CN109887754B - Monoatomic Pt counter electrode and preparation method and application thereof - Google Patents
Monoatomic Pt counter electrode and preparation method and application thereof Download PDFInfo
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- CN109887754B CN109887754B CN201910161919.1A CN201910161919A CN109887754B CN 109887754 B CN109887754 B CN 109887754B CN 201910161919 A CN201910161919 A CN 201910161919A CN 109887754 B CN109887754 B CN 109887754B
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Abstract
The application discloses a monatomic Pt counter electrode and a preparation method and application thereof, wherein the raw materials of the counter electrode comprise a conductive carbon material and a monatomic Pt catalyst, the monatomic Pt catalyst and the conductive carbon material are mixed, and a certain amount of organic solvent is added for ball milling to form dispersed slurry; and spraying the dispersed slurry on a clean conductive substrate, and heating to obtain the counter electrode. The monatomic Pt counter electrode can greatly reduce the consumption of Pt, thereby greatly reducing the cost of the counter electrode and being beneficial to promoting the industrialization of DSCs.
Description
Technical Field
The application relates to the field of new materials and new energy devices, in particular to a monatomic Pt counter electrode and a preparation method and application thereof
Background
Dye-sensitized solar cells (DSCs) are a representative third-generation photovoltaic technology, and are the only solar cells currently known that use liquid electrolytes. DSCs are generally composed of a photoanode, a dye, an electrolyte, and a counter electrode. The active components in the DSCs electrolyte are redox couples which play a role in charge transfer, wherein the most commonly used couple is an iodine couple which is formed as iodide/iodide (I-/I3-). After the iodophor pair transfers electrons to the excited dye molecules, the iodide ions become iodotriions. As one of the most important links to charge transfer, iodonium triions require reduction of the electrodes at the DSCs, a reaction commonly referred to as iodine reduction. The iodine reduction reaction affects the regeneration process of the iodophor pair and further affects the photoelectric conversion efficiency of the DSCs device. Therefore, the degree of electrocatalytic activity of the counter electrode directly determines the progress of the iodine reduction reaction. Currently, a commonly used counter electrode material is noble metal platinum (Pt). The traditional Pt counter electrode is formed by depositing a layer of Pt film on a conductive substrate by a vacuum evaporation, electroplating or chemical hot plating method, wherein the thickness of the Pt film is about 30 nm-50 nm. The Pt consumed by the counter electrode is huge, and particularly when the counter electrode is prepared by vacuum evaporation, the Pt is also wasted greatly. Pt is a noble metal, the storage amount of the Pt is very limited, and the preparation of the Pt counter electrode in the current mode inevitably causes the cost increase of the DSCs, so that the Pt counter electrode is not beneficial to the mass production and application in the future. Therefore, reducing the amount of Pt used and maintaining its high catalytic activity is an urgent problem to be solved in the art.
Reducing the size of catalyst particles and increasing the specific surface area of the catalyst particles are an important means for reducing the use amount of the noble metal Pt. The preparation of small-sized Pt nanoparticles and the preparation of DSCs counter electrodes based thereon have been reported for a long time, for example, Pt nanoparticles are prepared and supported on a conductive support. However, more and more studies have shown that the stability of Pt is greatly reduced when the particle size thereof is reduced to a certain extent. For example, when the Pt particle size is reduced to nanometer or even sub-nanometer size, the metal surface free energy increases significantly, easily forming aggregates and reducing catalytic activity. In addition, the use amount of Pt cannot be obviously reduced after Pt is prepared into nano particles, because the prepared counter electrode still needs more Pt. The monatomic catalyst means that a single metal atom is fixed on a carrier in a chemical bonding mode, so that the utilization rate of the metal atom can be 100%, and the use of the monatomic catalyst can be expected to reduce the consumption of noble metal to the maximum extent and reduce the manufacturing cost of devices.
Therefore, according to the existing problems of the DSCs counter electrode in the aspect of improving the utilization rate of Pt atoms, on one hand, the Pt is considered to be prepared into single atoms, so that the atom utilization rate of the Pt is improved to the maximum extent; on the other hand, it should be considered to find a suitable carrier material capable of firmly fixing the individual Pt atoms so that no agglomeration occurs in the operating state and long-term stability is ensured. Therefore, the development of the Pt monatomic catalyst with high activity and high stability has extremely important practical significance for reducing the production cost of the DSCs.
Disclosure of Invention
The invention provides a monatomic Pt counter electrode, which comprises a conductive carbon material and a monatomic Pt catalyst, wherein the monatomic Pt catalyst takes a transition metal compound as a carrier of monatomic Pt, and monatomic Pt is firmly fixed in a chemical bonding mode so as to prevent the monatomic Pt from agglomerating; the conductive carbon material functions to increase the conductivity of the counter electrode, thereby facilitating the transport of charges.
Specifically, the monatomic Pt catalyst is prepared by a coprecipitation method or a chemical adsorption method;
before preparing a counter electrode, carrying out hydrogen reduction on a monatomic Pt catalyst;
the transition metal compound is an oxide, sulfide or telluride of a transition metal element;
the conductive carbon material is activated carbon or superfine flake graphite;
the mass percentage of the single-atom Pt catalyst in the counter electrode raw material is 30-50%.
Preferably, the mass percent of Pt in the monatomic catalyst is 1.7% -2.32%;
the monatomic Pt catalyst is a Pt/FeOx monatomic catalyst; the preparation is carried out in an aqueous solution containing 1.0X 10-2mol L-1-0.8mol/L-1Chloroplatinic acid, 1.0mol/L-1Ferric nitrate and 1.0mol/L-1Sodium carbonate, carrying out precipitation reaction at 50 ℃ and about pH 8.0, after the reaction is completely carried out for about 1h, carrying out centrifugal separation, drying the precipitate at 60 ℃ for 5h, and then sintering the precipitate at 400 ℃ in a muffle furnace for 5 h;
the mass ratio of the conductive carbon material to the monatomic Pt catalyst is 1: 1;
the particle size of the conductive carbon material is 40 nm-50 nm;
before preparing the counter electrode, the monatomic Pt catalyst is subjected to hydrogen reduction, namely helium containing 10% of hydrogen is introduced into the monatomic Pt catalyst at the temperature of 200 ℃, and the reduction reaction is carried out for 0.5 h.
The invention also provides a preparation method of the monoatomic Pt counter electrode, which comprises the following steps:
(1) mixing a monatomic Pt catalyst with a conductive carbon material, adding a certain amount of organic solvent, and performing ball milling to form dispersed slurry;
(2) and spraying the dispersed slurry on a clean conductive substrate, and heating to obtain the counter electrode.
Specifically, the preparation method further comprises:
(1) the organic solvent is at least one of ethanol, isopropanol and cyclohexane;
(2) the ball milling dispersion time is 3-4 h;
(3) the ball milling adopts a planetary ball mill;
(4) the heating treatment is carried out at the temperature of 80-200 ℃ for 1-3 h;
(5) the conductive substrate is FTO glass, ITO/PEN flexible substrate, metal titanium sheet or metal titanium mesh;
(6) and (3) putting the conductive substrate into ultrasonic cleaning for 15min, taking out the conductive substrate, washing the conductive substrate with deionized water, sequentially and ultrasonically cleaning the conductive substrate with deionized water and absolute ethyl alcohol for 15min respectively, taking out the conductive substrate, washing the conductive substrate with absolute ethyl alcohol and blow-drying the conductive substrate to obtain the clean conductive substrate.
In the monatomic Pt counter electrode of the present invention, Pt exists in a single atomic form, and all atoms play a catalytic role, so that the noble metal atom utilization rate is maximized. The Pt atoms and the transition metal compound carrier have strong bonding effect, and the effect can firmly fix the single atoms so as to avoid the mutual agglomeration of the Pt single atoms. In addition, there is a degree of electron transfer between the support and the Pt atoms, which will affect the catalytic performance of Pt. The transition metal compound is an ideal material for fixing the monoatomic atom, but has poor conductivity, and thus, the conductivity of the counter electrode can be improved by mixing the monoatomic material with the conductive carbon material.
The invention also provides an application of the monatomic Pt counter electrode, and the monatomic Pt counter electrode is applied to the field of solar cells.
The invention also provides an application method of the monatomic Pt counter electrode, which comprises the following steps:
(1) a small hole is drilled on each diagonal vertex of the counter electrode.
(2) Taking the photo-anode after the dye sensitization, covering the photo-anode outside the active area of the photo-anode completely with a Shalin film, then covering a counter electrode and carrying out heat sealing, and determining that the photo-anode is tightly connected with the counter electrode.
(3) The air suction from one small hole generates negative pressure in the space between the counter electrode and the photo anode, and then the electrolyte is poured from the other small hole by using the negative pressure so as to ensure that the space between the photo anode and the counter electrode is completely filled with the electrolyte.
(4) And coating ultraviolet curing glue on the two small holes on the counter electrode, and then putting the counter electrode into an ultraviolet curing box to finish final packaging.
Specifically, the application method further comprises at least one of the following 1) to 6):
1) the active areas of the photo-anode and the counter electrode are 0.16cm2～100cm2。
2) The gap between the photo anode and the counter electrode is 20-45 μm.
3) The aperture of the small hole is about 0.5 mm.
4) And a plastic tube is communicated with the air pump, and one end of the plastic tube is tightly attached to the small hole on the counter electrode for air extraction.
5) The process of pouring the electrolyte is repeated 3-4 times.
6) The electrolyte may be a liquid electrolyte or a gel electrolyte.
Further, if a gel electrolyte is used, the battery needs to be heated in an oven after the packaging is finished, and the heating temperature is controlled to be about 80 ℃. The gel electrolyte comprises: 0.1M LiI,0.1mol L-1I of (A)2,0.6mol L-10.45mol L of 1, 2-dimethyl-3-propylimidazolium iodide-1The solvent is methoxypropionitrile, the gelling agent is polyethylene oxide (molecular weight is 200 ten thousand), and the addition amount of the N-methylimidazole is 5.0 percent of the mass of the liquid electrolyte.
If the gel electrolyte is used, the gel electrolyte plays a positive role in the stability of the device. On one hand, the gel electrolyte is not easy to volatilize and leak, and on the other hand, the gel electrolyte often contains a polymer gel agent, and the polymer material can generate a certain passivation effect on the solid surface of the photo-anode or the counter electrode, so that the occurrence of interface side reaction is inhibited.
The invention has the beneficial effects that:
the monatomic Pt counter electrode can greatly reduce the consumption of Pt (which is reduced to less than one percent of the conventional Pt electrode), thereby greatly reducing the cost of the counter electrode and being beneficial to promoting the industrialization of DSCs. The novel counter electrode has excellent catalytic effect, and can ensure smooth proceeding of iodine reduction reaction on the surface of the counter electrode, thereby ensuring that DSCs devices have excellent photoelectric characteristics. The counter electrode is assembled into a DSCs device, the DSCs device is effectively packaged, gel electrolyte is used, long-term stability of the device can be greatly improved, and the counter electrode is vital to long-time stable operation of a photovoltaic device.
Drawings
FIG. 1 shows Pt having a Pt content of 0.08% prepared in example 11/FeOxScanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs of the catalyst, wherein (a) is a Scanning Electron Microscope (SEM) photograph, and (b) is a Transmission Electron Microscope (TEM) photograph;
FIG. 2 is a graph of the results of the catalytic activity tests of the counter electrode prepared based on monatomic samples of different Pt contents, and a conventional Pt electrode of example 1, wherein (a) the graph is a cyclic voltammogram and (b) the graph is a Tafel curve;
FIG. 3 is a high resolution spherical aberration corrected TEM image of Pt1/FeOx as a monatomic catalyst with Pt content of 0.08% by mass prepared in example 1;
FIG. 4 is a graph of the photoelectric conversion performance of the assembled DSCs of example 2;
FIG. 5 is a transmission electron microscope image of high resolution spherical aberration correction of a Pt1/FeOx sample with a Pt mass percentage of 2.32% prepared in example 3;
FIG. 6 is a scanning electron micrograph of the facing electrode prepared in example 3;
FIG. 7 is a graph showing the results of the catalytic activity test of the counter electrode prepared in example 3, wherein (a) is a cyclic voltammogram and (b) is a Tafel curve;
FIG. 8 is a graph of the performance of assembled DSCs of example 4;
FIG. 9 is a graph of the performance of assembled flexible DSCs of example 5;
fig. 10 is a graph of the results of the stability tests on the assembled DSCs devices of example 6.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Mono-and monoatomic Pt catalyst material Pt1/FeOxPreparation of
Two monatomic catalysts (Pt content 0.08% and Pt content 1.70% by mass in the two samples, respectively) were first prepared with a coprecipitation method (refer specifically to "Nature Chemistry", 2011,3, p 634-641). The preparation of the sample is carried out in aqueous solution, the precursor comprises chloroplatinic acid solution, ferric nitrate solution and sodium carbonate solution, and the pH of the reaction system is controlled to be about 8.0. The chloroplatinic acid concentration was 2.12X 10 at the time of preparing a sample having a Pt content of 0.08%-2M, the concentration of ferric nitrate is 1.0M, the concentration of sodium carbonate solution is 1.0M, and the reaction temperature is 50 ℃; when a sample having a Pt content of 1.70% was prepared, the chloroplatinic acid concentration was 0.36M, the ferric nitrate concentration was 1.0M, the sodium carbonate solution concentration was 1.0M, and the reaction temperature was 50 ℃. After the precipitation reaction completely occurs (about 1 hour is needed in the process), centrifugally separating the sample, drying at 60 ℃ for 5 hours, and then sintering at 400 ℃ for 5 hours in a muffle furnace; before preparing the counter electrode, the sintered sample is subjected to hydrogen reduction, and the specific process is that mixed gas containing 10% of hydrogen (the other component in the mixed gas is He gas and acts as carrier gas) is introduced at 200 ℃ for reduction for 0.5 h. As can be seen from the TEM photograph in FIG. 1, the monoatomic Pt catalyst sample with a Pt content of 0.08% by mass prepared in this example is nano-particles with uniform size in the range of 20nm to 30 nm.
Preparation of diatomic and monoatomic Pt counter electrode
The method comprises the following specific steps:
(1) 100mg of iron oxide-supported monatomic Pt (hereinafter collectively referred to as Pt) was weighed out separately1/FeOx) And 100mg of conductive carbon black, adding 2ml of isopropanol after uniform mixing, and putting into a ball milling tank for ball milling for 3 hours.
(2) Taking out the slurry obtained in the step (1), and spraying the slurry on a surface cleaner by using a spray gunThe spraying area on the clean FTO conductive glass is about 20cm2。
(3) And (3) putting the sprayed sample into an oven, and heating for 4 hours at 120 ℃ to obtain the monatomic Pt counter electrode.
Third, testing the catalytic performance
(1) Adopting a three-electrode system to carry out cyclic voltammetry test, wherein a sample to be tested is a working electrode, a platinum wire is a counter electrode, and Ag/Ag is used as+As a reference electrode, the electrolyte solution had a composition of 10mM LiI, 1mM I2And 0.1M LiClO4The solvent is acetonitrile, the sweeping speed is 10 mV.s-1The results are shown in fig. 2 (a).
(2) The same electrolyte is adopted for testing the Tafel polarization curve, the voltage scanning range is-0.8V, and the scanning speed is 10mV · s-1The results are shown in fig. 2 (b).
As can be seen from (a) in FIG. 2, the blank sample (i.e., FeO)x) Hardly has any catalytic activity for the iodine reduction reaction, so that FeO can be judgedxThe surface does not have too many catalytically active sites; when a sample contains 0.08% of Pt monoatomic atoms (a high-resolution spherical aberration correction transmission electron microscope (HR-STEM) photo of the Pt monoatomic atoms is shown in figure 3), the catalytic activity is improved to a certain degree, but the performance of the Pt monoatomic atoms is still not as good as that of a traditional Pt electrode; as can be seen from (b) of fig. 2, as the content of the monoatomic Pt increases, the polarization current of the counter electrode increases, approaching the conventional platinum electrode.
Example 2
The counter electrode prepared by the sample with the Pt content of 0.08 percent by mass in the example 1 is assembled into a complete DSCs device, and the photoelectric conversion performance of the device is tested
(1) A regular square is drawn on the counter electrode prepared by the sample with the Pt content of 0.08 percent in mass in the example 1, and the area of the square is consistent with the active area of the photo-anode; and a small hole is drilled at each diagonal vertex of the square, and the hole diameter is about 0.5 mm.
(2) Taking the photo-anode after the dye sensitization, covering the photo-anode outside the active area of the photo-anode completely with a Shalin film, then covering a counter electrode and carrying out heat sealing, and determining that the photo-anode is tightly connected with the counter electrode.
(3) With having elastic plastic pipe intercommunication air pump, the aperture on the counter electrode is hugged closely to one end of plastic pipe, through the processing back of bleeding, and the space between counter electrode and the photoanode produces the negative pressure, later utilizes this negative pressure to fill the electrolyte from another aperture, and used electrolyte is organic solvent electrolyte, and wherein the solvent is acetonitrile, and the active ingredient and the concentration that contain are respectively: lithium iodide (LiI, 0.06M), elemental iodine (I)20.03M), guanidinium isothiocyanate (GuSCN, 0.1M), 1-butyl-trimethylimidazolium iodide (PMII, 0.6M), tert-butylpyridine (TBP, 0.5M). The infusion process was repeated 3 times to ensure that the space between the photoanode and the counter electrode was completely filled with electrolyte.
(4) And coating ultraviolet curing glue on the two small holes on the counter electrode, and then putting the counter electrode into an ultraviolet curing box to finish final packaging.
As shown in FIG. 4, the counter electrode prepared by using the Pt monatomic catalyst in example 1 was used to obtain good photoelectric conversion efficiency in DSCs, and the open-circuit voltage, short-circuit current and fill factor of the device were 0.74V and 15.46mA cm, respectively-20.65, the final photoelectric conversion efficiency is 7.49%, which is slightly lower than that of a device using a conventional Pt electrode. In the above counter electrode, the amount of Pt used was about 1/400 for the conventional photo-anode. This result achieves the object of a large reduction in the amount of Pt used.
Example 3
Firstly, preparing Pt with the Pt content of 2.32%1/FeOx
The method used is a coprecipitation method (ref. Nature Chemistry,2011,3, 634-. The preparation of the samples was carried out in aqueous solution with a chloroplatinic acid concentration of 4.09X 10-2M, the concentration of ferric nitrate is 1.0M, the concentration of sodium carbonate solution is 1.0M, and the reaction temperature is 50 ℃. After the precipitation reaction completely occurs (about 1 hour is needed in the process), centrifugally separating the sample, drying at 60 ℃ for 5 hours, and then sintering at 400 ℃ for 5 hours in a muffle furnace; before preparing the counter electrode, the sintered sample is reduced by hydrogen, which is specifically carried out by introducing mixed gas containing 10% of hydrogen (the other component in the mixed gas is He gas and acts as carrier gas) at 200 ℃ for 0.5h
Prepared byPt content of 2.32%1/FeOxThe high-resolution spherical aberration corrected transmission electron micrograph of (1) is shown in fig. 5, wherein the white bright spots are Pt atoms.
And secondly, preparing a DSCs counter electrode and carrying out electrocatalysis performance test.
(1) 100mg of iron oxide-supported monatomic Pt (hereinafter collectively referred to as Pt) was weighed out separately1/FeOx) And 100mg of conductive carbon black, adding 2ml of isopropanol after uniform mixing, and putting into a ball milling tank for ball milling for 3 hours.
(2) Taking out the slurry obtained in the step (1), and spraying the slurry on FTO conductive glass with a clean surface by using a spray gun, wherein the spraying area is about 20cm2。
(3) And (3) putting the sprayed sample into an oven, and heating for 4 hours at 120 ℃ to obtain the monatomic Pt counter electrode, wherein a scanning electron micrograph of the monatomic Pt counter electrode is shown in FIG. 6.
(4) Adopting a three-electrode system to carry out cyclic voltammetry test, wherein a sample to be tested is a working electrode, a platinum wire is a counter electrode, and Ag/Ag is used as+As a reference electrode, the electrolyte solution had a composition of 10mM LiI, 1mM I2And 0.1M LiClO4The solvent is acetonitrile, the sweeping speed is 10 mV.s-1。
(5) The test of Tafel polarization curve adopts the same electrolyte, the voltage scanning range is-0.8V, and the scanning speed is 10 mV.s-1。
As can be seen from (a) the peak position of the reduction peak in fig. 7 and (b) the current density in fig. 7, the electrocatalytic activity of this sample was higher than that of the conventional Pt electrode.
Example 4
The counter electrode prepared by the sample with the Pt content of 2.32 percent in the example 3 is assembled into a complete DSCs device, and the photoelectric conversion performance of the device is tested
The assembly method is the same as in example 2.
As shown in FIG. 8, the counter electrode prepared by using the Pt monatomic catalyst having the Pt content of 2.32% in example 3 achieved better photoelectric conversion efficiency in DSCs, and the open-circuit voltage, short-circuit current and fill factor of the device were 0.75V and 17.14mA cm, respectively-20.74, finalThe photoelectric conversion efficiency was 9.55%, which is higher than that of the device using the conventional Pt counter electrode under the same conditions (efficiency of 9.32%). The results show that the counter electrode prepared by using the monoatomic Pt can greatly reduce the use amount of the noble metal and can also obtain excellent catalytic performance.
Example 5
A sample with the Pt content of 2.32% in example 3 is used for preparing a flexible counter electrode, a complete DSCs (digital subscriber lines) device is assembled, and the photoelectric conversion performance of the device is tested
(1) 50mg of Pt was weighed out separately1/FeOxAnd 50mg of conductive carbon black, adding 1ml of isopropanol after uniform mixing, and putting into a ball milling tank for ball milling for 3 hours.
(2) Taking out the slurry obtained in the step (1), and spraying the slurry on ITO/PEN with a clean surface by using a spray gun, wherein the sprayed area is about 10cm2。
(3) And (3) putting the sprayed sample into an oven, and heating for 4h at 120 ℃ to obtain the flexible counter electrode.
(4) The flexible counter electrode prepared in the process (3) is assembled into a complete DSCs device by the same method as in example 2.
As shown in FIG. 9, the open-circuit voltage, short-circuit current and fill factor of the DSCs device assembled in this example were 0.74V and 15.61mA cm-20.61, the final photoelectric conversion efficiency was 7.04%. The above results show that the monatomic Pt catalyst with a Pt content of 2.32% in example 3 is suitable for preparing a flexible counter electrode.
Example 6
Pt having a Pt content of 2.32% prepared in example 3 was used1/FeOxPreparing flexible counter electrode, assembling into complete DSCs device, and testing photoelectric conversion performance of device
(1) 50mg of Pt having a Pt content of 2.32% prepared in example 3 were weighed out separately1/FeOxAnd 50mg of conductive carbon black, adding 1ml of isopropanol after uniform mixing, and putting into a ball milling tank for ball milling for 3 hours.
(2) Taking out the slurry obtained in the step (1), spraying the slurry on FTO conductive glass with a clean surface by using a spray gun, and spraying the sprayed surfaceThe product is about 10cm2。
(3) And (3) putting the sprayed sample into an oven, and heating for 4 hours at 120 ℃ to obtain the counter electrode.
(4) Drawing a regular square on the counter electrode, wherein the area of the square is consistent with the active area of the photo-anode; and a small hole is drilled at each diagonal vertex of the square, and the hole diameter is about 0.5 mm.
(5) Taking the photo-anode after the dye sensitization, covering the photo-anode outside the active area of the photo-anode completely with a Shalin film, then covering a counter electrode and carrying out heat sealing, and determining that the photo-anode is tightly connected with the counter electrode.
(6) Preparing a gel electrolyte, wherein the electrolyte comprises the following components: 0.1M LiI,0.1mol L-1I of (A)2,0.6 molL-10.45mol L of 1, 2-dimethyl-3-propylimidazolium iodide-1The solvent is methoxypropionitrile, the gelling agent is polyethylene oxide (molecular weight 200 ten thousand), and the addition amount is 5.0% of the mass of the liquid electrolyte (see the literature Phys. chem. Phys.,2009,11, 4230-one 4235).
(6) The air pump is communicated with the elastic plastic pipe, one end of the plastic pipe is tightly attached to the small hole in the counter electrode, negative pressure is generated in the space between the counter electrode and the photo-anode after air exhaust treatment, then gel electrolyte is filled from the other small hole by utilizing the negative pressure, and the filling process is repeated for 5 times to ensure that the space between the photo-anode and the counter electrode is completely filled with the electrolyte.
(7) Coating ultraviolet curing glue on two small holes on the counter electrode, then putting the counter electrode into an ultraviolet curing box to finish final packaging, and then heating the counter electrode in an oven at 80 ℃ for 2 h.
As shown in FIG. 10, the open-circuit voltage, the short-circuit current, the fill factor and the photoelectric conversion efficiency of the cell were 0.77V and 16.88mA cm after the cell was completely assembled and tested-20.68, 8.83%. After being placed for 207 days, the open-circuit voltage, the short-circuit current, the filling factor and the photoelectric conversion efficiency are respectively 0.77V and 16.26mA cm-20.69, 8.67%. After 423 days of placement, the open-circuit voltage, the short-circuit current, the filling factor and the photoelectric conversion efficiency are respectively 0.76V and 16.85mA cm-2、0.66、8.47％。It can be seen that the battery device has very good stability after the gel electrolyte is used.
It can be seen from the above examples that the monatomic Pt counter electrode has excellent catalytic performance for the iodine reduction reaction, and the use of the counter electrode can greatly improve the atom utilization rate of the noble metal and reduce the preparation cost thereof, which is beneficial to the industrialization process. In addition, in combination with the gel electrolyte, the assembled device has good stability.
Claims (7)
1. A monatomic Pt counter electrode is characterized in that raw materials of the counter electrode comprise a conductive carbon material and a monatomic Pt catalyst, wherein the monatomic Pt catalyst takes a transition metal compound as a support of monatomic Pt; the mass percentage of the single-atom Pt catalyst in the counter electrode raw material is 30-50%; the mass percentage content of Pt in the monatomic catalyst is 1.7% -2.32%; the mass ratio of the conductive carbon material to the monatomic Pt catalyst is 1: 1.
2. The monatomic Pt counter electrode of claim 1, characterized by comprising one or more of the following (1) - (4):
(1) preparing the monatomic Pt catalyst by adopting a coprecipitation method or a chemical adsorption method;
(2) before preparing a counter electrode, carrying out hydrogen reduction on the monatomic Pt catalyst;
(3) the transition metal compound is an oxide, sulfide or telluride of a transition metal element;
(4) the conductive carbon material is activated carbon or ultrafine flake graphite.
3. The monatomic Pt counter electrode of claim 2, characterized by comprising one or more of the following (1) - (3):
(1) the monatomic Pt catalyst is a Pt/FeOx monatomic catalyst;
(2) the particle size of the conductive carbon material is 40 nm-50 nm;
(3) before the counter electrode is prepared, the monatomic Pt catalyst is subjected to hydrogen reduction, namely helium containing 10% of hydrogen is introduced into the monatomic Pt catalyst at the temperature of 200 ℃, and the reduction reaction is carried out for 0.5 h.
4. A method of preparing a monatomic Pt counter electrode according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) mixing a monatomic Pt catalyst with a conductive carbon material, adding a certain amount of organic solvent, and performing ball milling to form dispersed slurry;
(2) and spraying the dispersed slurry on a clean conductive substrate, and heating to obtain the counter electrode.
5. The method for producing a monatomic Pt counter electrode according to claim 4, characterized by comprising one or more of the following (1) to (6):
(1) the organic solvent is at least one of ethanol, isopropanol and cyclohexane;
(2) the ball milling dispersion time is 3-4 h;
(3) the ball milling adopts a planetary ball mill;
(4) the heating treatment is heating for 1-3 h at the temperature of 80-200 ℃;
(5) the conductive substrate is FTO glass, ITO glass, an ITO/PEN flexible substrate, a metal titanium sheet or a metal titanium mesh;
(6) and (3) putting the conductive substrate into ultrasonic cleaning for 15min, taking out the conductive substrate, washing the conductive substrate with deionized water, sequentially and ultrasonically cleaning the conductive substrate with deionized water and absolute ethyl alcohol for 15min respectively, taking out the conductive substrate, washing the conductive substrate with absolute ethyl alcohol and blow-drying the conductive substrate to obtain the clean conductive substrate.
6. Use of a monatomic Pt counter electrode according to any of claims 1 to 3 in the field of solar cells, characterized in that the electrolyte is a gel electrolyte consisting of: 0.1M LiI,0.1mol L-1I of (A)2，0.6mol L-10.45mol L of 1, 2-dimethyl-3-propylimidazolium iodide-1The solvent is methoxy propionitrile, the gel agent is polyethylene oxide, and the addition amount is 5.0 of the mass of the liquid electrolyte％。
7. Use of a monatomic Pt counter electrode according to claim 6 in the field of solar cells, characterized in that when the electrolyte is a gel electrolyte, the cell needs to be heated in an oven after the encapsulation is completed, the heating temperature being controlled at 80 ℃.
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| CN101295586A (en) * | 2008-06-11 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Production method of nanocrystalline TiO2 solar battery prototype device |
| CN101930850A (en) * | 2009-06-26 | 2010-12-29 | 清华大学 | Gel electrolyte in dye-sensitized solar cell, special electrolyte and preparation method thereof |
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2019
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295586A (en) * | 2008-06-11 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Production method of nanocrystalline TiO2 solar battery prototype device |
| CN101930850A (en) * | 2009-06-26 | 2010-12-29 | 清华大学 | Gel electrolyte in dye-sensitized solar cell, special electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Experimental investigation and theoretical exploration of single-atom electrocatalysis in hybrid photovoltaics: The powerful role of Pt atoms in triiodide reduction;Suxia Liang等;《Nano Energy》;20170620;第39卷;第1-8页 * |
| Fe3O4–carbon black nanocomposite as a highly efficient counter electrode material for dye-sensitized solar cell;Muniyandi Bagavathi等;《Ceramics International》;20160518;第42卷;第13190-13198页 * |
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