CN111696788B - Counter electrode material for dye-sensitized solar cell and preparation method thereof - Google Patents
Counter electrode material for dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
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- 239000010941 cobalt Substances 0.000 claims abstract description 72
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- 229910003074 TiCl4 Inorganic materials 0.000 description 2
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- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for a dye-sensitized solar cell and a preparation method thereof, wherein the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material is composed of cobalt phosphide and nitrogen-doped porous carbon, the cobalt phosphide is embedded in the surface of a carbon wall of the nitrogen-doped porous carbon, and the mass fraction of the cobalt phosphide in the composite counter electrode material is 30-60wt.% of the total weight of the composition. The preparation method comprises the steps of synthesizing an organic-inorganic hybrid cobalt phosphonate precursor and an organic nitrogen source-formaldehyde-resorcinol resin/F127 copolymer serving as a carbon source and nitrogen source co-precursor in sequence, and obtaining the organic-inorganic hybrid cobalt phosphonate co-precursor through hydrothermal synergistic self-assembly, high-temperature carbonization, nitridation and other modes of the organic nitrogen source-formaldehyde-resorcinol resin/F127 copolymer. The novel structural cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material provided by the invention has the performance advantages of smaller charge transfer impedance, higher photoelectric conversion efficiency, long-period use stability and the like in the application of dye-sensitized solar cells, and is low in preparation cost, simple in method and easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of counter electrode materials of dye-sensitized solar cells, in particular to a cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for a dye-sensitized solar cell and a preparation method thereof.
Background
With the development of society and the progress of science and technology, the rapid development of social productivity is greatly promoted, and particularly, the wide application of electric energy is realized, and the powerful boosting force is provided for the development of multiple fields of society. The dye-sensitized solar cell has the advantages of high photoelectric conversion efficiency, simple manufacturing process, low price, environmental friendliness and the like, is widely concerned by scientific research and technical personnel at home and abroad, and becomes a new generation of photoelectric conversion device with the greatest development prospect.
The main structure of the dye-sensitized solar cell comprises a dye-sensitized porous titanium dioxide photo-anode, electrolyte and a counter electrode. The counter electrode plays an important role in dye-sensitized solar cell devices, and mainly collects and transmits external circuit electrons and catalytically reduces three ions of iodine in electrolyte. The electrocatalytic reduction reaction rate is closely related to the counter electrode catalyst, and plays a key role in improving the efficiency of the battery. Generally, an ideal counter electrode material needs to have several conditions of (i) excellent electron conductivity; fast electrolyte ion diffusion capacity; prominent electrocatalytic capacity; high chemical stability. Noble metal Pt is currently the most commonly used counter electrode material due to its outstanding catalytic ability and electronic conductivity. However, Pt is too expensive, has limited reserves, and has insufficient chemical stability, which limits its scale application in dye-sensitized solar cells. Therefore, the development of a novel, cheap and efficient non-platinum counter electrode material becomes the key of the development of the dye-sensitized solar cell.
Carbon-based materials, such as graphite, porous carbon, carbon black, carbon nanotubes, graphene, and the like, have been widely used as novel non-platinum counter electrode materials, and exhibit relatively high electronic conductivity, good corrosion resistance, and relatively high catalytic activity. Porous carbon materials exhibit structural characteristics such as a high specific surface area, an adjustable pore size, a large pore volume, and the like, and are receiving wide attention. In particular to a mesoporous carbon material, the aperture size of which is more than 2 nm and is far larger than the size of three ions of iodine (<1 nm) can enhance the diffusion rate of electrolyte ions in the pore channels of the counter electrode material, and can maintain a high catalytic activity area. However, for pure carbon materials, the adsorption capacity of the electrically neutral carbon atoms to the negatively charged iodine triplet is insufficient, so that the catalytic capacity is lower than that of the conventional Pt electrodes [1-3 ]]. One of the effective technical schemes for improving the catalytic activity of the carbon material in the prior art is to dope nitrogen atoms into the carbon material, break the electrical neutrality of adjacent carbon atoms and optimize the electronic structural characteristics by utilizing the larger electronegativity difference between the nitrogen atoms (3.04) and the carbon atoms (2.55), so that the adsorption capacity of the carbon material can be improved, and the electronic conductivity and catalytic active sites of the carbon material can be enhanced, thereby enhancing the nitrogen-doped porous catalytic activityCatalytic reduction Activity of carbon Material [3]. Therefore, the doping of nitrogen atoms with high concentration becomes the key for further improving the catalytic activity of the porous carbon material. However, the conventional preparation method is to obtain a nitrogen-doped carbon material by simply pyrolyzing commonly used organic nitrogen sources such as dicyandiamide, urea and melamine under a high temperature condition of 700 degrees or more. Due to the poor thermal stability of the organic nitrogen source, it readily decomposes into small gaseous molecules at high temperatures (eg. C2N2 +, C3N2 +, C3N3 +) And the volatilization loss is serious, so the nitrogen concentration obtained by the method is generally low and is about 4-7at.% [4-6]. Therefore, the development of an effective preparation method for realizing high-concentration nitrogen doping in the porous carbon material becomes a key for developing a high-performance counter electrode material.
In addition, cobalt phosphide has the characteristics of high activity, high conductivity, high stability, abundant reserves and the like, and becomes one of the promising counter electrode catalysts. At present, the preparation method of cobalt phosphide mainly comprises two synthesis methods of solid and solution. Wherein the solid-state synthesis method is to prepare cobalt phosphide by means of metal phosphide or metal oxide phosphide, but the prepared cobalt phosphide has large particles and low specific surface area [7 ]; the cobalt phosphide prepared by the solution synthesis method is nano-particles, but is generally a semiconductor phase rich in phosphorus, and has low conductivity, poor crystallinity and easy aggregation of particles [7,8 ]. The structure defect causes that the catalytic activity of cobalt phosphide is low, and the reaction rate of reducing three iodine ions into iodine ions is slow, so that the photoelectric conversion efficiency of the dye-sensitized solar cell is reduced.
Therefore, by developing an effective preparation method, a cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material structure which has strong electronic conductivity, good ion diffusivity, rich and uniform catalytic activity sites and good electrolyte corrosion resistance is accurately constructed, a synergistic catalytic effect among composite components can be realized, the catalytic activity and the long-period use stability of a counter electrode are improved, and therefore the application requirements of high photoelectric conversion efficiency and high stability of a dye-sensitized solar cell are met, and the problem to be solved urgently is solved.
Reference to the literature
[1]Lin, K. Y.; Nguyen, M. T.; Waki, K.; Jiang, J. C. J. Phys. Chem. C2018, 122, 26385-26392.
[2]Das, S.; Sudhagar, P.; Verma, V.; Song, D.; Ito, E.; Lee, S. Y.; Kang, Y. S.; Choi, W. Adv. Funct. Mater. 2011, 21, 3729-3736.
[3]Ju, M. J.; Jeon, I. Y.; Kim, J. C.; Lim, K.; Choi, H. J.; Jung, S. M.; Choi, I. T.; Eom, Y. K.; Kwon, Y. J.; Ko, J.et al. Adv. Mater. 2014, 26, 3055-3062.
[4]Yang, D.-S.; Kim, C.; Song, M. Y.; Park, H.-Y.; Kim, J. C.; Lee, J.-J.; Ju, M. J.; Yu, J.-S. J. Phys. Chem. C 2014, 118, 16694-16702.
[5]Zhong, H.; Zhang, S.; Jiang, J.; Li, D.; Tang, P.; Alonso-Vante, N.; Feng, Y. Chem. Electro. Chem 2018, 5, 1899-1904.
[6]Tang, J.; Liu, J.; Li, C.; Li, Y.; Tade, M. O.; Dai, S.; Yamauchi, Y. Angew. Chem. Int. Ed. 2015, 54, 588-593.
[7]Callejas, J. F.; Read, C. G.; Roske, C. W.; Lewis, N. S.; Schaak, R. E. Chem. Mater. 2016, 28, 6017-6044.
[8]Liu, Z.; Gao, Z.; Luo, F.; Yuan, S.; Wang, K.; Li, N.; Li, X. Chem.Cat.Chem. 2018, 10, 3441-3446.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell and the preparation method thereof, wherein the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material has the advantages of stronger electronic conductivity, good ion diffusivity, rich and uniform catalytic active sites and good electrolyte corrosion resistance, and can improve the catalytic activity and stability of a counter electrode and the photoelectric conversion efficiency of the dye-sensitized solar cell.
The purpose of the invention is realized as follows:
the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell comprises cobalt phosphide and nitrogen-doped porous carbon, wherein the cobalt phosphide is embedded into the surface of a carbon wall of the nitrogen-doped porous carbon, and the mass fraction of the cobalt phosphide in the composite counter electrode material is 30-60wt.%；
In the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material, the cobalt phosphide component is CoP;
in the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material, the pore diameter of the nitrogen-doped porous carbon is 2-20 nm, and the pore shape is a two-dimensional hexagonal structure;
in the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material, the nitrogen concentration of the nitrogen-doped porous carbon is 9-16at.%；
The invention also provides a preparation method of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell, which comprises the following steps:
step 1) adding 0.5-4 g of organic phosphonic acid into 40-60 mL of the organic phosphonic acid solution containing 0.1-1 g of Co (OH)2Stirring the deionized water and ethanol mixed solution to obtain a solution A, and then adjusting the pH value of the solution A to 3-7;
step 2) dissolving 1-4 g of resorcinol, 1-4 g of organic nitrogen source and 4-6 g of F127 in 50-70 mL of deionized water and ethanol mixed solution, stirring for 20-40 minutes, adjusting the pH value of the solution to 7-11, adding 5-11 g of formaldehyde solution into the stirred solution, and stirring at 70-90 DEGoC, heating in a water bath for 10-20 minutes, adjusting the pH value of the solution to 3-7, and stirring for 0.5-2 hours again to obtain a solution B;
step 3) adding the solution B into the solution A, stirring for 0.5-2 h, transferring the mixed solution into a reaction kettle, and stirring at 70-90 DEG CoC, heating for 60-80 hours to obtain a product of 700-1000%oAnd C, roasting for 0.5-2 hours in an argon atmosphere to finally obtain the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell.
In the preparation method, the organic phosphonic acid in the step 1) is ethylenediamine tetramethylene phosphonic acid.
In the preparation method, the organic nitrogen source in the step 2) is melamine.
In the above-described preparation process according to the invention, firstly, the organophosphonic acid is particularly selected as phosphorus source, and Co (OH)2And carrying out neutralization reaction in a liquid phase to synthesize the organic-inorganic hybrid cobalt phosphonate precursor. Secondly, polymerizing and synergistically self-assembling the organic nitrogen source, the resorcinol, the formaldehyde solution and the F127 under certain conditions to obtain an organic nitrogen source-formaldehyde-resorcinol resin/F127 compound serving as a carbon source and a nitrogen source precursor. And finally, mixing the carbon source precursor, the nitrogen source precursor and the cobalt phosphonate precursor, performing hydrothermal synergistic self-assembly on the components to obtain a cobalt phosphonate precursor/organic nitrogen source-formaldehyde-resorcinol resin/F127 compound, and carbonizing and nitriding at high temperature to obtain the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell.
Has the positive and beneficial effects that: the invention provides a cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for a dye-sensitized solar cell and a preparation method thereof, and compared with the prior art, the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material has the outstanding characteristics and excellent effects that: 1. the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material prepared by the method has a novel structure, wherein the porous structure of the nitrogen-doped porous carbon remarkably improves the diffusion performance of electrolyte ions in the counter electrode material, and simultaneously increases the active specific surface area of the composite material; 2. the electronic structure of the porous carbon material is further optimized by high-concentration nitrogen doping, the electronic conductivity and catalytic active sites of the porous carbon are obviously enhanced, and the adsorption and catalytic reduction capacity of adjacent carbon atoms on electrolyte ions is obviously enhanced; 3. the cobalt phosphide nano-particles uniformly embedded on the surface of the nitrogen-doped porous carbon-carbon wall can be used as a catalytic activity center to remarkably increase the density of active sites, improve the catalytic reaction rate and improve the overall catalytic activity, and the cobalt phosphide nano-particles are well fixed by a carbon matrix with higher corrosion resistance, so that the cobalt phosphide nano-particles have good chemical stability; 4. compared with a common Pt counter electrode, the cobalt phosphide/nitrogen doped porous carbon composite counter electrode material provided by the invention has the performance advantages of lower charge transfer impedance, higher photoelectric conversion efficiency, long-period stability and the like in the application of dye-sensitized solar cells; 4. the molecular-level multi-component cooperative co-assembly method designed in the preparation method can accurately synthesize the cobalt phosphide and nitrogen-doped porous carbon composite counter electrode material with specific components and specific structures. Furthermore, the type of precursor and the interaction between the components play an important role in the synthesis process. Firstly, the organic phosphonate is used as a phosphorus source, has adjustable inorganic metal units and organic phosphonic acid bridging groups, shows hydrophilic characteristics, can be used as a dispersing agent, and can be more uniformly dispersed into a carbon precursor through hydrogen bond interaction with a resin framework without causing phase separation. And the organic nitrogen source is introduced into the resin molecules in an organic nitrogen source-formaldehyde-resorcinol polymerization mode, and then subjected to hydrothermal cooperative self-assembly and polymerization reaction to obtain a high-molecular-weight nitrogen source-carbon source co-precursor, so that the thermal stability of the organic nitrogen source under high-temperature decomposition is improved, and the high nitrogen doping concentration is obtained in the prepared porous carbon skeleton. Finally, the preparation method is low in cost, simple in preparation process, economical and environment-friendly, and is expected to accelerate the commercial application of the counter electrode material of the dye-sensitized solar cell.
Drawings
FIG. 1 is a transmission electron microscope image and an element distribution diagram of a cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material prepared in example 1 of the present invention;
FIG. 2 is a diagram showing the impedance of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material prepared in example 1 of the present invention;
FIG. 3 is a photo-current-voltage curve diagram of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material prepared in example 1 of the present invention;
FIG. 4 shows the 200 h long-period stability of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material prepared in example 1 of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and specific embodiments:
comparative example 1
By coating 50 mM H on clean FTO conductive glass2PtCl6·6H2And (3) carrying out pyrolysis on the O isopropanol solution at 400 ℃ for 30 minutes to prepare a reference Pt counter electrode.
Example 1
1) 1.2 g of the organic phosphonic acid ethylenediaminetetramethylenephosphonic acid (EDTMPA) are added to 50 mL of a solution containing 0.5 g of Co (OH)2Stirring the deionized water and ethanol mixed solution to obtain a solution A, and then adjusting the pH value of the solution A to 5;
2) 2.3 g of resorcinol, 2.6 g of melamine and 5.0 g of F127 were dissolved in 60 mL of a mixed solution of deionized water and ethanol, stirred for 30 minutes, then the pH of the solution was adjusted to 9, then 8.5 g of formaldehyde solution was added to the stirred solution, then 80 deg.FoC, heating in water bath for 15 minutes, adjusting the pH value of the solution to 5, and stirring for 1 hour again to obtain a solution B;
3) solution B was added to solution A and stirred for 1h, and the mixed solution was transferred to a reaction kettle at 80 deg.CoHeating in C for 72 hours to obtain a product of 900%oAnd C, roasting for 1 hour in an argon atmosphere to finally obtain the CoP/nitrogen-doped mesoporous carbon composite counter electrode material for the dye-sensitized solar cell. In the composite material, the mass fraction of CoP in the composite counter electrode material is 42.4wt.%。
The prepared cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material can be prepared and electrochemically characterized by the following method.
Preparing a counter electrode: the prepared 250 mg of cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material, 30 mg of titanium dioxide and 25 mg of polyethylene glycol were dissolved in 2 mL of deionized water and stirred for 1 hour. The resulting homogeneous slurry was knife coated on FTO conductive glass and dried at 90 ℃ to obtain a counter electrode.
Preparing a photo-anode: first, FTO conductive glass was dipped in 50 mM TiCl4At 70 ℃ for 45 minutes, followed by water washing and drying. Then, 20 nm TiO was added2Slurry and 200 nm TiO2The slurry is respectively coated onAnd drying the mixture on FTO at 125 ℃ for 15 minutes, and sintering the mixture at 450 ℃ for 30 minutes. The sintered FTO glass was again immersed in 50 mM TiCl4The solution was held at 70 ℃ for 30 minutes and sintered at 450 ℃ for 30 minutes. Soaking the obtained photo-anode in 0.3 mM N719 anhydrous ethanol for 24 h to obtain the dye-sensitized titanium dioxide photo-anode with an active area of 0.25 cm2。
Assembling the dye-sensitized solar cell: the prepared counter electrode and a dye-sensitized titanium dioxide photo-anode are assembled into a dye-sensitized solar cell device, wherein the electrolyte contains 0.05M I20.5M LiI, 0.3M 1, 2-dimethyl-3-propylimidazolium iodide (DMPII) and 0.5M 4-tert-butylpyridine, and injected between the counter electrode and the photoanode.
Assembling virtual symmetrical batteries: and assembling the two prepared same counter electrodes into a virtual symmetrical battery, wherein the electrolyte component is the same as that in the battery device.
The electrochemical performance of the battery device is characterized: and carrying out electrochemical alternating current impedance performance test on the assembled virtual symmetrical cell, and carrying out photoelectric conversion efficiency and chemical stability test on the assembled dye-sensitized solar cell device.
As shown in figure 1, the porous carbon in the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material presents two-dimensional hexagonal mesoporous channels (p6 mm) and a pore size of about 4.4 nm. The pore structure is left after F127 pyrolysis, which is beneficial to the rapid diffusion of electrolyte ions and improves the catalytic reaction rate. Furthermore, the CoP particles are about 40 nm in size and embedded in the mesoporous carbon walls. In addition, the high resolution lens plot shows that the nanoparticle lattice fringe spacing is 0.19 nm, attributed to the (211) facet of CoP. The corresponding selected area electron diffraction pattern and transmission electron microscope element distribution diagram also show that the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material is constructed. The novel structure can ensure that the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material has good electronic conductivity, ion diffusivity and structural stability, thereby showing excellent photoelectric conversion efficiency and cycle in the application of the dye-sensitized solar cellRing stability.
As seen from fig. 2, the charge transfer resistance of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material is 1.35 Ω, which is significantly smaller than that of a reference Pt counter electrode (5.08 Ω), and the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material exhibits excellent catalytic reduction capability of iodine.
As seen from FIG. 3, the power is at 100 mW/cm2Under the irradiation of simulated sunlight, the open-circuit voltage of the solar cell assembled by the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode is 0.78V, and the photocurrent density is 16.24 mA-cm-2The fill factor is 0.67, and high photoelectric conversion efficiency of 8.53% is obtained, which is better than 7.52% of the solar cell device assembled by the Pt counter electrode.
As can be seen from fig. 4, after 200 h of continuous simulated solar irradiation, the photoelectric conversion efficiency of the solar cell assembled by the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode still maintained 92% of its initial value, while the photoelectric conversion efficiency of the solar cell assembled by the Pt counter electrode decreased to 62% of its initial value. The result shows that the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode still maintains long-period catalytic stability in corrosive electrolyte. Therefore, the novel material has great potential to replace a Pt counter electrode to be applied to a high-performance dye-sensitized solar cell device.
Example 2
In step 1), 1.0 g of the organic phosphonic acid aminotrimethylene phosphonic acid is added to 50 mL of a solution containing 0.4 g of Co (OH)2And stirring to obtain a solution a, and then adjusting the pH of the solution a to 5. The procedure of step (2-3) was the same as in example 1. In the prepared composite material, the mass fraction of the cobalt phosphide in the composite counter electrode material is 38.1wt% of the total weight of the composition. The electrochemical properties of the composite material are shown in table 1.
In addition, the nitrogen doping concentration obtained from the SEM-EDX test and the pore structure characteristics obtained from the nitrogen adsorption test are shown in table 1.
TABLE 1 Structure and electrochemical Properties of counter electrode materials in comparative examples and examples
From the above table, the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material has lower charge transfer impedance, higher photoelectric conversion efficiency and excellent long-period stability, and after being irradiated by simulated solar light for 200 hours, the photoelectric conversion efficiency can still be kept above 89% of the initial value, so that the application requirements of the high-performance and high-stability dye-sensitized solar cell are met.
The cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell has obvious structural advantages that: the porous structure of the nitrogen-doped porous carbon obviously improves the diffusion performance of electrolyte ions in the counter electrode material, and simultaneously increases the active specific surface area of the composite material; the electronic structure of the porous carbon material is further optimized by high-concentration nitrogen doping, the electronic conductivity and catalytic active sites of the porous carbon are obviously enhanced, and the adsorption catalytic capacity of adjacent carbon atoms on electrolyte ions is obviously enhanced; the cobalt phosphide nanoparticles uniformly embedded on the surface of the nitrogen-doped porous carbon-carbon wall can be used as a catalytic activity center to remarkably increase the density of active sites, improve the catalytic reaction rate and improve the overall catalytic activity of the catalyst. In addition, the cobalt phosphide nano-particles are fixed by the corrosion-resistant carbon matrix and are not easy to run off, and the chemical stability is good. The cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material with the novel structure provided by the invention has the advantages of smaller charge transfer impedance, higher photoelectric conversion efficiency, long-period stability and the like in the application of dye-sensitized solar cells.
The preparation method of the invention has the following obvious advantages: the designed molecular-level multi-component cooperative co-assembly mode can accurately synthesize the cobalt phosphide and nitrogen-doped porous carbon composite counter electrode material with specific components and specific structures. Furthermore, the type of precursor and the interaction between the components play an important role in the synthesis process. Firstly, compared with inorganic phosphate, the organic phosphonate has adjustable inorganic metal units and organic phosphonic acid bridging groups, shows hydrophilic characteristics, can be used as a dispersing agent, can be more uniformly dispersed in a carbon precursor through hydrogen bond interaction with a resin framework, and cannot cause a phase separation phenomenon; an organic nitrogen source is introduced into oligomeric resin molecules in an organic nitrogen source-formaldehyde-resorcinol polymerization mode, and then hydrothermal cooperative self-assembly and polymerization reaction are carried out, so that a resin precursor with high molecular weight is obtained, the thermal stability of the organic nitrogen source under high-temperature decomposition is improved, and the problem that the organic nitrogen source is easy to become gaseous molecules and seriously loses under the traditional pyrolysis condition is solved, so that high nitrogen doping concentration is obtained in a porous carbon skeleton prepared after heat treatment; the resin is used as an in-situ reducing agent to directly reduce the organic phosphonate dispersed in the resin into cobalt phosphide, and the preparation process is simple. The preparation method is low in cost, simple in preparation process, economical and environment-friendly, and is expected to accelerate the commercial application of the counter electrode material of the dye-sensitized solar cell.
The prepared cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material can be characterized by adopting the following method: the prepared 250 mg of cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material, 30 mg of titanium dioxide and 25 mg of polyethylene glycol were dissolved in 2 mL of deionized water and stirred for 1 hour. The resulting homogeneous slurry was knife coated on FTO conductive glass and dried at 90 ℃. And assembling the prepared counter electrode and the dye-sensitized titanium dioxide photo-anode into a dye-sensitized solar cell device, wherein the electrolyte contains three iodine ion/iodine ion redox couples and is injected between the counter electrode and the photo-anode. And (3) carrying out electrochemical alternating current impedance performance test on the virtual symmetrical battery consisting of the same two counter electrodes. And testing the photoelectric conversion efficiency and stability of the solar cell device prepared by the counter electrode and the photo-anode. The prepared counter electrode shows smaller charge transfer impedance, higher photoelectric conversion efficiency and cycle stability in application.
The whole preparation process is simple, the preparation cost is low, the industrial production of the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material is easy to realize, and the large-scale application requirements of the dye-sensitized solar cell can be met.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. The utility model provides a cobalt phosphide nitrogen doping porous carbon composite counter electrode material for dye-sensitized solar cell which characterized in that: the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material is composed of cobalt phosphide and nitrogen-doped porous carbon, the cobalt phosphide is embedded into the surface of a carbon wall of the nitrogen-doped porous carbon, and the mass fraction of the cobalt phosphide in the composite counter electrode material is 30-60wt.Percent; the diameter of a pore channel of the nitrogen-doped porous carbon is 2-20 nm, and the shape of the pore channel is a two-dimensional hexagonal structure.
2. The cobalt phosphide nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell according to claim 1, which is characterized in that: the cobalt phosphide is CoP.
3. The cobalt phosphide nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell according to claim 1, which is characterized in that: the nitrogen concentration of the nitrogen-doped porous carbon is 9-16 at.%。
4. A method for preparing a cobalt phosphide nitrogen-doped porous carbon composite counter electrode material for a dye-sensitized solar cell according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
step 1), adding 0.5-4 g of organic phosphonic acid into 40-60 mL of the organic phosphonic acid solution containing 0.1-1 g of Co (OH)2Stirring the deionized water and ethanol mixed solution to obtain a solution A, and then adjusting the pH value of the solution A to 3-7;
step 2), dissolving 1-4 g of resorcinol, 1-4 g of organic nitrogen source and 4-6 g of F127 in 50-70 mL of deionized water and ethanol mixed solution, and stirring for 2After 0-40 minutes, adjusting the pH value of the solution to 7-11, adding 5-11 g of formaldehyde solution into the stirred solution, and then adding 70-90 g of formaldehyde solutionoC, heating in a water bath for 10-20 minutes, adjusting the pH value of the solution to 3-7, and stirring for 0.5-2 hours again to obtain a solution B;
step 3), adding the solution B into the solution A, stirring for 0.5-2 h, transferring the mixed solution into a reaction kettle, and stirring at 70-90 DEG CoC, heating for 60-80 hours to obtain a product of 700-1000%oAnd C, roasting for 0.5-2 hours in an argon atmosphere to finally obtain the cobalt phosphide/nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell.
5. The preparation method of the cobalt phosphide nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell according to claim 4, wherein the preparation method comprises the following steps: the organic phosphonic acid in the step 1) is ethylenediamine tetramethylene phosphonic acid.
6. The preparation method of the cobalt phosphide nitrogen-doped porous carbon composite counter electrode material for the dye-sensitized solar cell according to claim 4, wherein the preparation method comprises the following steps: the organic nitrogen source in the step 2) is melamine.
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| CN102354614A (en) * | 2011-09-15 | 2012-02-15 | 南开大学 | Phosphide counter electrode for dye sensitized solar cell and preparation method for phosphide counter electrode |
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| CN102354614A (en) * | 2011-09-15 | 2012-02-15 | 南开大学 | Phosphide counter electrode for dye sensitized solar cell and preparation method for phosphide counter electrode |
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