Method for improving dispersibility of nano titanium dioxide, slurry and application thereof
Technical Field
The invention relates to the field of solar cells, in particular to a method for improving the dispersibility of nano titanium dioxide and a perovskite solar cell thereof.
Background
The perovskite cell is used as a third-generation novel solar cell, has wide raw material source, simple preparation process and lower cost, and can be used for preparing large-area flexible cells and transparent cells, so that the perovskite cell is paid more and more attention to and researched. At present, the material of an electron transport layer in a perovskite battery is generally metal oxide nanoparticles, the nanoparticles with small particle size can be applied to the aspects of energy, environment, catalysis and the like due to unique performance, and the nano titanium dioxide is the most commonly used material for photovoltaic solar energy due to the characteristics of good light stability, basically no scattering effect on incident visible light, large specific surface area and the like.
Because the nano titanium dioxide particles have small size, a large number of defects exist on the surface, the surface activity is large, the particles dispersed in a liquid medium are easy to agglomerate and coagulate to generate an agglomeration phenomenon, stable slurry cannot be formed, and the stability of the slurry influences the film uniformity when the nano titanium dioxide particles are used as an electron transport layer of a perovskite battery. The existing method for improving the dispersibility of the nano titanium dioxide is physical dispersion and chemical dispersion, wherein the physical dispersion mode is mainly mechanical stirring, and the nano particles are uniformly dispersed in the slurry by external acting force, but the physical dispersion mode cannot permanently stabilize the dispersion liquid, and when the external force disappears, the titanium oxide particles can be re-aggregated. The chemical dispersion is to reduce the interfacial tension between the nanoparticles and the dispersion liquid by means of a chemical surfactant, so as to improve the dispersibility of the dispersion liquid. Although the ideal dispersion effect can be achieved by the method, metal particles introduced into most of the surfactants can damage the mesoporous structure of the nano titanium oxide film, and further influence the overall efficiency of the perovskite battery, so that the method is not suitable for the field of the perovskite battery.
In view of this, a method for improving the dispersibility of nano titanium dioxide is urgently needed to solve the problems of film uniformity and slurry stability when the nano titanium dioxide is used as a perovskite electron transport layer.
Disclosure of Invention
The invention aims to solve the technical problems that the dispersing method of the nano titanium dioxide in the prior art is not ideal in dispersing effect and poor in stability of nano titanium dioxide slurry, and further provides a method for improving the dispersibility of the nano titanium dioxide.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for improving the dispersibility of nano titanium dioxide comprises the following steps:
(1) Dissolving nano titanium dioxide in a solvent to form a dispersion solution, and performing ultrasonic dispersion on the dispersion solution to obtain an ultrasonic dispersion solution;
(2) Adding hexadecyl trimethyl ammonium bromide into the ultrasonic dispersion liquid in the step (1), uniformly mixing, and performing ultrasonic dispersion to obtain a secondary ultrasonic dispersion liquid;
(3) And (3) dispersing the secondary ultrasonic dispersion liquid obtained in the step (2) by adopting a homogenizer to obtain nano titanium dioxide slurry.
Preferably, in step (1) and step (2), the ultrasonic dispersion comprises the following steps: dispersing for 1-3min under the condition of ultrasonic power of 2500-3500W, cooling for 1-3min at-5 deg.C-8 deg.C, and repeating for 2-10 times.
Preferably, in step (1), the solvent is one or more of water, ethanol and terpineol.
Preferably, in the step (1), the mass ratio of the nano titanium dioxide to the solvent is 1: (150-200).
Preferably, in the step (2), the mass ratio of the cetyl trimethyl ammonium bromide to the nano titanium dioxide is (10-15): 100.
Preferably, step (2) further comprises the step of adding polyvinylpyrrolidone to the ultrasonic dispersion.
Preferably, in the step (2), the mass ratio of the polyvinylpyrrolidone to the cetyltrimethylammonium bromide is 1: (1-2).
Preferably, in the step (3), the dispersion is performed by using a homogenizer, and the method comprises the following steps: and (3) adding the secondary ultrasonic dispersion liquid obtained in the step (2) accounting for 10-30% of the total amount into a homogenizer, homogenizing under the condition that a secondary homogenizing valve is 150bar, then adding the rest secondary ultrasonic dispersion liquid into the homogenizer, homogenizing under the condition that a primary homogenizing valve is 500bar, connecting a discharge hole and a feed inlet of the homogenizer, and circulating the secondary ultrasonic dispersion liquid in the homogenizer for ten times to obtain the nano titanium dioxide slurry.
The invention also provides nano titanium dioxide slurry which is obtained by adopting the method for improving the dispersibility of the nano titanium dioxide.
The invention also provides application of the nano titanium dioxide slurry in preparation of a perovskite solar cell.
The scheme of the invention at least comprises the following beneficial effects:
(1) The method for improving the dispersibility of the nano titanium dioxide comprises the following steps: dissolving nano titanium dioxide in a solvent to form a dispersion solution, and performing ultrasonic dispersion on the dispersion solution to obtain an ultrasonic dispersion solution; adding hexadecyl trimethyl ammonium bromide into the ultrasonic dispersion liquid, uniformly mixing, and performing ultrasonic dispersion to obtain a secondary ultrasonic dispersion liquid; and dispersing the secondary ultrasonic dispersion liquid by adopting a homogenizer to obtain the nano titanium dioxide slurry. According to the method for improving the dispersibility of the nano titanium dioxide, through a mode of combining physical dispersion and chemical dispersion, firstly, agglomerated titanium dioxide particles are scattered through external force by physical ultrasonic waves, then cetyl trimethyl ammonium bromide is added, cations capable of being adsorbed on the surfaces of the titanium dioxide particles are generated in dispersion liquid, the cations are wrapped on the surfaces of the particles and adsorb a layer of opposite charges around the particles to form an electric double layer, the system stability is realized through electrostatic repulsion, and the electric double layer electrostatic repulsion energy is caused by mutual repulsion among the electric double layers of the particles, so that the original agglomerated titanium dioxide particles cannot be tightly combined together. Then, a physical ultrasonic wave and a homogenizer are used to uniformly form an electric double layer structure, so as to form nano titanium dioxide slurry with uniform dispersion and stable state.
(2) According to the method for improving the dispersity of the nano titanium dioxide, in the step (1), the solvent is one or more of water, ethanol and terpineol. Because of the strong interaction of the hexadecyl ammonium bromide molecular tail group in an ethanol solution, the critical micelle concentration is higher, so that the hydrophobic molecule is more easily dissolved in ethanol, and therefore, the nano titanium oxide in the system is not easy to form micelles and has better dispersibility.
(3) The method for improving the dispersibility of the nano titanium dioxide further comprises the step of adding polyvinylpyrrolidone into the ultrasonic dispersion liquid. Due to the strong repulsion action of hydrophobic carbon chains in the polyvinylpyrrolidone in water, namely steric hindrance, the mutual aggregation of nano titanium dioxide particles can be prevented, and the effect of stabilizing a reaction system is achieved. On mutually exclusive polyvinylpyrrolidone molecules, due to the existence of carbonyl groups, solvent molecules can be hydrogen bonded, and under the mutual exclusion action of hydrophobic groups, the distance between nano titanium dioxide particles is very far excluded, so that the stability of the system is further enhanced.
More importantly, the mutual cooperation between the hexadecyl trimethyl ammonium bromide and the polyvinylpyrrolidone greatly improves the dispersibility of the nano titanium oxide, on one hand, the polyvinylpyrrolidone molecules contain a large amount of N-C = O oxygen atom lone-pair electrons, and the nano titanium dioxide is rich in empty tracks, in the dispersing process, due to the action of ultrasonic waves, coordination bonds are easily generated among titanium dioxide particles, so that the polyvinylpyrrolidone is coated on the surfaces of the nano titanium dioxide particles, and meanwhile, due to the surface electronegativity of the nano titanium dioxide particles, the polyvinylpyrrolidone can generate stronger electrostatic attraction with the cationic dispersant hexadecyl trimethyl ammonium bromide to be adsorbed on the surfaces of the particles, so that better dispersibility is achieved; on the other hand, because of the containing and attracting effects of the pyrrole rings on cations, the polyvinylpyrrolidone has a certain attracting effect on the cationic dispersant cetyl trimethyl ammonium bromide, and the adsorption quantity and strength of the cetyl trimethyl ammonium bromide on the surfaces of the nano titanium dioxide particles are greatly enhanced.
In addition, the nanometer titanium dioxide slurry added with the hexadecyl trimethyl ammonium bromide and the polyvinylpyrrolidone is sintered to form a film, and due to the interaction of the quaternary ammonium salt and the long-chain macromolecules, particles among titanium oxide molecules can be uniformly dispersed, the Zeta potential is increased, the electron mobility is higher, and the efficiency of the prepared perovskite battery can be obviously improved.
Drawings
FIG. 1 is a film made of the nano-titania slurry of example 1 of the present invention;
FIG. 2 is a film made of the nano-titania slurry of example 2 of the present invention;
FIG. 3 is a film made of the nano-titania slurry of example 3 of the present invention;
FIG. 4 is a film made from the nano-titania slurry of example 4 of the present invention;
FIG. 5 is an SEM image of a membrane prepared from the nano-titania slurry in example 1 of the present invention;
FIG. 6 is an SEM image of a membrane prepared from the nano-titania slurry in example 2 of the present invention
FIG. 7 is an SEM image of a membrane prepared from nano-titania slurry in example 3 of the present invention
FIG. 8 is an SEM image of a membrane prepared from the nano-titania slurry in example 4 of the present invention.
Detailed Description
The examples of the present invention, which do not indicate specific conditions, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, but are conventional products which can be obtained commercially, and the implementation of the technical scheme and the realization of the technical effect are not influenced by the raw materials of different manufacturers and models.
Example 1
The method for improving the dispersibility of the nano titanium dioxide comprises the following steps:
(1) Dissolving nano titanium dioxide in a solvent to form a dispersion solution, performing ultrasonic dispersion on the dispersion solution, dispersing for 3min under the condition of the ultrasonic power of 2500W, cooling for 1min at 2 ℃, and repeating for 10 times to obtain an ultrasonic dispersion liquid; wherein the solvent is water;
(2) Adding hexadecyl trimethyl ammonium bromide and polyvinylpyrrolidone into the ultrasonic dispersion liquid obtained in the step (1), uniformly mixing, performing ultrasonic dispersion, dispersing for 3min under the condition that the ultrasonic power is 3500W, cooling for 1min at-5 ℃, and repeating for 2 times to obtain secondary ultrasonic dispersion liquid; wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the nano titanium dioxide is 15; the mass ratio of the polyvinylpyrrolidone to the hexadecyl trimethyl ammonium bromide is 1:1.
(3) And (3) dispersing the secondary ultrasonic dispersion liquid obtained in the step (2) by adopting a homogenizer to obtain nano titanium dioxide slurry.
The nano titanium dioxide slurry obtained in the embodiment is used as an electron transport layer to prepare a perovskite solar cell.
It should be noted that, in this embodiment, the nano titanium dioxide is commercially available commercial nano titanium dioxide of model P25, and hereinafter, the details are not described again. The skilled person can select other types of nano titanium dioxide according to the actual situation.
Example 2
The method for improving the dispersibility of the nano titanium dioxide comprises the following steps:
(1) Dissolving nano titanium dioxide in a solvent to form a dispersion solution, performing ultrasonic dispersion on the dispersion solution, dispersing for 2min under the condition that the ultrasonic power is 3500W, cooling for 2min at 8 ℃, and repeating for 2 times to obtain an ultrasonic dispersion solution; wherein the solvent is ethanol;
(2) Adding hexadecyl trimethyl ammonium bromide and polyvinylpyrrolidone into the ultrasonic dispersion liquid obtained in the step (1), uniformly mixing, performing ultrasonic dispersion, dispersing for 2min under the condition of ultrasonic power of 3000W, cooling for 2min at 8 ℃, and repeating for 10 times to obtain a secondary ultrasonic dispersion liquid; wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the nano titanium dioxide is 12; the mass ratio of the polyvinylpyrrolidone to the hexadecyl trimethyl ammonium bromide is 1:1.5.
(3) And (3) dispersing the secondary ultrasonic dispersion liquid obtained in the step (2) by using a homogenizer, adding the secondary ultrasonic dispersion liquid which accounts for 30% of the total amount and is obtained in the step (2) into the homogenizer, homogenizing under the condition that a secondary homogenizing valve is 150bar, then adding the rest secondary ultrasonic dispersion liquid into the homogenizer, homogenizing under the condition that a primary homogenizing valve is 500bar, connecting a discharge hole and a feed inlet of the homogenizer, and circulating the secondary ultrasonic dispersion liquid in the homogenizer for ten times to obtain the nano titanium dioxide slurry.
The nano titanium dioxide slurry obtained in the embodiment is used as an electron transport layer to prepare a perovskite solar cell.
Example 3
The method for improving the dispersibility of the nano titanium dioxide comprises the following steps:
(1) Dissolving nano titanium dioxide in a solvent to form a dispersion solution, performing ultrasonic dispersion on the dispersion solution, dispersing for 1min under the condition of the ultrasonic power of 3000W, cooling for 3min at the temperature of-5 ℃, and repeating for 6 times to obtain an ultrasonic dispersion liquid; wherein the solvent is terpineol;
(2) Adding cetyl trimethyl ammonium bromide and polyvinylpyrrolidone into the ultrasonic dispersion liquid in the step (1), uniformly mixing, performing ultrasonic dispersion, dispersing for 1min under the condition of ultrasonic power of 2500W, cooling for 3min at 2 ℃, and repeating for 6 times to obtain a secondary ultrasonic dispersion liquid; wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the nano titanium dioxide is 10; the mass ratio of the polyvinylpyrrolidone to the hexadecyl trimethyl ammonium bromide is 1:2.
(3) And (3) dispersing the secondary ultrasonic dispersion liquid obtained in the step (2) by using a homogenizer, adding the secondary ultrasonic dispersion liquid which accounts for 20% of the total amount and is obtained in the step (2) into the homogenizer, homogenizing under the condition that a secondary homogenizing valve is 150bar, then adding the rest secondary ultrasonic dispersion liquid into the homogenizer, homogenizing under the condition that a primary homogenizing valve is 500bar, connecting a discharge hole and a feed inlet of the homogenizer, and circulating the secondary ultrasonic dispersion liquid in the homogenizer for ten times to obtain the nano titanium dioxide slurry.
The nano titanium dioxide slurry obtained in the embodiment is used as an electron transport layer to prepare a perovskite solar cell.
Example 4
The method for improving the dispersibility of the nano titanium dioxide in the embodiment is the same as the embodiment 2, and the difference is only that: in the step (2), polyvinylpyrrolidone is not added.
Example 5
The method for improving the dispersibility of the nano titanium dioxide in the embodiment is the same as the embodiment 2, and the difference is only that: in the step (2), the mass ratio of the polyvinylpyrrolidone to the hexadecyl trimethyl ammonium bromide is 1:0.5.
example 6
The method for improving the dispersibility of the nano titanium dioxide in the embodiment is the same as the embodiment 2, and the difference is only that: in the step (2), the mass ratio of the polyvinylpyrrolidone to the cetyltrimethylammonium bromide is 1:3.
comparative example 1
The method for dispersing the nano titanium dioxide of the comparative example is the same as that of the example 2, and the difference is only that: in the step (2), only physical dispersion is carried out without adding cetyltrimethylammonium bromide and polyvinylpyrrolidone.
Comparative example 2
The method for dispersing the nano titanium dioxide of the comparative example is the same as that of the example 2, and the difference is only that: in the step (2), cetyltrimethylammonium bromide is not added.
Comparative example 3
The method for dispersing the nano titanium dioxide of the comparative example is the same as that of the example 2, and the difference is only that: step (3) is not included.
Comparative example of Effect
In order to verify the technical effect of the method for improving the dispersibility of the nano titanium dioxide, the following tests are carried out:
the nano titanium dioxide slurry obtained in the examples 1 to 6 and the comparative examples 1 to 3 was coated on FTO conductive glass to form a film with a thickness of 450nm, and the transmittance of light of each film was measured by using a light transmittance tester and a solar simulator to obtain the transmittance, and the photoelectric conversion efficiency of the examples was measured. Wherein, as shown in fig. 1 to 4, the films obtained from the nano titania slurries obtained in examples 1 to 4, and as shown in fig. 5 to 8, the SEM images of the films obtained from the nano titania slurries obtained in examples 1 to 4.
The results of the experiment are as follows:
according to the comparison between examples 1-6 and comparative example 1, the method for improving the dispersibility of the nano titanium dioxide has better transmittance (lower transmittance) compared with the nano titanium dioxide slurry obtained by only performing physical dispersion, i.e., shows that the method has better dispersion effect and better photoelectric conversion efficiency. It is understood from the comparison of examples 1 to 6 with comparative example 2 that the dispersibility can be improved to some extent by adding polyvinylpyrrolidone alone without adding cetyltrimethylammonium bromide, but the improvement of the dispersing effect is limited. As can be seen from the comparison between examples 1-6 and comparative example 3, the dispersing effect of the nano titanium dioxide can be improved to some extent by adding the cetyl trimethyl ammonium bromide and the polyvinylpyrrolidone and then homogenizing. It is understood from the comparison between examples 1-3 and examples 4-6 that the addition of polyvinylpyrrolidone significantly improves the dispersion effect, but too small an amount of polyvinylpyrrolidone does not significantly contribute to the dispersion effect, and too much an amount of polyvinylpyrrolidone lowers the photoelectric conversion efficiency of the cell.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.