubular reaction furnace, regulating and controlling the heating speed in a carbonization furnace to be 1 ℃/min, heating the inside of the carbonization furnace from room temperature to 320 ℃, and keeping the temperature to be 0.5 h, so that polyacrylonitrile is pre-oxidized; pre-oxidized polyacrylonitrile is added in N 2 Under protection, the temperature rising speed is regulated to be 1 ℃/min, the temperature is increased to 900 ℃, the polyacrylonitrile carbon nanofiber is cooled to room temperature, and the black fiber cloth is prepared, and the thickness of the black fiber cloth is measured to be 1.28 mu m.
0.8g sodium carboxymethyl cellulose, 8 mL ethanol and 4 mL isopropanol are weighed and mixed uniformly, and then the mixture is continuously stirred for 12 h, so as to obtain the organic adhesive. Weighing 0.3. 0.3 g carbon fiber, grinding into powder, dropwise adding 3. 3 mL binder, and continuously grinding for 40min to obtain carbon paste. The method comprises the steps of taking a titanium mesh with a size of 2000 meshes and a size of 1.5 cm multiplied by 2.5 cm, controlling the coating thickness through the number of adhesive tape layers, pasting 6 layers of transparent adhesive tapes (the thickness of a single layer is 0.15 mm), uniformly coating the transparent adhesive tapes on the surface of the titanium mesh by using a glass rod, and drying the titanium mesh in a 60 ℃ oven for 3 h.
Placing the dried titanium mesh electrode into a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 5 ℃/min, and adding the titanium mesh electrode into N 2 And (3) heating from room temperature to 700 ℃ under protection, preserving heat for 20 min, and naturally cooling to room temperature to obtain the carbon nanofiber/titanium mesh counter electrode material. The photoelectric conversion efficiency of the counter electrode made of the material is 7.93 percent according to the measurement.
Example 4:
firstly, polyacrylonitrile (PAN) is dissolved in 25 mL Dimethylformamide (DMF), wherein the mass percentage content of the PAN is 15 percent, and the PAN is stirred at room temperature to be uniform, transparent and sticky and then is transferred into a 10mL syringeA needle having a diameter of about 0.7 mm and a length of about 25 cm is attached to the front end of the syringe; starting a high-voltage static device, adjusting the voltage to be 10 kV, starting spinning, collecting uniformly distributed PAN filaments at a receiving plate, placing the spun PAN filaments in a tubular reaction furnace, regulating and controlling the heating speed in the carbonization furnace to be 1 ℃/min, heating the carbonization chamber to 300 ℃ from room temperature, and keeping for 1h to pre-oxidize polyacrylonitrile; pre-oxidized polyacrylonitrile is added in N 2 Under protection, the temperature rising speed is regulated to be 1 ℃/min, the temperature is raised to 1000 ℃, the polyacrylonitrile carbon nanofiber is cooled to room temperature, and the black fiber cloth is prepared, and the thickness of the black fiber cloth is measured to be 1.32 mu m.
0.8g sodium carboxymethyl cellulose, 8 mL ethanol and 4 mL isopropanol are weighed and mixed uniformly, and then the mixture is continuously stirred for 12 h, so as to obtain the organic adhesive. Weighing 0.3. 0.3 g carbon fiber, grinding into powder, dropwise adding 4. 4 mL binder, and continuously grinding for 40min to obtain carbon paste. The method comprises the steps of taking a titanium mesh with a size of 2000 meshes and a size of 1.5 cm multiplied by 2.5 cm, controlling the coating thickness through the number of adhesive tape layers, pasting 5 layers of transparent adhesive tapes (the thickness of a single layer is 0.15 mm), uniformly coating the transparent adhesive tapes on the surface of the titanium mesh by using a glass rod, and drying the titanium mesh in a 60 ℃ oven for 3 h.
Placing the dried titanium mesh electrode into a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 5 ℃/min, and adding the titanium mesh electrode into N 2 And (3) heating from room temperature to 600 ℃ under protection, preserving heat for 30 min, and naturally cooling to room temperature to obtain the carbon nanofiber/titanium mesh counter electrode material. The photoelectric conversion efficiency of the counter electrode made of the material is 8.14 percent according to the measurement.
Example 5:
firstly, polyacrylonitrile (PAN) is dissolved in 25 mL Dimethylformamide (DMF), wherein the mass percentage content of the PAN is 15%, the PAN is stirred at room temperature to be uniform, transparent and sticky, and then the PAN is transferred into a 10mL syringe, and a needle head with the length of about 25 cm and the diameter of about 0.7 mm is arranged at the front end of the syringe; starting a high-voltage static device, adjusting the voltage to be 10 kV, starting spinning, collecting uniformly distributed PAN filaments at a receiving plate, placing the spun PAN filaments in a tubular reaction furnace, regulating and controlling the heating rate in the carbonization furnace to be 1 ℃/min, heating the carbonization chamber to 300 ℃ from room temperature, and keeping the temperature to be 1h, so that polyacrylonitrile is pre-oxidized; pre-oxidized poly (ethylene oxide)Acrylonitrile in N 2 Under protection, the temperature rising speed is regulated to be 1 ℃/min, the temperature is raised to 1000 ℃, the polyacrylonitrile carbon nanofiber is cooled to room temperature, and the black fiber cloth is prepared, and the thickness of the black fiber cloth is measured to be 1.3 mu m.
0.8g sodium carboxymethyl cellulose, 8 mL ethanol and 4 mL isopropanol are weighed and mixed uniformly, and then the mixture is continuously stirred for 12 h, so as to obtain the organic adhesive. Weighing 0.3. 0.3 g carbon fiber, grinding into powder, dropwise adding 4. 4 mL binder, and continuously grinding for 40min to obtain carbon paste. Taking 1.5 cm multiplied by 2.5 cm specification FTO conductive glass, controlling the coating thickness by the number of adhesive tape layers, sticking 5 layers of transparent adhesive tape (the thickness of a single layer is 0.15 mm), uniformly coating the transparent adhesive tape on the surface of the glass by using a glass rod, and drying the glass rod in a 60 ℃ oven for 3 h.
(3) Placing the dried electrode into a tubular reaction furnace, regulating and controlling the heating rate in a carbonization furnace to be 5 ℃/min, and adding the electrode into N 2 And (3) heating from room temperature to 600 ℃ under protection, preserving heat for 30 min, and naturally cooling to room temperature to obtain the carbon nanofiber/conductive glass counter electrode material. The photoelectric conversion efficiency of the counter electrode made of the material is 6.06 percent according to the measurement.
Example 6:
the electrode prepared in example 1, the electrode prepared in example 5 and the commonly used Pt counter electrode are respectively assembled into a quantum dot sensitized solar cell counter electrode, and the cell performance is measured, and as shown in a result of fig. 2, the same carbon fiber material has more excellent short-circuit current density when taking a titanium mesh as a substrate than when taking an FTO as a substrate, so that the counter electrode performance of the material is greatly enhanced, and further the photoelectric conversion efficiency of DSSCs is enhanced.
Claims (7)
1. The quantum dot sensitized solar cell counter electrode is characterized by being prepared by the following steps:
(a) Taking polyacrylonitrile as a solute and dimethylformamide as a solvent, preparing a polyacrylonitrile solution with the mass concentration of 10-15%, stirring to be transparent and viscous, injecting into a high-voltage electrostatic spinning machine for spinning, and carbonizing a spun polyacrylonitrile precursor to obtain the polyacrylonitrile carbon nanofiber;
(b) Uniformly mixing sodium carboxymethyl cellulose, isopropanol and ethanol, and magnetically stirring for 10-14 h to obtain an adhesive; the dosage ratio of the sodium carboxymethyl cellulose to the isopropanol to the ethanol is 0.8g:3-5mL:6-10mL;
(c) Grinding the carbon nanofibers obtained in the step (a) into powder, dropwise adding the adhesive, and continuously grinding to prepare carbon paste; the dosage ratio of the carbon nanofiber to the binder is 0.3-3 g:3 mL;
(d) Uniformly coating the carbon paste on a titanium mesh substrate, and placing the titanium mesh substrate in an oven for drying;
(e) And (3) placing the dried titanium mesh in a nitrogen-protected tubular furnace, calcining for 20-40 min at 500-700 ℃, and naturally cooling to obtain the quantum dot sensitized solar cell counter electrode.
2. The counter electrode of claim 1 wherein in step (a), the electrospinning process is: the flow rate of the polyacrylonitrile solution is 20-30 uL/min, the total liquid supply rate is 1.2-1.8 mL/h, the voltage of the high-voltage electrostatic spinning machine is 8-12 kv, the needle length is 20-30 cm, and the diameter is 0.5-0.9 mm.
3. The counter electrode of claim 1 wherein in step (a), the carbonization process is: placing polyacrylonitrile precursor into a carbonization furnace, heating the inside of the carbonization furnace from room temperature to 280-320 ℃, and keeping the temperature to 0.5-1.5 h to pre-oxidize the polyacrylonitrile; then heating to 900-1100 ℃ under the protection of nitrogen, keeping 0.5-1 h, and cooling to room temperature.
4. The counter electrode of claim 1 wherein in step (d) the drying temperature is 50-70 ℃ for a period of time 2-4 h; the mesh number of the titanium mesh is 1500-2500 meshes, and the thickness of the titanium mesh is 0.1-0.3 mm; the carbon paste coating thickness is 0.4-0.9mm.
5. The preparation method of the quantum dot sensitized solar cell counter electrode is characterized by comprising the following steps of:
(a) Taking polyacrylonitrile as a solute and dimethylformamide as a solvent, preparing a polyacrylonitrile solution with the mass concentration of 10-15%, stirring to be transparent and viscous, injecting into a high-voltage electrostatic spinning machine for spinning, and carbonizing a spun polyacrylonitrile precursor to obtain the polyacrylonitrile carbon nanofiber;
(b) Uniformly mixing sodium carboxymethyl cellulose, isopropanol and ethanol, and magnetically stirring for 10-14 h to obtain an adhesive;
(c) Grinding the carbon nanofibers obtained in the step (a) into powder, dropwise adding the adhesive, and continuously grinding to prepare carbon paste;
(d) Uniformly coating the carbon paste on a titanium mesh substrate, and placing the titanium mesh substrate in an oven for drying;
(e) And (3) placing the dried titanium mesh in a nitrogen-protected tubular furnace, calcining for 20-40 min at 500-700 ℃, and naturally cooling to obtain the quantum dot sensitized solar cell counter electrode.
6. The method of claim 5, wherein in step (a), the electrospinning process comprises: the flow rate of the polyacrylonitrile solution is 20-30 uL/min, the total liquid supply rate is 1.2-1.8 mL/h, the voltage of the high-voltage electrostatic spinning machine is 8-12 kv, the needle length is 20-30 cm, and the diameter is 0.5-0.9 mm;
the carbonization process comprises the following steps: placing polyacrylonitrile precursor into a carbonization furnace, heating the inside of the carbonization furnace from room temperature to 280-320 ℃, and keeping the temperature to 0.5-1.5 h to pre-oxidize the polyacrylonitrile; then heating to 900-1100 ℃ under the protection of nitrogen, keeping 0.5-1 h, and cooling to room temperature.
7. The method according to claim 5, wherein in the step (b), the ratio of the amounts of sodium carboxymethyl cellulose, isopropyl alcohol and ethanol is 0.8g:3-5mL:6-10mL; in the step (c), the dosage ratio of the carbon nano fiber to the binder is 0.3-3 g:3 mL; in the step (d), the drying temperature is 50-70 ℃ and the time is 2-4 h; the mesh number of the titanium is 1500-2500 meshes, and the thickness is 0.1-0.3 mm; the carbon paste coating thickness is 0.4-0.9mm.
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| CN104810158A (en) * | 2015-04-29 | 2015-07-29 | 河北大学 | Counter electrode material of sensitized solar battery and manufacturing method of counter electrode material |
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