Quantum dot composite material and preparation method and application thereof

Abstract

The invention discloses a quantum dot composite material as well as a preparation method and application thereof. The method for preparing the quantum dot composite material comprises the following steps: carrying out first mixing on a first solution and a first silicon source with a coordination group, and carrying out hydrolytic condensation reaction on the first silicon source to obtain a first mixed solution; performing second mixing on the first mixed solution and a second silicon source to obtain a second mixed solution; performing solid-liquid separation on the second mixed solution to obtain a silicon ball material; performing third mixing on a perovskite raw material, a second solvent and a silicon ball material to obtain a third mixed solution; and performing fourth mixing and purification treatment on the third mixed solution and a third solvent to obtain the quantum dot composite material. According to the method, the stability of the perovskite quantum dots can be improved, and the loss of the perovskite quantum dots on the cell efficiency is reduced, so that the perovskite quantum dots can be effectively added into an antireflection coating layer, an adhesive film and other base materials, the effective utilization of ultraviolet light is realized, and the cell efficiency is further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of quantum dots, and in particular relates to a quantum dot composite material and a preparation method and application thereof. Background Art

[0002] With years of technological advancement, the efficiency of crystalline silicon solar cell modules has gradually approached its theoretical limit. Improvements in the formulation and manufacturing process of crystalline silicon cells alone have only limited potential for efficiency gains. Further improving the utilization of solar energy is a key issue under the goal of carbon neutrality. Anti-reflective (AR) coating is a widely used method for improving solar cell performance. AR coating forms a silica-based coating on the glass surface, creating a gradient of refractive index from air to coating layer to glass. This effectively reduces sunlight reflection from the air to the glass surface, increasing the solar cell's absorption of sunlight, thereby improving cell efficiency.

[0003] However, due to the glass layer's absorption of UV light and the effects of the UV absorber in the adhesive layer, the anti-reflective coating's UV gain effect doesn't translate into improved cell efficiency. To effectively utilize UV light, a down-conversion technology based on perovskite quantum dots has been proposed, known as quantum shearing. By absorbing high-energy UV photons and releasing more infrared photons, this technology effectively utilizes UV light, further improving cell efficiency. One related technique is to achieve a conversion efficiency of 170% by doping CsPbCl3 quantum dots with Yb. Although quantum shearing has a foreseeable broad market prospect, it is still restricted by the stability of perovskite quantum dots themselves. Water, oxygen, heat and ultraviolet light will damage perovskite quantum dots. Therefore, perovskite quantum dots cannot tolerate anti-reflective coating solutions based on ethanol / water or adhesive films that require high-temperature lamination processes. At the same time, long-term exposure to ultraviolet light will lead to decomposition quenching. Moreover, due to the high refractive index of the perovskite material itself, the addition of the substrate will cause the overall refractive index of the substrate to increase, and the addition of the perovskite material will cause the light transmittance of the substrate to decrease, resulting in a loss in battery efficiency. Summary of the Invention

[0004] The present invention aims to at least partially address one of the technical problems in the related art. To this end, one object of the present invention is to provide a quantum dot composite material, its preparation method, and its application. The method of preparing the quantum dot composite material according to the present invention can improve the stability of perovskite quantum dots and reduce the loss of battery efficiency caused by perovskite quantum dots. This allows the composite material to be effectively added to substrates such as anti-reflective coatings and adhesive films, effectively utilizing ultraviolet light and thereby improving battery efficiency.

[0005] In a first aspect of the present invention, a method for preparing a quantum dot composite material is provided. According to an embodiment of the present invention, the method comprises:

[0006] (1) performing a first mixing of a first solution and a first silicon source having a coordination group, causing the first silicon source to undergo a hydrolysis-condensation reaction, so as to obtain a first mixed solution containing first hollow silica microspheres having a coordination group;

[0007] (2) performing a second mixing of the first mixed solution and a second silicon source to obtain a second mixed solution containing second hollow silica microspheres having a coordination group therein;

[0008] (3) performing solid-liquid separation on the second mixed liquid to obtain a silicon sphere material containing second hollow silica microspheres having coordination groups therein;

[0009] (4) performing a third mixing of the perovskite raw material, the second solvent, and the silicon sphere material to obtain a third mixed solution;

[0010] (5) performing a fourth mixing and purification process on the third mixed solution and the third solvent to obtain a quantum dot composite material comprising perovskite quantum dots coated with the second hollow silica microspheres.

[0011] According to the method for preparing a quantum dot composite material according to the above embodiment of the present invention, a first solution and a first silicon source having a coordination group are first mixed, so that the first silicon source having the coordination group can undergo a hydrolysis reaction under the action of the first solution to form a silicate group, and at the same time, the silicate groups can undergo a condensation reaction to form a first hollow silica microsphere having a coordination group, thereby obtaining a first mixed solution containing the first hollow silica microsphere having a coordination group; the first mixed solution is second mixed with a second silicon source, the second silicon source does not contain a coordination group, and the second silicon source can undergo a hydrolysis and condensation reaction under the action of the first mixed solution, and a layer of silica is coated on the surface of the first hollow silica microsphere having a coordination group to form a second hollow silica microsphere having a coordination group inside, and the outer wall of the shell of the second hollow silica microsphere does not contain a coordination group, thereby obtaining a second mixed solution containing the second hollow silica microsphere having a coordination group inside. That is, the coordination group only exists inside the second hollow silica microspheres, and the second mixed liquid is subjected to solid-liquid separation to obtain a silica ball material containing the second hollow silica microspheres with coordination groups inside; the perovskite raw material, the second solvent and the silica ball material are mixed for the third time to obtain a third mixed liquid. After the reaction, the third mixed liquid contains the blended quantum dot composite material and the quantum dots located outside the silica ball material. The third mixed liquid and the third solvent are mixed for the fourth time, the quantum dots located outside the silica ball material are dissolved in the third solvent, and the second hollow silica microspheres coated with quantum dots are precipitated in the third solvent. Purification treatment is performed to retain the quantum dot composite material. The quantum dot composite material contains the second hollow silica microspheres coated with quantum dots inside and the third hollow silica microspheres not coated with perovskite quantum dots inside. When used in photovoltaic cells, it can convert ultraviolet light, and the quantum dot composite material can also improve light transmittance.

[0012] In addition, in the present invention, the coordination group is located in the inner cavity of the second hollow silica microsphere and is a functional group of the first silicon source itself. During the synthesis of quantum dots, the quantum dots can have a very strong anchoring effect with the silica shell through the coordination group, preventing the quantum dots from detaching. Moreover, compared with the prior art method of infiltrating the ligand material into the inner cavity of the silica microsphere, which occupies the space inside the silicon shell, in the present invention, the volume of the inner cavity of the second hollow silica microsphere is larger and can accommodate more quantum dots. At the same time, under the anchoring effect of the coordination group, perovskite quantum dots are formed inside the second hollow silica microspheres to obtain a quantum dot composite material containing perovskite quantum dots coated with the second hollow silica microspheres, which is beneficial to prevent the perovskite quantum dots from being exposed to the outside of the second hollow silica microspheres and contacting with water, ethanol, and oxygen. At the same time, the perovskite quantum dots are connected to the coordination group through coordination, which can improve the stability of the perovskite quantum dots, thereby helping to prevent water, ethanol, oxygen, heat and ultraviolet light from damaging the perovskite quantum dots. Therefore, it can be effectively added to substrates such as anti-reflective coating layers and adhesive films to achieve effective utilization of ultraviolet light, thereby improving battery efficiency, and the process is simple and the cost is low. At the same time, the refractive index of the perovskite quantum dots coated with the second hollow silica microspheres can be significantly reduced compared to the perovskite quantum dots themselves, thereby improving the problem of increased refractive index of the substrate caused by the introduction of perovskite quantum dots, thereby helping to reduce the loss of battery efficiency caused by the perovskite quantum dots. Therefore, the method for preparing quantum dot composite materials of the present invention can improve the stability of perovskite quantum dots and reduce the loss of battery efficiency caused by perovskite quantum dots, so that they can be effectively added to substrates such as anti-reflective coating layers and adhesive films to achieve effective utilization of ultraviolet light, thereby improving battery efficiency.

[0013] In addition, the method for preparing a quantum dot composite material according to the above embodiment of the present invention may also have the following additional technical features:

[0014] In some embodiments of the present invention, the first solution includes a first solvent, water, and a catalyst.

[0015] In some embodiments of the present invention, the first solvent comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, preferably ethanol. Ethanol has a suitable boiling point and volatility, is low in cost, and is low in toxicity, and is one of the commonly used organic solvents in industry.

[0016] In some embodiments of the present invention, the catalyst comprises at least one of ammonia, diethanolamine, and triethanolamine. Ammonia, diethanolamine, and triethanolamine are all alkaline catalysts commonly used in the alkaline method for synthesizing silicon spheres, and help promote the hydrolysis and condensation of siloxane.

[0017] In some embodiments of the present invention, the coordination group includes at least one of a thiol group, an amino group, a carboxyl group, and a sulfonic acid group. Through the coordination of the thiol group, the amino group, the carboxyl group, and the sulfonic acid group, quantum dots can be generated and anchored within the silicon sphere, while also improving the stability of the quantum dots.

[0018] In some embodiments of the present invention, the first silicon source further comprises a methoxy group and / or an ethoxy group. During the reaction, the methoxy group or ethoxy group hydrolyzes to produce methanol or ethanol, while the Si group connected thereto forms SiOH. This facilitates the formation of the first hollow silica microspheres.

[0019] In some embodiments of the present invention, the first silicon source is Si(OR1) x R2 y R3 z , wherein x+y+z=4, x≥2, 0≤y≤1 and z≥1, R1 is a methyl group or an ethyl group, R2 is a short-chain alkyl group with a carbon number ≤2, and R3 is a thiol group, an amino group or an alkyl chain containing a thiol group and / or an amino group functional group.

[0020] In some embodiments of the present invention, the first silicon source includes at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropylmethyldimethoxysilane.

[0021] In some embodiments of the present invention, the molar ratio of the first solvent, water, catalyst, and first silicon source having a coordinating group is 1:(0.01-0.03):(0.01-0.05):(0.05-0.3), thereby facilitating the formation of first hollow silica microspheres having a coordinating group.

[0022] In some embodiments of the present invention, the first mixing time is 8 hours to 48 hours, thereby facilitating the formation of first hollow silica microspheres of suitable size and having coordination groups.

[0023] In some embodiments of the present invention, the second silicon source includes tetramethyl silicate and / or tetraethyl silicate, thereby facilitating the formation of second hollow silica microspheres having no coordination groups on the outside and coordination groups on the inside.

[0024] In some embodiments of the present invention, the molar ratio of the first silicon source to the second silicon source is (0.01-10):1, and preferably, the molar ratio of the first silicon source to the second silicon source is (0.05-1):1. This facilitates the formation of first hollow silica microspheres having coordination groups therein.

[0025] In some embodiments of the present invention, the second mixing time is 1 hour to 24 hours, thereby facilitating the formation of second hollow silica microspheres having coordination groups inside.

[0026] In some embodiments of the present invention, in step (3), the silicon sphere material further includes third hollow silica microspheres formed from the second silicon source and having no ligand groups therein. Thus, when subsequently added to a substrate for application, the overall light transmittance of the substrate can be increased.

[0027] In some embodiments of the present invention, the perovskite raw material includes a first precursor, a second precursor, a third precursor, and a ligand. The amount of the third precursor added can be zero. When the third precursor is added, rare earth-doped perovskite quantum dots are prepared. When the third precursor is not added, undoped perovskite quantum dots are prepared.

[0028] In some embodiments of the present invention, the first precursor is at least one of a cesium salt, a formamidine salt, and a methylamine salt.

[0029] In some embodiments of the present invention, the second precursor is at least one of a lead salt, a tin salt, and a copper salt.

[0030] In some embodiments of the present invention, the third precursor is at least one of ytterbium salt, cerium salt, praseodymium salt, europium salt and lutetium salt.

[0031] In some embodiments of the present invention, the first precursor, the second precursor, and the third precursor each independently include at least one of chloride, bromide, iodide, acetate, nitrate, and sulfate.

[0032] In some embodiments of the present invention, the ligand comprises oleic acid and / or oleylamine.

[0033] In some embodiments of the present invention, the second solvent includes dimethylformamide and / or dimethyl sulfoxide.

[0034] In some embodiments of the present invention, the third solvent includes at least one of toluene, n-hexane, n-octane, n-heptane, cyclohexane and methyl acetate.

[0035] In some embodiments of the present invention, the molar ratio of the silicon sphere material, the first precursor, the second precursor, the third precursor, and the ligand is 1:(0.1-1):(0.1-1):(0-10):(0.2-20). This facilitates the formation of perovskite quantum dots in the second hollow silica microspheres having the coordination groups therein.

[0036] In some embodiments of the present invention, the third mixed liquid contains a blended quantum dot composite material and quantum dots located outside the silicon sphere material. After the third mixed liquid is mixed with the third solvent for the fourth time, the quantum dots located outside the silicon sphere material are dissolved and dispersed, and a purification treatment is performed to retain the quantum dot composite material.

[0037] In some embodiments of the present invention, the quantum dot composite material further comprises third hollow silica microspheres not coated with perovskite quantum dots, thereby improving battery efficiency.

[0038] In its second aspect, the present invention provides a quantum dot composite material. According to an embodiment of the present invention, the quantum dot composite material is prepared using the aforementioned method. As a result, the perovskite quantum dots in the quantum dot composite material have high stability and can reduce the loss of battery efficiency caused by the perovskite quantum dots. This allows the composite material to be effectively added to substrates such as anti-reflective coatings and adhesive films, effectively utilizing ultraviolet light and thereby improving battery efficiency.

[0039] In its third aspect, the present invention provides anti-reflective coated glass. According to an embodiment of the present invention, the anti-reflective coated glass comprises a glass substrate and an anti-reflective coating layer. The anti-reflective coating layer is formed on at least one side of the glass substrate and comprises the quantum dot composite material prepared using the above-described method or the aforementioned quantum dot composite material. This reduces the impact of quantum dots on light transmittance, improving light transmission performance. Furthermore, by encapsulating the quantum dots with hollow silicon spheres, their stability and service life are enhanced, effectively utilizing ultraviolet light and improving battery efficiency.

[0040] In its fourth aspect, the present invention provides an adhesive film. According to embodiments of the present invention, the adhesive film comprises the quantum dot composite material prepared using the above-described method, or the aforementioned quantum dot composite material. This allows for efficient utilization of ultraviolet light and improved battery efficiency.

[0041] In a fifth aspect, the present invention provides a solar cell module. According to an embodiment of the present invention, the solar cell module includes the aforementioned anti-reflective coated glass or the aforementioned adhesive film. This effectively utilizes ultraviolet light and improves cell efficiency.

[0042] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0044] Figure 1 The figure is a flow chart of a method for preparing a quantum dot composite material according to one embodiment of the present invention. DETAILED DESCRIPTION

[0045] The following describes embodiments of the present invention in detail, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and are not to be construed as limiting the present invention.

[0046] In the description of the present invention, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of the technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of such features. In the description of the present invention, "plurality" means at least two, for example, two, three, etc., unless otherwise specifically defined.

[0047] In the first aspect of the present invention, the present invention provides a method for preparing a quantum dot composite material. Figure 1 , the method comprising:

[0048] S100: first mixing the first solution and the first silicon source having a coordination group

[0049] In this step, the first solution and the first silicon source having a coordinating group are first mixed, and the first silicon source undergoes a hydrolysis-condensation reaction to obtain a first mixed solution containing first hollow silica microspheres having coordinating groups. Specifically, by first mixing the first solution and the first silicon source having a coordinating group, the first silicon source having a coordinating group undergoes a hydrolysis reaction under the action of the first solution to form silicic acid groups, and simultaneously, the silicic acid groups undergo a polycondensation reaction to form first hollow silica microspheres having coordinating groups.

[0050] According to some embodiments of the present invention, the coordination group may include at least one of a thiol group, an amino group, a carboxyl group, and a sulfonic acid group. Through the coordination of the thiol group, the amino group, the carboxyl group, and the sulfonic acid group, quantum dots can be generated and anchored within the silicon sphere, while also improving the stability of the quantum dots.

[0051] In some embodiments of the present invention, the first silicon source is Si(OR1) x R2 y R3 z, wherein x+y+z=4, x≥2, 0≤y≤1 and z≥1, R1 is a methyl group or an ethyl group, R2 is a short-chain alkyl group with a carbon number ≤2, and R3 is a thiol group, an amino group or an alkyl chain containing a thiol group and / or an amino group functional group.

[0052] According to some embodiments of the present invention, the first silicon source further comprises a methoxy group and / or an ethoxy group. When the methoxy group or ethoxy group is hydrolyzed to generate methanol or ethanol during the reaction, the Si connected thereto forms SiOH. Thus, it is beneficial for the first silicon source to undergo a hydrolysis and polycondensation reaction under the action of the first solution, thereby forming a first hollow silica microsphere having a coordination group. Specifically, the first silicon source may include at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and aminopropylmethyldimethoxysilane.

[0053] According to some embodiments of the present invention, the first solution may include a first solvent, water, and a catalyst, thereby obtaining a hydrolysis-condensation reaction system, causing the first silicon source to undergo a hydrolysis-condensation reaction to form first hollow silica microspheres containing coordination groups.

[0054] According to some embodiments of the present invention, the specific type of the first solvent is not particularly limited and can be selected by those skilled in the art according to actual needs. For example, the first solvent may include at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, preferably ethanol. Ethanol has a relatively suitable boiling point and volatility, is low in cost, and is less toxic, and is one of the commonly used organic solvents in industry. Therefore, using ethanol as the first solvent can facilitate the formation of hollow silica microspheres.

[0055] According to some embodiments of the present invention, the specific type of catalyst is not particularly limited and can be selected by those skilled in the art based on actual needs. For example, the catalyst may include at least one of ammonia, diethanolamine, and triethanolamine. Ammonia, diethanolamine, and triethanolamine are all alkaline catalysts commonly used in the synthesis of silicon spheres using alkaline methods, and help promote the hydrolysis and condensation of siloxane.

[0056] According to some embodiments of the present invention, the molar ratio of the first solvent, water, catalyst and the first silicon source having a coordination group can be 1:(0.01-0.03):(0.01-0.05):(0.05-0.3), for example, it can be 1:0.01:0.01:0.05, 1:0.02:0.03:0.05, 1:0.03:0.05:0.05, 1:0.01:0.01:0.2, 1:0.02:0.03:0.2, 1:0.03:0.05:0.2, 1:0.01:0.01:0.3, 1:0.02:0.03:0.3, 1:0.03:0.05:0.3, etc. The inventors found that if the first solvent is too much, the intermolecular collisions are reduced, and the first hollow silica microspheres are difficult to form. If the first solvent is too little, the intermolecular collisions are too much, the reaction is accelerated, and the thickness of the first hollow silica microspheres increases. If there is too little water, the hydrolysis time is prolonged, the reaction is slow, and the reaction time is increased. If there is too much water, the reaction is too fast, resulting in excessive hydrolysis of the first silicon source. If there is too little catalyst, effective catalysis cannot be achieved, resulting in too few first hollow silica microspheres formed, too small a volume, and insufficient internal space. If there is too much catalyst, the catalysis is too intense, the first hollow silica microspheres are too large or even precipitate, and cannot be well dispersed. If there is too little first silicon source, it is difficult to form the first hollow silica microspheres. If the first silicon source is too much, the first hollow silica microspheres formed are too large, the reaction is too fast, and the reaction time is difficult to control. The present invention can facilitate the formation of first hollow silica microspheres with coordination groups, with a size (diameter) of about 20-40 nm, by controlling the molar ratio of the first solvent, water, catalyst and the first silicon source with coordination groups within the above range.

[0057] According to some embodiments of the present invention, the time of the first mixing can be 8h-48h, for example, it can be 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 48h, etc. The inventors found that when the mixing time is too short, the first hollow silica microspheres cannot be effectively formed; when the mixing time is too long, the size of the first hollow silica microspheres is too large. The present invention can facilitate the formation of first hollow silica microspheres of appropriate size and having a coordination group by controlling the time of the first mixing within the above range. Further, in order to increase the reaction rate, the first mixing can be carried out under stirring conditions.

[0058] S200: performing a second mixing of the first mixed liquid and the second silicon source

[0059] In this step, the first mixed liquid is mixed with the second silicon source for a second time to obtain a second mixed liquid containing second hollow silica microspheres having a coordination group inside. Specifically, by mixing the first mixed liquid with the second silicon source for a second time, the second silicon source does not contain a coordination group, and the second silicon source can undergo a hydrolysis and polycondensation reaction under the action of the first mixed liquid, and a layer of silicon dioxide is further coated on the surface of the first hollow silica microspheres having the coordination group, thereby forming second hollow silica microspheres having the coordination group inside, and the outer wall of the shell of the second hollow silica microsphere does not contain a coordination group, that is, the coordination group is only present inside the second hollow silica microsphere.

[0060] According to some embodiments of the present invention, the second silicon source may include tetramethyl silicate and / or tetraethyl silicate. Since tetramethyl silicate and / or tetraethyl silicate do not contain ligands, a layer of functional-group-free silica can be coated on the surface of the first hollow silica microspheres containing functional groups. This ensures that the functional groups appear only within the second hollow silica microspheres, preventing exposed functional groups from reacting with the precursor to form quantum dots. This also increases the thickness of the second hollow silica microspheres and improves their stability. This facilitates the formation of second hollow silica microspheres that have no ligands on the exterior and ligands on the interior.

[0061] According to some embodiments of the present invention, the molar ratio of the first silicon source to the second silicon source can be (0.01-10):1, for example, it can be 0.01:1, 0.03:1, 0.05:1, 0.08:1, 1:1, 3:1, 5:1, 10:1, etc. The inventors have found that when the molar ratio of the first silicon source to the second silicon source is too large, the silicon dioxide formed by the second silicon source cannot completely coat the first hollow silica microspheres, resulting in the coordination group being exposed outside the first hollow silica microspheres. When the molar ratio of the first silicon source to the second silicon source is too small, the coating is excessive, and the thickness of the obtained second hollow silica microspheres increases, resulting in excessive size. The present invention, by controlling the molar ratio of the first silicon source to the second silicon source within the above range, can facilitate coating a layer of silicon dioxide on the surface of the second hollow silica microspheres having the coordination group, thereby forming the second hollow silica microspheres having the coordination group inside.

[0062] Preferably, the molar ratio of the first silicon source to the second silicon source is (0.05-1):1. When the molar ratio of the first silicon source to the second silicon source is within the range of (0.05-1):1, the second silicon source can completely coat the first hollow silica microspheres. If the first silicon source is excessive, first hollow silica microspheres that are not coated with the second silicon source will exist in the first mixed solution. Due to the presence of ligands on the outer walls of the first hollow silica microspheres, their dispersibility in the solvent will increase, making it difficult to precipitate and separate them from the solvent, resulting in material waste.

[0063] According to some embodiments of the present invention, the second mixing time can be 1 hour to 24 hours, for example, 1 hour, 3 hours, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours, 24 hours, etc. The inventors have found that by controlling the second mixing time within the above range, the present invention can facilitate the formation of second hollow silica microspheres having coordination groups inside. Furthermore, to increase the reaction rate, the second mixing can be carried out under stirring conditions.

[0064] It should be noted that, during the second mixing of the first mixed liquid and the second silicon source, the second silicon source may also form hollow silica microspheres without coordination groups under the action of water and the catalyst, namely, third hollow silica microspheres.

[0065] S300: solid-liquid separation of the second mixed liquid

[0066] In this step, the second mixed liquid is subjected to solid-liquid separation to obtain a silica sphere material containing second hollow silica microspheres having ligand groups therein. Specifically, by solid-liquid separation (such as centrifugation or filtration), the solid is retained to obtain a silica sphere material containing at least the second hollow silica microspheres having ligand groups therein.

[0067] According to some embodiments of the present invention, after the second mixed liquid is subjected to solid-liquid separation, the obtained silicon sphere material can be dried, thereby further removing the liquid in the silicon sphere material and retaining only the silicon sphere material. It should be noted that the drying temperature is not particularly limited, and those skilled in the art can select it according to actual needs. The inventors found in their research that when ethanol is used as the first solvent, the drying temperature can be no less than 80°C. Furthermore, the silicon sphere material can also be dried under vacuum conditions.

[0068] According to some embodiments of the present invention, before drying, the obtained silicon sphere material containing the second hollow silica microspheres with coordination groups inside can be cleaned with a first solvent, thereby helping to reduce the first solvent, water, catalyst and other substances attached to the shell surface of the silicon sphere material.

[0069] According to some embodiments of the present invention, the silicon sphere material further includes third hollow silica microspheres formed from a second silicon source, which do not contain ligand groups. The first hollow silica microspheres produced by hydrolysis and condensation of the first silicon source are coated with silica formed from the second silicon source. If the yield of the first silicon source during the hydrolysis and condensation process is slightly low, the second silicon source will be excessive, and the second silicon source will hydrolyze and condense to form third hollow silica microspheres without ligand groups. These microspheres are mixed with the silicon sphere material and, when subsequently added to a substrate for application, can increase the overall light transmittance of the substrate.

[0070] S400: The perovskite raw material, the second solvent and the silicon ball material are mixed for the third time

[0071] In this step, the perovskite raw material, the second solvent, and the silicon sphere material are mixed for a third time to obtain a third mixed liquid. Specifically, the perovskite raw material, the second solvent, and the silicon sphere material can be mixed for a third time under stirring conditions, which can facilitate the uniform mixing of the perovskite raw material, the second solvent, and the silicon sphere material, so that the perovskite raw material enters the inner cavity of the silicon sphere material and combines with the ligand groups embedded in the shell of the silicon sphere material to generate perovskite quantum dots. At this time, the perovskite quantum dots are anchored inside the shell of the silicon sphere material. After the reaction, the third mixed liquid contains the blended quantum dot composite material and the quantum dots located outside the silicon sphere material.

[0072] According to some embodiments of the present invention, the perovskite raw material may include a first precursor, a second precursor, a third precursor, and a ligand. During the quantum dot synthesis process, a portion of the first precursor, the second precursor, and the third precursor enter the interior of the silicon sphere material to form perovskite quantum dots. At the same time, another portion of the first precursor, the second precursor, and the third precursor react with the ligand in the second solvent in the second solvent to generate uncoated quantum dots located outside the silicon sphere material.

[0073] It should be noted that the amount of the third precursor added can be zero. When the third precursor is added, rare earth-doped perovskite quantum dots are prepared. When the third precursor is not added, undoped perovskite quantum dots are prepared.

[0074] According to some embodiments of the present invention, the first precursor may be at least one of a cesium salt, a formamidine salt, and a methylamine salt.

[0075] According to some embodiments of the present invention, the second precursor may be at least one of a lead salt, a tin salt, and a copper salt.

[0076] According to some embodiments of the present invention, the third precursor may be at least one of ytterbium salt, cerium salt, praseodymium salt, europium salt, and lutetium salt.

[0077] According to some embodiments of the present invention, the first precursor, the second precursor, and the third precursor may each independently include at least one of chloride, bromide, iodide, acetate, nitrate, and sulfate.

[0078] According to some embodiments of the present invention, the ligand may include oleic acid and / or oleylamine. Thus, oleic acid / oleylamine, as a ligand for quantum dot synthesis, is used in the third mixed solution to combine with the perovskite raw material outside the silicon sphere material (not entering the inner cavity of the silicon sphere material), thereby producing quantum dots outside the silicon sphere material. It should be emphasized that the oleic acid oleylamine ligand in the present invention is not used for quantum dot synthesis inside the silicon sphere material, but for quantum dot synthesis outside the silicon sphere material. The reason for this arrangement is that: after the reaction is completed, if there is unreacted perovskite raw material in the third mixed solution, when the quantum dot composite material is separated and purified from the solution, whether by centrifugation or precipitation, if there is no oleic acid oleylamine in the third solution to form quantum dots, then a large portion of the raw material will precipitate along with the quantum dot composite material, resulting in the quantum dot composite material being unable to be separated from the perovskite raw material.

[0079] According to some embodiments of the present invention, the second solvent may include dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO), which can dissolve the perovskite raw material and facilitate uniform mixing of the perovskite raw material, the second solvent, and the silicon sphere material.

[0080] According to some embodiments of the present invention, the molar ratio of the silicon sphere material, the first precursor, the second precursor, the third precursor and the ligand can be 1:(0.1-1):(0.1-1):(0-10):(0.2-20), for example, it can be 1:0.1:0.1:0.1:0.2, 1:0.5:0.5:5:0.2, 1:1:1:10:0.2, 1:0.1:0.1:0.1:10, 1:0.5:0.5:5:10, 1:1:1:10:10, 1:0.1:0.1:0.1:20, 1:0.5:0.5:5:20, 1:1:1:10:20, etc. The inventors have found that too much or too little of any of the component ratios will result in the failure to generate quantum dots or the generation of non-luminescent phase quantum dots, resulting in reduced conversion efficiency and yield. The present invention controls the molar ratio of the silicon sphere material, the first precursor, the second precursor, the third precursor and the ligand within the above range, thereby reducing the waste of perovskite raw materials while synthesizing quantum dots.

[0081] It should be noted that the third precursor is a rare earth element, which is generally difficult to incorporate into perovskite quantum dots, requiring either a high addition level or high temperature. The higher addition level was chosen here. When undoped, perovskite quantum dots are formed for light conversion, while when doped, they are used for photon quantum tailoring.

[0082] S500: performing a fourth mixing and purification process on the third mixed liquid and the third solvent

[0083] In this step, the third mixed liquid and the third solvent are subjected to a fourth mixing and purification process to obtain a quantum dot composite material comprising perovskite quantum dots coated with second hollow silica microspheres. Specifically, by subjecting the third mixed liquid and the third solvent to a fourth mixing process, the uncoated quantum dots located on the outside of the silica sphere material are dissolved in the third solvent, and the second hollow silica microspheres coated with quantum dots are precipitated in the third solvent. Purification is then performed to retain the quantum dot composite material while removing the uncoated quantum dots and solvent. The quantum dot composite material comprises second hollow silica microspheres coated with quantum dots and third hollow silica microspheres not coated with perovskite quantum dots. When used in photovoltaic cells, it can convert ultraviolet light, and the quantum dot composite material can also improve light transmittance.

[0084] In addition, in the present invention, the coordination group is located in the inner cavity of the second hollow silica microsphere and is a functional group of the first silicon source itself. During the synthesis of quantum dots, the quantum dots can have a very strong anchoring effect with the silica shell through the coordination group, preventing the quantum dots from detaching. Moreover, compared with the prior art method of infiltrating the ligand material into the inner cavity of the silica microsphere, which occupies the space inside the silicon shell, in the present invention, the volume of the inner cavity of the second hollow silica microsphere is larger and can accommodate more quantum dots. At the same time, under the anchoring effect of the coordination group, perovskite quantum dots are formed in the second hollow silica microspheres having the coordination group inside, and a quantum dot composite material containing perovskite quantum dots coated with the second hollow silica microspheres is obtained, which is beneficial to prevent the perovskite quantum dots from being exposed to the outside of the second hollow silica microspheres and contacting with water, ethanol, and oxygen. At the same time, the perovskite quantum dots are connected to the coordination group through coordination, which can improve the stability of the perovskite quantum dots, thereby helping to prevent water, ethanol, oxygen, heat and ultraviolet light from damaging the perovskite quantum dots. Therefore, it can be effectively added to substrates such as anti-reflective coating layers and adhesive films to achieve effective utilization of ultraviolet light, thereby improving battery efficiency, and the process is simple and the cost is low. At the same time, the refractive index of the perovskite quantum dots coated with the second hollow silica microspheres can be significantly reduced compared to the perovskite quantum dots themselves, thereby improving the problem of increased refractive index of the substrate caused by the introduction of perovskite quantum dots, thereby helping to reduce the loss of battery efficiency caused by the perovskite quantum dots. Furthermore, in order to increase the reaction rate, the fourth mixing can be performed under stirring conditions.

[0085] According to some embodiments of the present invention, the third mixed liquid contains a blended quantum dot composite material and quantum dots located outside the silicon sphere material. After the third mixed liquid is mixed with the third solvent for the fourth time, the quantum dots located outside the silicon sphere material are dissolved and dispersed, and a purification treatment is performed to retain the quantum dot composite material.

[0086] According to some embodiments of the present invention, the purification process may include solid-liquid separation, thereby removing the liquid in the system to obtain a quantum dot composite material comprising perovskite quantum dots coated with the second hollow silica microspheres.

[0087] According to some embodiments of the present invention, the third solvent may include a low-grade solvent. Specifically, the third solvent may include at least one of toluene, n-hexane, n-octane, n-heptane, cyclohexane, and methyl acetate, and is used to disperse the uncoated quantum dots to facilitate subsequent solid-liquid separation.

[0088] According to some embodiments of the present invention, to reduce impurities in the resulting quantum dot composite material, primarily by removing ligands attached to the outer surface of the silica, uncoated quantum dots, and organic solvent, the resulting quantum dot composite material may be cleaned and dried using a third solvent. It should be noted that the drying conditions are not particularly limited and can be selected by those skilled in the art based on actual needs.

[0089] According to some embodiments of the present invention, the resulting quantum dot composite material includes not only second hollow silica microspheres with perovskite quantum dots encapsulated therein, but also third hollow silica microspheres without perovskite quantum dots encapsulated therein. Because the silicon sphere material also includes third hollow silica microspheres without coordination groups formed from a second silicon source, during the fourth mixing of the third mixed liquid with the third solvent, no perovskite quantum dots are formed within the third hollow silica microspheres without coordination groups. That is, the quantum dot composite material further includes third hollow silica microspheres without perovskite quantum dots encapsulated therein. This can reduce the effect of the increase in refractive index caused by the addition of quantum dots while further reducing the refractive index of the incorporated substrate, reducing light reflectivity, and increasing light transmittance, thereby improving battery efficiency.

[0090] Therefore, the method for preparing quantum dot composite materials of the present invention can improve the stability of perovskite quantum dots and reduce the loss of battery efficiency caused by perovskite quantum dots, so that they can be effectively added to substrates such as anti-reflective coating layers and adhesive films, thereby achieving effective utilization of ultraviolet light and improving light transmittance, thereby improving battery efficiency.

[0091] It should be noted that in step S400, a hot injection method can also be used to prepare a quantum dot composite material, that is, after adding the synthesized silicon sphere material to the reaction solvent, the synthesis is carried out according to the steps of synthesizing quantum dots by the hot injection method. During purification in step S500, methyl acetate is first used for precipitation to obtain the solid, and then n-hexane is used for dispersion, and the solid is obtained by centrifugation to obtain a quantum dot composite material containing perovskite quantum dots coated with a second hollow silica microsphere.

[0092] In its second aspect, the present invention provides a quantum dot composite material. According to an embodiment of the present invention, the quantum dot composite material is prepared using the above-described method. As a result, the perovskite quantum dots in the quantum dot composite material have high stability and can reduce the loss of battery efficiency caused by the perovskite quantum dots. This allows the composite material to be effectively added to substrates such as anti-reflective coatings and adhesive films, effectively utilizing ultraviolet light and thereby improving battery efficiency. It should be noted that the features and effects described for the above-described method for preparing the quantum dot composite material also apply to the quantum dot composite material and will not be elaborated upon here.

[0093] In its third aspect, the present invention provides anti-reflective coated glass. According to an embodiment of the present invention, the anti-reflective coated glass comprises a glass substrate and an anti-reflective coating layer. The anti-reflective coating layer is formed on at least one side of the glass substrate and comprises the quantum dot composite material prepared using the above-described method or the aforementioned quantum dot composite material. This reduces the impact of quantum dots on light transmittance, improving light transmittance. Furthermore, by encapsulating the quantum dots with hollow silicon spheres, their stability and service life are enhanced, effectively utilizing ultraviolet light and improving battery efficiency. Specifically, the anti-reflective coating layer can be formed by mixing the quantum dot composite material with a room-temperature curing anti-reflective coating solution, then applying the mixture to the surface of the glass substrate to form the anti-reflective coating layer.

[0094] According to some embodiments of the present invention, the mass ratio of the quantum dot composite material to the room temperature curing anti-reflective coating solution can be (0.2-10):1000, for example, 0.2:1000, 0.5:1000, 1:1000, 2:1000, 4:1000, 6:1000, 8:1000, 10:1000, etc. In the present invention, by controlling the mass ratio of the quantum dot composite material to the room temperature curing anti-reflective coating solution within the above range, a very uniformly dispersed anti-reflective layer can be formed, which is conducive to the effective use of ultraviolet light and reduces the quantum dot composite material's shielding of visible light, thereby facilitating improved battery efficiency.

[0095] In addition, it should be noted that the characteristics and effects described for the above-mentioned method for preparing the quantum dot composite material or the above-mentioned quantum dot composite material are also applicable to the anti-reflection coated glass, and will not be described in detail here.

[0096] In its fourth aspect, the present invention provides an adhesive film. According to an embodiment of the present invention, the adhesive film comprises the quantum dot composite material prepared by the above-mentioned method or the aforementioned quantum dot composite material. Specifically, the adhesive film can be prepared by mixing the quantum dot composite material with an adhesive film masterbatch, and then subjecting the mixture to extrusion molding, casting, embossing, cooling, and other processes to obtain the adhesive film. This allows for effective utilization of ultraviolet light and improves battery efficiency. It should be noted that the features and effects described for the above-mentioned method for preparing the quantum dot composite material or the aforementioned quantum dot composite material also apply to the adhesive film and will not be further elaborated here.

[0097] In a fifth aspect of the present invention, a solar cell module is provided. According to an embodiment of the present invention, the solar cell module includes the above-mentioned anti-reflective coated glass or the above-mentioned adhesive film. Specifically, the solar cell module can be obtained by laminating the above-mentioned anti-reflective coated glass, adhesive film, and solar cells (such as crystalline silicon cells, cadmium telluride cells, copper indium gallium selenide cells, perovskite cells, etc.). In this way, effective utilization of ultraviolet light can be achieved, and cell efficiency can be improved. In addition, it should be noted that the features and effects described for the above-mentioned anti-reflective coated glass or the above-mentioned adhesive film are also applicable to the solar cell module and will not be repeated here.

[0098] The present invention is described below with reference to specific examples. It should be noted that these examples are merely illustrative and do not limit the present invention in any way.

[0099] Example 1

[0100] Hollow silica microspheres with coordination groups were synthesized by using ethanol, deionized water, ammonia water and aminopropyltriethoxysilane in a molar ratio of 1:0.015:0.013:0.15. First, ethanol, deionized water and ammonia water were mixed in the above proportions and stirred for 1 hour to obtain a solution. Then, aminopropyltriethoxysilane was added dropwise to the solution. After the addition was completed, the stirring reaction was continued for 24 hours to obtain a first mixed solution.

[0101] Tetraethyl silicate was added dropwise to the obtained first mixed solution at a molar ratio of aminopropyltriethoxysilane to tetraethyl silicate of 0.08:1. After the addition was completed, stirring and reacting were continued for 8 hours to obtain a second mixed solution.

[0102] The second mixed solution was centrifuged at a speed of 8000 rpm for 5 minutes, and the precipitate was collected and washed with ethanol three times, and then vacuum-dried at 80° C. to obtain a silica sphere material containing hollow silica microspheres with amino groups inside.

[0103] The obtained silicon sphere material, chloromethylamine, lead chloride, ytterbium chloride, oleic acid and oleylamine as reaction raw materials are added into DMSO in a molar ratio of 1:0.5:0.5:2:3:3, and stirred until the solution is clear. After the reaction raw materials are completely dissolved, stirring is continued for 2 hours to obtain a third solution.

[0104] The third solution was added to a large amount of methanol for precipitation, and the mixture was centrifuged at 8000 rpm for 5 min to collect the solid.

[0105] The solid was washed three times with n-hexane and centrifuged three times at 8000 rpm for 5 min each time. The solid was taken and dried under vacuum at 80° C. to obtain a quantum dot composite material comprising hollow silica microspheres-encapsulated perovskite quantum dots.

[0106] A quantum dot composite material containing perovskite quantum dots coated with hollow silica microspheres was mixed with a commercially available room-temperature curing anti-reflection coating liquid at a mass ratio of 1:1000 and stirred for 1 hour. The mixture was then coated on 300mm*300mm ultra-clear non-tempered glass and allowed to stand for a period of time to completely cure. The anti-reflection coated glass was then obtained and its transmittance was tested.

[0107] The anti-reflective coated glass was laminated with PVB film and crystalline silicon cells to prepare a crystalline silicon solar cell module. After the crystalline silicon solar cell module was left to stabilize for 24 hours, its efficiency was tested.

[0108] The crystalline silicon solar cell components were placed in 85°C / 85% RH for aging for 1000 hours and then taken out to test their efficiency.

[0109] Comparative Example 1

[0110] Hollow silica microspheres with coordination groups were synthesized by using ethanol, deionized water, ammonia water and aminopropyltriethoxysilane in a molar ratio of 1:0.015:0.013:0.15. First, ethanol, deionized water and ammonia water were mixed in the above proportions and stirred for 1 hour to obtain a solution. Then, aminopropyltriethoxysilane was added dropwise to the solution. After the addition was completed, the stirring reaction was continued for 24 hours to obtain a first mixed solution.

[0111] Tetraethyl silicate was added dropwise to the obtained first mixed solution at a molar ratio of aminopropyltriethoxysilane to tetraethyl silicate of 0.08:1. After the addition was completed, stirring and reacting were continued for 8 hours to obtain a second mixed solution.

[0112] The second mixed solution was centrifuged at a speed of 8000 rpm for 5 minutes, and the precipitate was collected and washed with ethanol three times, and then vacuum-dried at 80° C. to obtain a silica sphere material containing hollow silica microspheres with amino groups inside.

[0113] The silica sphere material was mixed with a commercially available room-temperature curing anti-reflection coating liquid at a mass ratio of 1:1000 and stirred for 1 hour. The mixture was then coated on 300mm*300mm ultra-clear non-tempered glass. After being left for a period of time to completely cure, the anti-reflection coated glass was obtained and its transmittance was tested.

[0114] The anti-reflective coated glass was laminated with polyvinyl butyral (PVB) film and crystalline silicon cells to prepare a crystalline silicon cell module. After the crystalline silicon cell module was allowed to stand for 24 hours to stabilize, its efficiency was tested.

[0115] The crystalline silicon solar cell components were placed in 85°C / 85% RH for aging for 1000 hours and then taken out to test their efficiency.

[0116] Comparative Example 2

[0117] A conventional commercially available room temperature curing anti-reflection coating liquid was coated on 300mm*300mm ultra-clear non-tempered glass. After being left for a period of time to completely cure, an anti-reflection coated glass was obtained, and its transmittance was tested.

[0118] The anti-reflective coated glass was laminated with PVB film and crystalline silicon cells to prepare a crystalline silicon solar cell module. After the crystalline silicon solar cell module was left to stabilize for 24 hours, its efficiency was tested.

[0119] The crystalline silicon solar cell components were placed in 85°C / 85% RH for aging for 1000 hours and then taken out to test their efficiency.

[0120] Comparative Example 3

[0121] The difference from Example 1 is that when synthesizing perovskite quantum dots, no silicon sphere material is added to the reaction raw materials, and the rest remains unchanged. The obtained perovskite quantum dots are mixed with a commercially available room-temperature curing anti-reflection coating liquid in a mass ratio of 1:1000 and stirred for 1 hour, and then coated on 300mm*300mm ultra-clear non-tempered glass. After being left for a period of time to allow it to completely cure, anti-reflection coated glass is obtained, and its transmittance is tested.

[0122] The anti-reflective coated glass was laminated with PVB film and crystalline silicon cells to prepare a crystalline silicon solar cell module. After the crystalline silicon solar cell module was left to stabilize for 24 hours, its efficiency was tested.

[0123] The crystalline silicon solar cell components were placed in 85°C / 85% RH for aging for 1000 hours and then taken out to test their efficiency.

[0124] The transmittance test results of the anti-reflection coated glass obtained in Example 1 and Comparative Examples 1-3, and the cell efficiency test results of the crystalline silicon cell assembly before and after aging for 1000 hours at 85°C / 85%RH are shown in Table 1.

[0125] Table 1

[0126] Transmittance Battery efficiency DH1000 battery efficiency Example 1 93.8％ 21.0％ 20.9％ Comparative Example 1 94.0％ 20.4％ 20.4％ Comparative Example 2 93.2％ 20.2％ 20.1％ Comparative Example 3 92.5％ 20.7％ 19.8％

[0127] Example 1 is a battery assembly for anti-reflective coated glass prepared by mixing the quantum dot composite material prepared by the present invention with a conventional anti-reflective coating solution; Comparative Example 1 is a battery assembly for anti-reflective coated glass prepared by adding only the silicon ball material prepared by the present invention to a conventional anti-reflective coating solution; Comparative Example 2 is a battery assembly for anti-reflective coated glass prepared by using a conventional anti-reflective coating solution; Comparative Example 3 is a battery assembly for anti-reflective coated glass prepared by mixing uncoated quantum dots with a conventional anti-reflective coating solution without adding the silicon ball material.

[0128] As can be seen from Table 1, the initial cell efficiency and the cell efficiency after aging of the cell assembly obtained in Example 1 are both higher than those in Comparative Example 1. The transmittance of the anti-reflective coated glass obtained in Example 1 is slightly lower than that in Comparative Example 1. This is because the silicon ball material in Example 1 contains tailored quantum dots, which can significantly improve the initial cell efficiency and the cell efficiency after aging when the transmittance is similar.

[0129] The transmittance of the anti-reflective coated glass obtained in Example 1, the initial battery efficiency of the obtained battery assembly, and the battery efficiency of the obtained battery assembly after aging are all higher than those in Comparative Examples 2-3. This shows that by adding the quantum dot composite material of the present invention, the light transmittance and battery efficiency can be greatly improved.

[0130] It can be seen from Comparative Examples 1 and 2 that the light transmittance and battery efficiency can be greatly improved by adding the silicon ball material of the present invention.

[0131] It can be seen from Example 1 and Comparative Example 3 that the rare earth-doped quantum dots coated with silicon spheres have stronger stability and higher light conversion efficiency.

[0132] Compared with Comparative Examples 1-3, the crystalline silicon solar cell assembly obtained in Example 1 exhibited higher cell efficiency before and after aging at 85°C / 85% RH for 1000 hours. This indicates that the method for preparing a quantum dot composite material according to the present invention can improve the stability of perovskite quantum dots and reduce the loss of cell efficiency caused by perovskite quantum dots. This allows them to be effectively added to substrates such as anti-reflective coating layers, achieving effective utilization of ultraviolet light and thereby improving cell efficiency.

[0133] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0134] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a quantum dot composite material, characterized in that: include: (1) performing a first mixing of a first solution and a first silicon source having a coordination group, causing the first silicon source to undergo a hydrolysis-condensation reaction, so as to obtain a first mixed solution containing first hollow silica microspheres having a coordination group; (2) performing a second mixing of the first mixed solution and a second silicon source to obtain a second mixed solution containing second hollow silica microspheres having a coordination group therein; (3) performing solid-liquid separation on the second mixed liquid to obtain a silicon sphere material containing second hollow silica microspheres having coordination groups therein; (4) performing a third mixing of the perovskite raw material, the second solvent, and the silicon sphere material to obtain a third mixed solution; (5) performing a fourth mixing and purification process on the third mixed solution and the third solvent to obtain a quantum dot composite material comprising perovskite quantum dots coated with the second hollow silica microspheres.

2. The method according to claim 1, characterized in that The first solution includes a first solvent, water and a catalyst.

3. The method according to claim 2, characterized in that The first solvent comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, preferably ethanol; Optionally, the catalyst comprises at least one of aqueous ammonia, diethanolamine and triethanolamine; Optionally, the coordinating group includes at least one of a thiol group, an amino group, a carboxyl group, and a sulfonic acid group; Optionally, the first silicon source further has a methoxy group and / or an ethoxy group; Optionally, the first silicon source is Si(OR1) x R2 y R3 z , wherein x+y+z=4, x≥2, 0≤y≤1 and z≥1, R1 is a methyl group or an ethyl group, R2 is a short-chain alkyl group having ≤2 carbon atoms, and R3 is a thiol group, an amino group or an alkyl chain containing a thiol group and / or an amino group; Optionally, the first silicon source includes at least one of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropylmethyldimethoxysilane.

4. The method according to claim 2, characterized in that The molar ratio of the first solvent, water, catalyst and the first silicon source having a coordination group is 1:(0.01-0.03):(0.01-0.05):(0.05-0.3); Optionally, the first mixing time is 8h-48h.

5. The method according to claim 1, wherein The second silicon source includes tetramethyl silicate and / or tetraethyl silicate; Optionally, the molar ratio of the first silicon source to the second silicon source is (0.01-10):1, preferably (0.05-1):1; Optionally, in step (3), the silicon sphere material further comprises third hollow silica microspheres formed from a second silicon source and having no coordination groups therein; Optionally, the second mixing time is 1 hour to 24 hours.

6. The method according to claim 1, characterized in that The perovskite raw material includes a first precursor, a second precursor, a third precursor and a ligand; Optionally, the first precursor is at least one of a cesium salt, a formamidine salt, and a methylamine salt; Optionally, the second precursor is at least one of a lead salt, a tin salt, and a copper salt; Optionally, the third precursor is at least one of ytterbium salt, cerium salt, praseodymium salt, europium salt and lutetium salt; Optionally, the first precursor, the second precursor, and the third precursor each independently include at least one of chloride, bromide, iodide, acetate, nitrate, and sulfate; Optionally, the ligand comprises oleic acid and / or oleylamine; Optionally, the second solvent comprises dimethylformamide and / or dimethyl sulfoxide; Optionally, the third solvent comprises at least one of toluene, n-hexane, n-octane, n-heptane, cyclohexane and methyl acetate; Optionally, the molar ratio of the silicon sphere material, the first precursor, the second precursor, the third precursor and the ligand is 1:(0.1-1):(0.1-1):(0-10):(0.2-20); Optionally, the third mixed liquid contains a blended quantum dot composite material and quantum dots located outside the silicon sphere material, and after the third mixed liquid is subjected to a fourth mixing with a third solvent, the quantum dots located outside the silicon sphere material are dissolved and dispersed, and a purification treatment is performed to retain the quantum dot composite material; Optionally, the quantum dot composite material further comprises third hollow silica microspheres which are not coated with perovskite quantum dots.

7. A quantum dot composite material, characterized in that: The quantum dot composite material is prepared by the method according to any one of claims 1 to 6. 8.An anti-reflection coated glass, characterized in that: The invention comprises a glass substrate and an anti-reflection coating layer, wherein the anti-reflection coating layer is formed on at least one side of the glass substrate, and the anti-reflection coating layer comprises a quantum dot composite material prepared by the method according to any one of claims 1 to 6 or the quantum dot composite material according to claim 7.

9. A film, characterized in that: The invention comprises the quantum dot composite material prepared by the method according to any one of claims 1 to 6 or the quantum dot composite material according to claim 7.

10. A solar cell module, characterized in that: It includes the anti-reflection coated glass according to claim 8 or the adhesive film according to claim 9.

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