Modified light conversion agent, light conversion adhesive film composition, light conversion adhesive film and photovoltaic module
By modifying the V-shaped and star-shaped structures of the light-converting agent, the problems of low stability and efficiency of triazole-based light-converting agents are solved, achieving high-efficiency light conversion and reducing migration, thus extending the service life of photovoltaic modules.
Patent Information
- Application Number
- CN202411513661.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-28
- Publication Date
- 2026-04-28
AI Technical Summary
Existing triazole-based light conversion agents have poor stability and low light conversion efficiency, which cannot meet the long-term use requirements of photovoltaic modules.
By using modified light-converting agents and designing V-shaped and star-shaped structures, the spatial effect is increased, reducing the possibility of luminescence quenching caused by molecular stacking. Furthermore, a dendritic structure design is achieved through more substitution sites, which improves light conversion efficiency and reduces migration rate.
It improves the light conversion efficiency and stability of the light conversion film, reduces the migration rate of the modified light conversion agent, and extends the service life of photovoltaic modules.
Smart Images
Figure CN121930180A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of optoelectronic technology, and more specifically, to a modified light-converting agent, a light-converting film composition, a light-converting film, and a photovoltaic module. Background Technology
[0002] Replacing traditional fossil fuels, which are limited in resources and highly polluting, with inexhaustible and clean solar energy is an inevitable path for human development. This necessity is concretely reflected in the rapid development of the photovoltaic industry worldwide in recent years. With the continuous upgrading of solar cell technology, N-type cells, due to their higher theoretical power and stronger application potential, are gradually replacing P-type cells as the mainstream in the market. During this process, the degradation problem of solar cells under high-intensity ultraviolet radiation has become increasingly prominent.
[0003] Currently, while encapsulating solar cells with UV-blocking films can effectively prevent UV degradation, this comes at the cost of increased module power and longer lifespan, making UV-blocking films not the optimal choice. Light-conversion films, on the other hand, can effectively solve this problem. Whether in TOPCon or HJT cells, light-conversion films not only effectively absorb UV light from sunlight to protect the module, but also convert it into visible light, which is more efficient for module utilization, thus ensuring or even improving module power. Therefore, developing high-performance light-conversion films is crucial for the long-term development of N-type cell technology.
[0004] The light conversion performance of a light-converting film comes from the light-converting agent within the film. The quality of the light-converting agent largely determines the performance of the film. Based on material type, light-converting agents can be categorized into small-molecule organic light-converting agents, quantum dot light-converting agents, and rare-earth light-converting agents (organic-inorganic composites), etc. However, considering factors such as cost, dispersibility, light conversion performance, and visible light transmittance, small-molecule organic light-converting agents show the greatest application potential. However, due to the inherent characteristics of organic materials, organic light-converting agents exhibit poor photostability. Under strong ultraviolet light and high temperatures, their light conversion ability easily weakens rapidly due to changes in the organic molecular structure. This is often an unacceptable defect for film products.
[0005] In recent years, researchers have developed a series of small-molecule organic light-converting agents based on triazole structures, and these agents have exhibited good photostability. This research indicates that the shortcomings of small-molecule organic light-converting agents in terms of photostability are not insurmountable. However, in general, there are currently few light-converting agents that have withstood market scrutiny, and existing agents still have significant room for improvement in terms of conversion efficiency, absorption, emission, and mobility. Summary of the Invention
[0006] One of the main objectives of this invention is to provide a modified light-converting agent, a light-converting film composition, a light-converting film, and a photovoltaic module, in order to solve the problems of poor stability and low light conversion efficiency of the triazole-based light-converting agents in the prior art.
[0007] To achieve the above objectives, according to one aspect of the present invention, a modified light-converting agent is provided, the general structural formula of which is shown in Formula I:
[0008]
[0009] Where n is 2 or 3; R is Multiple Rs exist in a meta-positional relationship on their respective benzene rings, with "*" indicating the connection position of R on its benzene ring; R1 is selected from H, Substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 20 Any one of the alkyl groups; or, C 10 ~C 20 Fused ring aryl group; R2 and R3 are each independently selected from H, diphenylamino, substituted or unsubstituted C1-C2 groups. 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 20 Any one of the alkyl groups.
[0010] Furthermore, R2 and R3 are each independently selected from diphenylamino, substituted, or unsubstituted C1-C1 groups. 10 Alkyl, substituted or unsubstituted C1-C 10 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 10Alkyl group; preferably R2 and R3 are each independently selected from diphenylamino, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, at least one methylene group of any one of the following groups is independently substituted with -COO- or -O-, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octenyl, nonenyl, decenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl.
[0011] Furthermore, R2 and R3 are each independently selected from diphenylamine,
[0012]
[0013]
[0014] Any one or more of the following; further, preferably R2 and R3 are each independently selected from diphenylamine,
[0015] Any one or more of the following.
[0016] Furthermore, the aforementioned R1 is selected from H, C1~C 10 The hydrocarbon group, at least one methylene group is replaced by -COO-, C3~C 10 Hydrocarbon group, substituted or unsubstituted C2-C 10 alkenyl groups, C1-C1 groups with carboxyl groups at the end. 10 R1 is selected from any one or more alkyl groups, preferably R1 is selected from
[0017]
[0018] Any one or more of them; further, preferably R1 is selected from Any one or more of the following; where "*" represents the linking site of R1 on its benzene ring.
[0019] Furthermore, the modified light-converting agent is a combination of the modified light-converting agent when n is 2 and the modified light-converting agent when n is 3, wherein the modified light-converting agent when n is 2 accounts for 50-100% of the total mass of the modified light-converting agent; and / or, when there are substituents in R1, R2 and R3, each substituent is independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, nitro, hydroxy and carboxyl groups.
[0020] Furthermore, the modified light-converting agent mentioned above is selected from...
[0021]
[0022]
[0023]
[0024] Any one or more of the following.
[0025] According to another aspect of this application, a light-converting film composition is provided, which, by weight percentage, comprises 80-99.98% of a matrix resin, 0.01-10% of a light-converting agent, and 0.01-10% of an additive, wherein the light-converting agent is the modified light-converting agent described above.
[0026] Furthermore, the matrix resin is selected from any one or more of EVA, PVA, PMMA, POE, and silicone; and / or, the additives include crosslinking agents and / or co-crosslinking agents; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the co-crosslinking agent is 0.005 to 5%.
[0027] According to another aspect of this application, a light-converting adhesive film is provided, comprising the above-described light-converting adhesive film composition.
[0028] According to another aspect of this application, a photovoltaic module is provided, including a light transfer film, which is the light transfer film described above.
[0029] By applying the technical solution of this invention, the modified light-converting agent of this application, through the design of V-shaped and star-shaped structures, increases the spatial effect of the modified light-converting agent, reduces the possibility of luminescence quenching caused by the accumulation of modified light-converting agent molecules, thereby improving the light conversion efficiency of the light-converting film; on the other hand, the more substitution sites make the modified light-converting agent have an overall dendritic structure design, which not only provides more possibilities for the modification of the modified light-converting agent, but also more effectively anchors the modified light-converting agent to the film by modifying the periphery with groups that can undergo cross-linking reaction with the light-converting film, thereby reducing the migration rate of the modified light-converting agent. Detailed Implementation
[0030] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.
[0031] As analyzed in the background section of this application, the existing triazole-based light-converting agents have problems such as poor stability and low light conversion efficiency. To solve this technical problem, this application provides a modified light-converting agent, a light-converting film composition, a light-converting film, and a photovoltaic module.
[0032] In a typical embodiment of this application, a modified light-converting agent is provided, the general structural formula of which is shown in Formula I:
[0033]
[0034] Where n is 2 or 3; R is Multiple Rs exist in a meta-positional relationship on their respective benzene rings, with "*" indicating the connection position of R on its benzene ring; R1 is selected from H, Substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 20 Any one of the alkyl groups;
[0035] or, C 10 ~C 20 Fused ring aryl group; R2 and R3 are each independently selected from H, diphenylamino, substituted or unsubstituted C1-C2 groups. 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 20 any one of the alkyl groups
[0036] The modified light-converting agent of this application, through the design of V-shaped and star-shaped structures, increases the spatial effect of the modified light-converting agent, reduces the possibility of luminescence quenching caused by the accumulation of modified light-converting agent molecules, thereby improving the light conversion efficiency of the light-converting film; on the other hand, the more substitution sites make the modified light-converting agent have an overall dendritic structure design, which not only provides more possibilities for the modification of the modified light-converting agent, but also more effectively anchors the modified light-converting agent to the film by modifying the periphery with groups that can undergo cross-linking reaction with the light-converting film, thereby reducing the migration rate of the modified light-converting agent.
[0037] In one embodiment of this application, R2 and R3 are each independently selected from diphenylamine, substituted or unsubstituted C1-C1 groups. 10 Alkyl, substituted or unsubstituted C1-C 10 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl groups and C2-C3 groups with carboxyl groups at the end. 10 Alkyl group; preferably R2 and R3 are each independently selected from diphenylamino, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, at least one methylene group of any one of the following groups is independently substituted with -COO- or -O-, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octenyl, nonenyl, decenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl.
[0038] The preferred substituents further enrich the selectivity of R2 and R3, thereby contributing to improving the overall performance of the modified light-converting agent.
[0039] In one embodiment of this application, R2 and R3 are each independently selected from diphenylamine groups.
[0040]
[0041] Any one or more of the following; further, preferably R2 and R3 are each independently selected from R2 selected from diphenylamine,
[0042] Any one or more of the following.
[0043] In one embodiment of this application, when there are substituents in R1, R2 and R3, each substituent is independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, nitro, hydroxy and carboxyl groups.
[0044] The preferred types of substituents help to further increase the abundance of R1, R2 and R3 substituents in the peripheral modification, thereby obtaining a modified light-converting agent with higher overall light conversion efficiency under the synergistic effect of each group.
[0045] In one embodiment of this application, R1 is selected from H, C1~C 10 The hydrocarbon group, at least one methylene group is replaced by -COO-, C3~C10 Hydrocarbon group, substituted or unsubstituted C2-C 10 alkenyl groups, C1-C1 groups with carboxyl groups at the end. 10 R1 is selected from any one or more alkyl groups, preferably R1 is selected from
[0046] Any one or more of them; further, preferably R1 is selected from Any one or more of the following; where "*" represents the linking site of R1 on its benzene ring.
[0047] The preferred R1 improves the spatial effect of the V-shaped and star-shaped modified light-converting agents, which is more conducive to reducing the possibility of light quenching caused by the accumulation of modified light-converting agent molecules, thereby improving the light conversion efficiency of the light-converting film and reducing the migration rate of the modified light-converting agent.
[0048] In one embodiment of this application, the modified light-converting agent is a combination of the modified light-converting agent when n is 2 and the modified light-converting agent when n is 3, wherein the modified light-converting agent when n is 2 accounts for 50-100% of the total mass of the modified light-converting agent; and / or, when there are substituents in R1, R2 and R3, each substituent is independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, nitro, hydroxy and carboxyl groups.
[0049] The modified light-converting agent with n=2 has a better light conversion efficiency, while the modified light-converting agent with n=3 has a lower migration rate. Therefore, the preferred mass ratio above helps the modified light-converting agent to achieve both high light conversion efficiency and low migration rate.
[0050] To improve the photostability of the modified light-converting agent, reduce its migration rate, and maintain its excellent light conversion efficiency, the modified light-converting agent is preferably selected from...
[0051]
[0052]
[0053]
[0054]
[0055] Any one or more of the following.
[0056] In another typical embodiment of this application, a light-converting film composition is provided, which, by weight percentage, comprises 80-99.98% of a matrix resin, 0.01-10% of a light-converting agent, and 0.01-10% of an additive, wherein the light-converting agent is the aforementioned modified light-converting agent.
[0057] The modified light-converting agent of this application, through the design of V-shaped and star-shaped structures, increases the spatial effect of the modified light-converting agent, reducing the possibility of luminescence quenching caused by the accumulation of modified light-converting agent molecules, thereby improving the light conversion efficiency of the light-converting film. On the other hand, the more substitution sites make the modified light-converting agent have an overall dendritic structure design, which not only provides more possibilities for the modification of the modified light-converting agent, but also more effectively anchors the modified light-converting agent to the film by modifying the periphery with groups that can undergo cross-linking reactions with the light-converting film, thereby reducing the migration rate of the modified light-converting agent. Furthermore, the light-converting film composition including the modified light-converting agent also has excellent light conversion efficiency and migration rate.
[0058] In one embodiment of this application, the matrix resin is selected from any one or more of EVA, PVA, PMMA, POE, and silicone; and / or, the additives include crosslinking agents and / or co-crosslinking agents; preferably, the weight percentage of the crosslinking agent is 0.005 to 5%, and / or the weight percentage of the co-crosslinking agent is 0.005 to 5%.
[0059] The preferred matrix resin described above helps to better cooperate with components such as the light-converting agent to obtain a high-performance light-converting film. The matrix resin described above is inexpensive, which helps to reduce costs. Of course, those skilled in the art can also use other matrix resins, which will not be elaborated here.
[0060] Crosslinking agents are molecules with multiple olefinic unsaturated groups that can promote polymer crosslinking and achieve a higher degree of crosslinking. The crosslinking agent in the above composition can be selected from those commonly used in the art, preferably selected from any one or more of the following: tert-butyl peroxycarbonate, 2,5-dimethyl-2,5-(bis-tert-butylperoxy)hexane, tert-butyl peroxycarbonate-2-ethylhexyl ester, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-pentylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-pentylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-pentyl peroxycarbonate, 2,5-dimethyl-2,5-dimethyl-2,5-dimethyl-2,5-bis(benzoylperoxy)-hexane, tert-pentyl peroxycarbonate, and tert-butyl peroxy3,3,5-trimethylhexanoate. Preferred crosslinking agents are selected from triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propionylated trimethylolpropane triacrylate, ethoxylated glycerol triacrylate, propionylated glycerol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, and bis(trimethylolpropane tetraacrylate). Acrylates, bis(trimethylolpropane)tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, 2,4,6-tris(2-propenyloxy)-1,3,5-triazine, tricyclodecanedimethylethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate are any one or more of these.
[0061] In another typical embodiment of this application, a light-converting adhesive film is provided, the film composition comprising the above-described light-converting adhesive film composition.
[0062] In some preferred embodiments of this application, the aforementioned light-converting film composition is mixed evenly and then prepared by a preparation process such as melt extrusion molding at 80-120°C to obtain a light-converting film. The resulting light-converting film has both excellent stability and high luminous efficiency, and can play a long-term and effective role, thereby improving the service life of photovoltaic devices.
[0063] In another typical embodiment of this application, a photovoltaic module is provided, including a light transfer film, which is the light transfer film described above.
[0064] Photovoltaic modules using the light conversion films described in this application have excellent light conversion efficiency. Of course, there are many other options available depending on different needs and application scenarios. The light conversion films described in this application are not limited to photovoltaic devices, agricultural films, architectural glass, or other fields.
[0065] Typically, a photovoltaic module includes a crystalline silicon solar cell, a front glass panel, a rear glass panel or a polymer backsheet, and a light transfer film between the front glass panel and the solar cell. The light transfer film between the front glass panel and the solar cell is the light transfer film described in this application. The light transfer film between the rear glass panel or the polymer backsheet and the solar cell can be the light transfer film described in this application or any other conventional encapsulation film in the prior art.
[0066] The beneficial effects of this application will be further illustrated below with reference to the embodiments.
[0067] Example 1
[0068] The light-converting film composition comprises, by weight, 98.8 parts of ethylene-vinyl acetate, 0.2 parts of modified light-converting agent 1, 0.5 parts of crosslinking agent tert-butyl peroxycarbonate, and 0.5 parts of co-crosslinking agent trimethylolpropane tetraacrylate. The synthesis route of modified light-converting agent 1 is shown below:
[0069]
[0070] After the light-converting adhesive film composition is mixed evenly, it is melt-extruded at 100°C to form a film, thus obtaining the light-converting adhesive film.
[0071] 1. M1 Synthesis
[0072] A mixture of benzotriazole (20 g, 168 mmol), isobutane (27.4 g, 201.6 mmol), sodium hydroxide (8 g, 200 mmol), and DMSO (90 mL) was stirred under nitrogen and reacted at room temperature for 24 h. The reaction mixture was poured into ice water and extracted with dichloromethane. The resulting organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a crude product as a clear, oily droplet. The product was purified by column chromatography using a petroleum ether / dichloromethane mixture as eluent, ultimately yielding 14.4 g of a pale yellow, oily pure product in 49% yield.
[0073] 2. M2 Synthesis
[0074] M1 (10 g, 86.5 mmol) was dissolved in 100 mL of glacial acetic acid and heated to 100 °C. Liquid bromine (41.5 g, 260 mmol) was slowly added dropwise to the reaction system with stirring, and the mixture was refluxed and stirred at 135 °C for 24 h. The reaction was quenched with a saturated sodium bisulfite aqueous solution, washed with water, extracted, and dried under vacuum. A pale yellow oily crude product was obtained. The product was purified by column chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, ultimately yielding 25.1 g of a pale yellow solid powder, with a yield of 75%.
[0075] 3. M3 Synthesis
[0076] M2 (20 g, 51.7 mmol), 4-tert-butylphenylboronic acid (9.2 g, 51.7 mmol), potassium carbonate (16.6 g, 120 mmol), and tetrakis(triphenylphosphine)palladium (1 g, 0.87 mmol) were mixed in a double-necked flask and purged with nitrogen. 90 mL of toluene and 60 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 18.48 g of off-white solid product, with a yield of 81%.
[0077] 4. Synthesis of Light Conversion Agent 1
[0078] M3 (15 g, 38.8 mmol), 1,3-phenylenediboric acid (3.1 g, 18.5 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a double-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 9.6 g of a white solid product, with a yield of 75%.
[0079] Example 2
[0080] The difference from Example 1 is that the light-converting agent is modified light-converting agent 2, and its synthesis route is shown below:
[0081]
[0082] 1. M1 Synthesis
[0083] A mixture of benzotriazole (20 g, 168 mmol), bromooctane (38.7 g, 201.6 mmol), sodium hydroxide (8 g, 200 mmol), and DMSO (100 mL) was stirred under nitrogen and reacted at room temperature for 24 h. The reaction mixture was poured into ice water and extracted with dichloromethane. The resulting organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a crude product as a transparent oil droplet. The product was purified by column chromatography using a petroleum ether / dichloromethane mixture as eluent, ultimately yielding 21 g of a pale yellow oily pure product in 54% yield.
[0084] 2. M2 Synthesis
[0085] M1 (20 g, 86.5 mmol) was dissolved in 100 mL of glacial acetic acid and heated to 100 °C. Liquid bromine (41.5 g, 260 mmol) was slowly added dropwise to the reaction system with stirring, and the mixture was refluxed and stirred at 135 °C for 24 h. The reaction was quenched with a saturated sodium bisulfite aqueous solution, washed with water, extracted, and dried under vacuum. A pale yellow oily crude product was obtained. The product was purified by column chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, ultimately yielding 24.6 g of a pale yellow solid powder, with a yield of 73%.
[0086] 3. M3 Synthesis
[0087] M2 (20 g, 51.4 mmol), 4-tert-butylphenylboronic acid (9.1 g, 51.4 mmol), potassium carbonate (16.6 g, 120 mmol), and tetrakis(triphenylphosphine)palladium (1 g, 0.87 mmol) were mixed in a double-necked flask and purged with nitrogen. 90 mL of toluene and 60 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 17.7 g of off-white solid product, with a yield of 78%.
[0088] 4. Synthesis of light-converting agent 2
[0089] M3 (15 g, 34 mmol), 1,3-phenylenediboric acid (2.7 g, 16.2 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a two-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 9.1 g of a white solid product, with a yield of 70%.
[0090] Example 3
[0091] The difference from Example 1 is that the light-converting agent is modified light-converting agent 3, and its synthesis route is shown below:
[0092]
[0093] 1. M1 Synthesis
[0094] A mixture of benzotriazole (40 g, 336 mmol), 4-bromobutyric acid (67.3 g, 403.2 mmol), sodium hydroxide (16 g, 400 mmol), and DMSO (150 mL) was stirred under nitrogen and reacted at room temperature for 24 h. The reaction mixture was poured into ice water and extracted with dichloromethane. The resulting organic phase was dried over anhydrous magnesium sulfate and then distilled under reduced pressure to obtain a crude product as a transparent oily droplet. The product was purified by column chromatography using a petroleum ether / dichloromethane mixture as eluent, ultimately yielding 35.2 g of a creamy white pure product in 51% yield.
[0095] 2. M2 Synthesis
[0096] M1 (20 g, 97.5 mmol) was dissolved in 100 mL of glacial acetic acid and heated to 100 °C. Liquid bromine (62.3 g, 389.8 mmol) was slowly added dropwise to the reaction system with stirring, and the mixture was refluxed and stirred at 135 °C for 24 h. The reaction was quenched with a saturated sodium bisulfite aqueous solution, washed with water, extracted, and dried under vacuum. A pale yellow oily crude product was obtained. The product was purified by column chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, ultimately yielding 26.9 g of a pale yellow solid powder, with a yield of 76%.
[0097] 3. M3 Synthesis
[0098] M2 (20 g, 55 mmol), 4-tert-butylphenylboronic acid (9.8 g, 55 mmol), potassium carbonate (16.6 g, 120 mmol), and tetrakis(triphenylphosphine)palladium (1 g, 0.87 mmol) were mixed in a double-necked flask and purged with nitrogen. 90 mL of toluene and 60 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 17.9 g of off-white solid product, with a yield of 78%.
[0099] 4. M4 Synthesis
[0100] M3 (15 g, 36 mmol), 1,3-phenylenediboric acid (2.8 g, 17.1 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a two-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 8.7 g of a white solid product, with a yield of 68%.
[0101] 5. Synthesis of light-converting agent 3
[0102] M4 (8 g, 10.7 mmol) and NaOH (0.6 g, 15 mmol) were dissolved in 30 mL of tetrahydrofuran and stirred at room temperature for 2 hours. Allyl bromodiphenyl ether (1.6 g, 13 mmol) was diluted in tetrahydrofuran and slowly added dropwise to the reaction system, with stirring continued for 2 hours. The reaction was stopped, and the organic phase was separated by extraction through a simple aqueous system. The organic phase was concentrated and recrystallized to obtain 8.4 g of a white crystalline powder, with a yield of 95%.
[0103] Example 4
[0104] The difference from Example 1 is that the light-converting agent is modified light-converting agent 4, and its synthesis route is shown below:
[0105]
[0106] 1. The synthesis of intermediates M1, M2, and M3 is the same as in Example 2.
[0107] 2. Synthesis of light-converting agent 4
[0108] M3 (15 g, 34 mmol), benzene-1,3,5-trimethyltriboronic acid (2.3 g, 11 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a two-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 9.2 g of a white solid product, with a yield of 72%.
[0109] Example 5
[0110] The difference from Example 1 is that the light-converting agent is modified light-converting agent 5, and its synthesis route is shown below:
[0111]
[0112] 1. The synthesis of intermediates M1, M2, and M3 is the same as in Example 1.
[0113] 2. Synthesis of light-converting agent 5
[0114] M3 (15 g, 38.8 mmol), benzene-1,3,5-trimethyltriboronic acid (2.5 g, 12 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a two-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated, and mixed. The mixture was purified by column chromatography using ethyl acetate / petroleum ether as eluent, yielding 8.6 g of a white solid product (72% yield).
[0115] Example 6
[0116] The difference from Example 1 is that the light-converting agent is modified light-converting agent 6, and its synthesis route is shown below:
[0117]
[0118] 1. The synthesis of intermediates M1 and M2 is the same as in Example 3.
[0119] 2. Synthesis of M3
[0120] M2 (20 g, 55 mmol), 4-4-(carboxymethyl)phenylboronic acid (9.9 g, 55 mmol), potassium carbonate (16.6 g, 120 mmol), and tetrakis(triphenylphosphine)palladium (1 g, 0.87 mmol) were mixed in a double-necked flask and purged with nitrogen. 90 mL of toluene and 60 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 16.1 g of off-white solid product, with a yield of 70%.
[0121] 3. Synthesis of Light Conversion Agent 6
[0122] M3 (15 g, 35.9 mmol), benzene-1,3,5-trimethyltriboronic acid (2.4 g, 11.6 mmol), potassium carbonate (11.1 g, 80 mmol), and tetraphenylphosphine palladium (0.75 g, 0.65 mmol) were mixed in a two-necked flask and purged with nitrogen. 60 mL of toluene and 40 mL of deionized water were added to the reaction mixture. The mixture was stirred and refluxed for 24 h. The reaction was quenched in ice water, washed with water, and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and mixed. Column chromatography was used for separation and purification, with ethyl acetate / petroleum ether as the eluent, to obtain 8.2 g of a white solid product, with a yield of 65%.
[0123] Example 7
[0124] The difference from Example 1 is that, by weight, the light-converting film composition includes 99.95 parts by weight of ethylene-vinyl acetate, 0.01 parts by weight of modified light-converting agent 1, 0.02 parts by weight of crosslinking agent tert-butyl peroxycarbonate isopropyl ester, and 0.02 parts by weight of co-crosslinking agent trimethylolpropane tetraacrylate, ultimately yielding a light-converting film.
[0125] Example 8
[0126] The difference from Example 1 is that, by weight, the light-converting film composition includes 80 parts by weight of ethylene-vinyl acetate, 10 parts by weight of modified light-converting agent 1, 5 parts by weight of crosslinking agent tert-butyl peroxycarbonate isopropyl ester, and 5 parts by weight of co-crosslinking agent trimethylolpropane tetraacrylate, ultimately yielding a light-converting film.
[0127] Example 9
[0128] The difference from Example 1 is that, by weight, the matrix resin is ethylene-1 octene, and the final product is a light-converting film.
[0129] Example 10
[0130] The difference from Example 1 is that the modified light-converting agent includes the modified light-converting agents of Example 1 and Example 5. The modified light-converting agent of Example 1 accounts for 50% of the total mass of the modified light-converting agent, and the final result is a light-converting film.
[0131] Example 11
[0132] The difference from Example 10 is that the modified light-converting agent includes the modified light-converting agents of Example 1 and Example 5. The modified light-converting agent of Example 5 accounts for 70% of the total mass of the modified light-converting agent, and the final light-converting film is obtained.
[0133] Comparative Example 1
[0134] The difference from Example 1 is that the light-converting agent is a benzotriazole compound, with the following structural formula:
[0135]
[0136] Finally, a light-converting film is obtained.
[0137] Comparative Example 2
[0138] The coated light-converting powder consists of a benzotriazole derivative organic light-converting agent and a silica ALD coating layer. The light-converting agent has a particle size D50 of 10 nanometers and a specific surface area of 2000 m². 2 / g, silica coating thickness 1 nm, organic light-converting agent molecular formula as shown in formula B-1:
[0139]
[0140] The above-mentioned light-converting powder was used in EVA photovoltaic film. In addition to 100 parts EVA resin and 0.05 parts light-converting powder, the film also contained 0.5 parts peroxide crosslinking agent, 0.1 parts co-crosslinking agent, and 0.5 parts silane coupling agent. After lamination and crosslinking, the film exhibited a light transmittance of 91% in the 400-700 nm range. When applied to HJT modules, the initial power generation was increased by 1% compared to the same formulation film without light-converting powder. The power generation of this module decreased by 1.3% after damp heat aging and by 1.8% after UV aging.
[0141] Comparative Example 3
[0142] The difference from Example 1 is that, by weight, the light-converting film composition includes 70 parts by weight of matrix resin, 15 parts by weight of modified light-converting agent 1, 0.5 parts by weight of crosslinking agent tert-butyl peroxycarbonate isopropyl ester, and 0.5 parts by weight of co-crosslinking agent trimethylolpropane tetraacrylate, ultimately yielding a light-converting film.
[0143] Test methods
[0144] Light conversion efficiency: Absolute quantum efficiency was measured using an integrating sphere on a Horiba FL-3 spectrometer at room temperature.
[0145] Aging test: The upper and lower surfaces of the adhesive film obtained in the above examples and comparative examples were laminated with glass layers to obtain a pre-pressed component, and a UV300 aging test was conducted in a multi-times UV aging chamber (power 142W, temperature 70℃).
[0146] Yellowing index: The yellowing index (ΔYI) of the pre-compression components before and after the aging test was determined according to the national standard GB 2409 "Test Method for Yellowing Index of Plastics". The test results are listed in Table 1.
[0147] Table 1
[0148]
[0149]
[0150] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:
[0151] The modified light-converting agent of this application, through the design of a V-shaped or star-shaped structure, increases the spatial effect of the modified light-converting agent, reducing the possibility of luminescence quenching caused by the accumulation of modified light-converting agent molecules, thereby improving the light conversion efficiency of the light-converting film. On the other hand, the more substitution sites make the modified light-converting agent have an overall dendritic structure design, which not only provides more possibilities for the modification of the modified light-converting agent, but also more effectively anchors the modified light-converting agent to the film by modifying the periphery with groups that can undergo cross-linking reactions with the light-converting film, thereby reducing the migration rate of the modified light-converting agent.
[0152] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A modified light-converting agent, characterized in that, The general structural formula of the modified light-converting agent is shown in Formula I: Where n is 2 or 3; R is The multiple Rs exist in a meta-positional relationship on their respective benzene rings, and "*" represents the connection position of the R on its respective benzene ring; R1 is selected from H, Substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups, C2-C6 groups with carboxyl groups at the end. 20 Any one of the alkyl groups; Or, the aforementioned C 10 ~C 20 Fused-ring aryl groups; R2 and R3 are each independently selected from H, diphenylamine, substituted or unsubstituted C1-C2 groups. 20 Alkyl, substituted or unsubstituted C1-C 20 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 20 Alkyl, substituted or unsubstituted C2-C 20 alkenyl groups, C2-C6 groups with carboxyl groups at the end. 20 Any one of the alkyl groups.
2. The modified light-converting agent according to claim 1, characterized in that, R2 and R3 are each independently selected from diphenylamine, substituted or unsubstituted C1-C1 groups. 10 Alkyl, substituted or unsubstituted C1-C 10 The alkoxy group, at least one methylene group is substituted by -COO- or -O- at C3 to C4. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl groups, C2-C6 groups with carboxyl groups at the end. 10 Alkyl groups; Preferably, R2 and R3 are each independently selected from diphenylamino, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, where at least one methylene group of any one of these groups is independently substituted with -COO- or -O-, or methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octenyl, nonenyl, decenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl.
3. The modified light-converting agent according to claim 1 or 2, characterized in that, R2 and R3 are each independently selected from diphenylamine groups. Any one or more of the following; further, preferably, R2 and R3 are each independently selected from diphenylamine. Any one or more of the following.
4. The modified light-converting agent according to any one of claims 1 to 3, characterized in that, R1 is selected from H, C1~C 10 The hydrocarbon group, at least one methylene group is replaced by -COO-, C3~C 10 Hydrocarbon group, substituted or unsubstituted C2-C 10 alkenyl groups, C1-C1 groups with carboxyl groups at the end. 10 R1 is selected from any one or more alkyl groups, preferably R1 is selected from Any one or more of the following; Furthermore, it is preferable that R1 is selected from... Any one or more of the following; Wherein, "*" represents the connection site of R1 on its benzene ring.
5. The modified light-converting agent according to any one of claims 1 to 4, characterized in that, The modified light-converting agent is a combination of the modified light-converting agent when n is 2 and the modified light-converting agent when n is 3, wherein the modified light-converting agent when n is 2 accounts for 50-100% of the total mass of the modified light-converting agent; And / or, when R1, R2 and R3 contain substituents, each substituent is independently selected from any one or more of methyl, ethyl, propyl, butyl, trifluoromethyl, nitro, hydroxy and carboxyl groups.
6. The modified light-converting agent according to any one of claims 1 to 5, characterized in that, The modified light-converting agent is selected from... Any one or more of the following.
7. A light-converting adhesive film composition, characterized in that, The light-converting film composition comprises, by weight percentage: 80–99.98% of the matrix resin; 0.01–10% of a light-converting agent; and 0.01% to 10% of adjuvants, The light-converting agent is the modified light-converting agent according to any one of claims 1 to 6.
8. The light-converting adhesive film composition according to claim 7, characterized in that, The matrix resin is selected from any one or more of EVA, PVA, PMMA, POE, and organosilicon; And / or, the additives include crosslinking agents and / or co-crosslinking agents; preferably, the weight percentage of the crosslinking agent is 0.005-5%, and / or the weight percentage of the co-crosslinking agent is 0.005-5%.
9. A light-converting adhesive film, characterized in that, The light-converting film comprises the light-converting film composition of claim 7 or 8.
10. A photovoltaic module, comprising a light-converting adhesive film, characterized in that, The light-converting adhesive film is the light-converting adhesive film according to claim 9.