A kind of preparation method of tin chloride acetylacetonate and its product and application
Through the reaction of acetylacetone salt and tetravalent tin salt and solid phase grinding technology, the complex and cost of acetylacetone tin chloride preparation process is solved, high-purity and low-cost mass production are achieved, and the development of perovskite solar cells is promoted.
Patent Information
- Application Number
- CN202411839016.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-13
- Publication Date
- 2025-04-04
AI Technical Summary
In the prior art, the preparation process of tin acetylacetonate chloride is complex, has high cost, and cannot achieve large-scale mass production, resulting in high prices of perovskite solar cells, which is not conducive to its development in the field of solar energy.
The reaction of acetylacetone salt and tetravalent tin salt was used to prepare tin acetylacetone chloride, and it was purified by solid phase grinding and multiple extractions, combined with low-temperature rotary vaporization and column chromatography to obtain high-purity tin acetylacetone chloride.
It has achieved high purity preparation of tin chloride in acetylacetonate, reduced production costs, and was able to carry out kilogram production, which has promoted the industrialization of solar photovoltaics.
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Figure CN119751498A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of solar energy, in particular to the field of nanomaterial technology, and specifically relates to a preparation method of tin acetylacetonate chloride, a product thereof and an application thereof. Background Art
[0002] SnO 2 Nanomaterials have been widely used as electron transport layer materials in perovskite solar cells. Perovskite solar cells are considered by researchers to be the best alternative to silicon-based solar cells due to their simple manufacturing process and low cost. In order to reduce the cost of perovskite solar cells, SnO 2 The selling price of nanomaterials and their precursors should be kept low.
[0003] The existing technology is to use SnCl 2 In the presence of oxygen, it reacts with acetylacetone. Since acetylacetone will oxidize and change color in an oxygen atmosphere, the purification is complicated, the yield is low, and it cannot be mass-produced, and high-purity products cannot be obtained. 2 +1 / 2O 2 +2Hacac======SnCl 2 (acac) 2 +H 2 At present, the synthesis of acetylacetonate tin (IV) chloride is a liquid phase synthesis reaction, with low yield, cumbersome post-processing, and purity always lower than 99%. The commercially available acetylacetonate tin (IV) chloride is expensive, which makes the SnO prepared by it 2 The high cost has raised the price of perovskite solar cells, which is not conducive to their development in the solar energy field. Summary of the invention
[0004] The purpose of the present invention is to provide a preparation method of tin acetylacetonate chloride and a product and application thereof, aiming to solve the problems that the traditional process is complicated, the cost is high, and the large-scale production of tin (IV) acetylacetonate chloride cannot be achieved.
[0005] The technical solution of the present invention is as follows:
[0006] A method for preparing tin acetylacetonate chloride comprises the following steps:
[0007] S1. At 0-20°C, acetylacetone and a base are respectively charged into a grinder in a certain proportion for rotary grinding, the system is filled with nitrogen, protected from light, and the mixture undergoes a liquid state and a gel state until a solid acetylacetone salt powder is obtained;
[0008] S2. The tin salt was added to the acetylacetone salt grinder and mixed and ground in proportion, and nitrogen was continued to protect from light to obtain a crude acetylacetone tin chloride;
[0009] S3. Extract tin chloride with acetylacetonate several times with an organic solvent, the insoluble matter is a metal chloride salt, and the multiple extracts are combined, subjected to low-temperature rotary evaporation, and purified by column chromatography to obtain a white crystalline powder;
[0010] S4. The white powder is placed in a sublimator, heated to 100-200° C. under vacuum conditions, and sublimated to obtain tin acetylacetonate chloride.
[0011] Furthermore, the base described in S1 is an inorganic base or an organic base, and the molar ratio of acetylacetone to the base is: (0.5-1.5):1.
[0012] Furthermore, the tin salt in S2 is one of tin tetrachloride and its pentahydrate, and the ratio of the tin salt to the acetylacetonate, by mole ratio, is 1:(2-3).
[0013] Furthermore, the grinding time in S1 and S2 is not less than 2 h.
[0014] Furthermore, the vacuum degree of sublimation in S4 can be selected but not limited to 10 -5 ~10 -3 Torr.
[0015] Acetylacetonate tin chloride prepared by any of the above methods.
[0016] It was used as a tin precursor to prepare SnO 2 The nanomaterial is used as an electron transport layer material, comprising the following steps:
[0017] S1. At room temperature, a certain amount of tin chloride acetylacetonate and a first solvent are mixed to obtain a first reaction system;
[0018] S2. Mix a certain amount of organic base and the second organic solvent to form a second reaction system, add the second reaction system to the first reaction system and mix well to obtain transparent SnO 2 Precursor solution;
[0019] S3. The precursor in S2 is placed in a hydrothermal reactor and reacted at a temperature of 120-150°C for 2-24 hours to obtain SnO 2 Nanomaterial mother liquor;
[0020] S4. Add precipitant to the mother liquor in S3 and centrifuge to obtain SnO 2 Nanomaterials are then dissolved in solvent, precipitants are added, and centrifugation is performed to obtain relatively pure SnO 2 , and finally dissolved in isopropanol to prepare 2.5wt% SnO 2The nano-dispersion liquid is spin-coated on an ITO glass substrate as an electron transport layer of a formal structure; it can also be spin-coated on a perovskite layer as an electron transport layer of a trans structure.
[0021] Furthermore, the molar concentration of tin chloride acetylacetonate in S1 is 0.01-0.3 mol / L, and the first solvent is one of ethanol, n-propanol, isopropanol, and n-butanol.
[0022] Furthermore, the organic base in S2 is one or more of monoethanolamine, diethylamine, triethylamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide.
[0023] Furthermore, the precipitant in S4 is one of diethyl ether, tert-methyl ether, petroleum ether and ethyl acetate.
[0024] The beneficial effects of the present invention are as follows:
[0025] The invention is based on the reaction of acetylacetonate and tetravalent tin salt to prepare acetylacetonate tin chloride, and the acetylacetonate can be prepared from acetylacetone with low cost and alkali, the whole process has high reaction degree, short time, easy removal of impurities, high purity and can meet the subsequent synthesis needs.
[0026] The present invention adopts solid phase grinding, shortens the intermolecular reaction distance, increases the activity of the reaction, improves the reaction rate, and shortens the reaction time. The solid phase grinding reaction process of acetylacetonate and acetylacetonate tin chloride is exothermic, so the present application is carried out in a low temperature environment, which can ensure that the reaction is carried out at a high speed and safely, and can be synthesized on a large scale through equipment to increase the yield. In the process of preparing acetylacetonate tin chloride, freshly prepared acetylacetonate is selected, which has high stability. Acetylacetone is relatively sensitive to light, heat, and oxygen. The present application is carried out in a low temperature, light-proof, nitrogen-filled environment to ensure that the prepared product has high purity, simple post-processing, and the solvent is recyclable, environmentally friendly, and green and pollution-free.
[0027] The cost of acetylacetonate tin (IV) chloride synthesized by the method of the present invention is 0.5 yuan per gram, and the commercially available acetylacetonate tin (IV) chloride is analytically pure and sold at a price of 132 yuan per gram. The method of the present invention can be produced at the kilogram level, thereby realizing large-scale production, with a purity of up to 99.5%, lower cost, and can promote the development of solar photovoltaic industrialization. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 This is the infrared spectrum of tin chloride acetylacetonate.
[0029] Figure 2 This is the mass spectrum of tin chloride acetylacetonate.
[0030] Figure 3 TEM image of SnO2 nanomaterials prepared by tin chloride acetylacetonate.
[0031] Figure 4 This is the thermogravimetric analysis diagram of SnO2 nanomaterials prepared by tin chloride acetylacetonate. DETAILED DESCRIPTION
[0032] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
[0033] A method for preparing tin acetylacetonate chloride comprises the following steps:
[0034] S1. At 0-20°C, acetylacetone and a base are respectively charged into a grinder in a certain proportion for rotary grinding, the system is filled with nitrogen, protected from light, and the mixture undergoes a liquid state and a gel state until a solid acetylacetone salt powder is obtained;
[0035] S2. The tin salt was added to the acetylacetone salt grinder and mixed and ground in proportion, and nitrogen was continued to protect from light to obtain a crude acetylacetone tin chloride;
[0036] S3. Extract acetylacetonate tin chloride multiple times with an organic solvent, the insoluble matter is metal chloride, combine the multiple extracts, perform low-temperature rotary evaporation, and purify by column chromatography. The product is a white crystalline powder with a purity of 98%, which can be mass-produced at the kilogram level;
[0037] S4. The white powder is placed in a sublimator, heated to 100-200°C under vacuum conditions, and sublimated to obtain tin acetylacetonate chloride with a purity of 99.5%.
[0038] The base in S1 can be selected from inorganic bases: sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide; organic bases: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, sodium methoxide, potassium ethoxide, potassium tert-butoxide. Preferably: sodium hydroxide, potassium hydroxide, small molecular weight, low cost, strong alkalinity.
[0039] The organic solvent in S3 can be selected from: dichloromethane, chloroform, ethanol, toluene, benzene, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide and ether, etc., preferably: dichloromethane, which has high solubility, low toxicity, low price, and almost no dissolution of inorganic salts.
[0040] The present application also discloses a method for preparing SnO2 nanomaterials using tin chloride acetylacetonate as a tin precursor, and applying the method as an electron transport layer material in perovskite solar cells to achieve higher light conversion performance and longer service life.
[0041] The details are as follows:
[0042] S1. At room temperature, a certain amount of tin chloride acetylacetonate and a first solvent are mixed to obtain a first reaction system;
[0043] S2. A certain amount of an organic base and a second organic solvent are mixed to form a second reaction system, and the second reaction system is added to the first reaction system and mixed to obtain a transparent SnO2 precursor solution;
[0044] S3. The precursor in S2 is loaded into a hydrothermal reactor, and the reaction temperature is 120-150°C, and the reaction is performed for 2-24h to obtain a mother solution of SnO2 nanomaterials;
[0045] S4. Add a precipitant to the mother liquor in S3, centrifuge to obtain SnO2 nanomaterials, dissolve it with a solvent, add a precipitant, centrifuge to obtain relatively pure SnO2, and finally dissolve it in isopropanol to prepare a 2.5wt% SnO2 nanodispersion liquid, which can be spin-coated on an ITO glass substrate as a formal structure electron transport layer, or spin-coated on a perovskite layer as a trans-structure electron transport layer.
[0046] The device preparation process described in S4 is as follows:
[0047] The above-mentioned SnO2 dispersion is spin-coated on the IT0 anode layer, and then annealed at 100°C for 10 minutes to form an electron transport layer; the absorption layer is formed by spin-coating the perovskite solution on the electron transport layer as the carrier; the hole transport layer material is spin-coated on the absorption layer, and the hole transport layer is formed after drying; finally, the Au cathode electrode layer is evaporated and packaged to form a formal perovskite solar cell device.
[0048] A NiOx aqueous dispersion is spin-coated on the IT0 anode layer, and then annealed at 150°C for 30 minutes to form a hole transport layer; an absorption layer is formed by spin-coating a perovskite solution on the hole transport layer serving as a carrier; the above-mentioned SnO2 isopropanol dispersion is spin-coated on the absorption layer, and after drying, an electron transport layer is formed; finally, an Au cathode electrode layer is evaporated and packaged to form an inverted perovskite solar cell device.
[0049] Embodiment 1
[0050] 1. Put 20 mol of acetylacetone and 20 mol of sodium hydroxide into a grinder, fill it with nitrogen protective gas, and grind it. The reaction temperature is 10°C and the reaction time is 3 hours. The mixture goes through liquid and gel state until a white solid sodium acetylacetonate powder is obtained;
[0051] 2. Pour 10 mol of tin tetrachloride pentahydrate into the above grinder, fill with nitrogen protective gas, mix and grind, reaction temperature 20 ° C, reaction time 3h, to obtain a mixture of acetylacetonate tin (IV) chloride and NaCl.
[0052] 3. Extract acetylacetonate tin (IV) chloride with 15L of dichloromethane three times. The insoluble matter is sodium chloride. Combine the multiple extracts, evaporate at 30°C with a vacuum degree of -0.1Mpa, purify by column chromatography, and then evaporate at 30°C. The product is a white crystalline powder with a yield of 90%.
[0053] 4. Place the white powder in a sublimator and heat to 120°C under a vacuum of 10^-5Torr.
[0054] Sublime for 5 hours to obtain acetylacetonate tin chloride white powder with a purity of 99.5%.
[0055] Embodiment 2
[0056] 1. Put 20 mol of acetylacetone and 22 mol of potassium hydroxide into a grinder, fill it with nitrogen protective gas, and grind it. The reaction temperature is 20°C and the reaction time is 3 hours. The mixture goes through liquid and gel state until a white solid sodium acetylacetonate powder is obtained;
[0057] 2. Pour 11 mol of tin tetrachloride pentahydrate into the above grinder, fill with nitrogen protective gas, mix and grind, reaction temperature 20 ° C, reaction time 4h, to obtain a mixture of acetylacetonate tin (IV) chloride and KCl.
[0058] 3. Extract acetylacetonate tin (IV) chloride three times with 20 L of dichloromethane. The insoluble matter is potassium chloride. Combine the multiple extracts, evaporate at 30 ° C, vacuum degree of -0.1 MPa, and purify by column chromatography. The product is a white crystalline powder with a yield of 91%.
[0059] 4. The above white powder was placed in a sublimator, heated to 110°C under a vacuum degree of 10^-5 Torr, and sublimated for 6 hours to obtain acetylacetonate tin chloride white powder with a purity of 99.9%.
[0060] Embodiment 3
[0061] 1. Put 20 mol of acetylacetone and 30 mol of sodium hydroxide into a grinder, fill it with nitrogen protective gas, and grind it. The reaction temperature is 20°C and the reaction time is 3 hours. The mixture goes through liquid and gel state until a white solid sodium acetylacetonate powder is obtained;
[0062] 2. Pour 15 mol of tin tetrachloride pentahydrate into the above grinder, fill with nitrogen protective gas, mix and grind, reaction temperature 15 ° C, reaction time 6h, to obtain a mixture of acetylacetonate tin (IV) chloride and NaCl.
[0063] 3. Extract acetylacetonate tin (IV) chloride with 15L dichloromethane three times. The insoluble matter is sodium chloride. Combine the multiple extracts, evaporate at 30℃, vacuum degree is -0.1MPa, purify by column chromatography, and then purify at 30℃.
[0064] The product was a white crystalline powder after rotary evaporation, with a yield of 89%.
[0065] 4. The above white powder was placed in a sublimator, heated to 130°C under a vacuum degree of 10^-5 Torr, and sublimated for 8 hours to obtain acetylacetonate tin chloride white powder with a purity of 99.6%.
[0066] Comparative Example 1
[0067] 1. Add acetylacetone and stannous chloride in a molar ratio of 1:1 into a reactor, introduce oxygen, and react for 1 day. The solution will gradually turn white to generate acetylacetone tin chloride, but the solution is yellowish brown with a yield of 34%. After purification by column chromatography, the color is yellowish.
[0068] 2. Add acetylacetone and tin tetrachloride pentahydrate in a molar ratio of 1.2:1 into a three-necked flask, use dichloromethane as the solvent, and stir for 2 days. The liquid will gradually turn white to generate acetylacetone tin chloride, but the solution is light yellow with a yield of 50%. The color is light yellow after purification by column chromatography.
[0069] The data of tin chloride acetylacetonate in the above examples and comparative examples are shown in Table 1
[0070] The performance data of the devices made of tin chloride acetylacetonate in the above examples and comparative examples are shown in Table 2
[0071] Table 1: Comparison of products obtained in various embodiments
[0072] Time (h) Yield (%) Product color Price per gram (yuan) Embodiment 1 15 92 White 0.5 Embodiment 2 18 90 White 0.8 Embodiment 3 20 87 White 1.4 Comparative Example 1 50 34 tan 75 Comparative Example 2 40 50 yellow 25
[0073] Table 2: Comparison of device performance obtained in various embodiments
[0074]
[0075] The above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the scope of protection of the invention.
Claims
1. A method for preparing tin acetylacetonate chloride, characterized in that: The following steps are involved: S1. At 0-20°C, acetylacetone and a base are respectively charged into a grinder in a certain proportion for rotary grinding, the system is filled with nitrogen, protected from light, and the mixture undergoes a liquid state and a gel state until a solid acetylacetone salt powder is obtained; S2. The tin salt was added to the acetylacetone salt grinder and mixed and ground in proportion, and nitrogen was continued to protect from light to obtain a crude acetylacetone tin chloride; S3. Extract tin chloride with acetylacetonate several times with an organic solvent, the insoluble matter is a metal chloride salt, and the multiple extracts are combined, subjected to low-temperature rotary evaporation, and purified by column chromatography to obtain a white crystalline powder; S4. The white powder is placed in a sublimator, heated to 100-200° C. under vacuum conditions, and sublimated to obtain tin acetylacetonate chloride.
2. The method for preparing tin chloride acetylacetonate according to claim 1, wherein: The base described in S1 is an inorganic base or an organic base, and the molar ratio of acetylacetone to the base is: (0.5-1.5):
1.
3. The method for preparing tin chloride acetylacetonate according to claim 1, characterized in that: The tin salt in S2 is one of tin tetrachloride and its pentahydrate, and the ratio of the tin salt to the acetylacetonate, by mass, is 1:(2-3).
4. The method for preparing tin chloride acetylacetonate according to claim 1, characterized in that: The grinding time in S1 and S2 is not less than 2h.
5. The method for preparing tin chloride acetylacetonate according to claim 1, characterized in that: The vacuum degree of sublimation in S4 can be selected but is not limited to 10 -5 ~10 -3 Torr.
6. Acetylacetonate tin chloride obtained by the method according to any one of claims 1 to 5.
7. A use of tin chloride acetylacetonate as claimed in claim 6, characterized in that: The SnO2 nanomaterial is prepared as a tin precursor for use as an electron transport layer material, comprising the following steps: S1. At room temperature, a certain amount of tin chloride acetylacetonate and a first solvent are mixed to obtain a first reaction system; S2. A certain amount of an organic base and a second organic solvent are mixed to form a second reaction system, and the second reaction system is added to the first reaction system and mixed to obtain a transparent SnO2 precursor solution; S3. The precursor in S2 is loaded into a hydrothermal reactor, and the reaction temperature is 120-150°C, and the reaction is performed for 2-24h to obtain a mother solution of SnO2 nanomaterials; S4. Add a precipitant to the mother liquor in S3, centrifuge to obtain SnO2 nanomaterials, dissolve it with a solvent, add a precipitant, centrifuge to obtain relatively pure SnO2, and finally dissolve it in isopropanol to prepare a 2.5wt% SnO2 nanodispersion liquid, and spin-coat it on an ITO glass substrate as an electron transport layer with a formal structure; it can also be spin-coated on a perovskite layer as an electron transport layer with a trans structure.
8. The use of tin chloride acetylacetonate according to claim 7, characterized in that: The molar concentration of tin chloride acetylacetonate in S1 is 0.01-0.3 mol / L, and the first solvent is one of ethanol, n-propanol, isopropanol, and n-butanol.
9. The use of tin chloride acetylacetonate according to claim 7, characterized in that: The organic base in S2 is one or more of monoethanolamine, diethylamine, triethylamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide.
10. The use of tin chloride acetylacetonate according to claim 7, characterized in that: The precipitant in S4 is one of diethyl ether, tertiary methyl ether, petroleum ether and ethyl acetate.