High-dispersion red light conversion adhesive film, preparation method thereof and photovoltaic module

Abstract

The invention relates to the technical field of photovoltaic materials, in particular to a high-dispersion red light conversion adhesive film, a preparation method thereof and a photovoltaic module. The high-dispersion red light conversion adhesive film comprises an adhesive film main body and red light conversion powder dispersed in the adhesive film main body, the mass fraction of the red light conversion powder in the red light conversion adhesive film is 0.005%-1%; the red light conversion powder is mainly prepared from europium chloride, 2-thiophenoyl trifluoroacetone and a compound as shown in the following formula I in a molar ratio of 1: (2.5-3.5): (0.5-1.5); according to the invention, a proper siloxane structure is introduced into the red light conversion powder, so that the dispersibility of the red light conversion powder in the adhesive film is ensured, the light transmittance at the wave band of 280-380nm is low, and more ultraviolet rays can be absorbed and converted into red light; and meanwhile, the light transmittance of the wave band of 380-1100 nm is high, the long wave band is better utilized, and the power of the module is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photovoltaic materials, and in particular to a highly dispersed red light-transfer adhesive film, a preparation method thereof, and a photovoltaic module. Background Art

[0002] Light-converting adhesive film is an encapsulation material made by dispersing a light-converting functional material in a polymer matrix. Red light-converting adhesive film, by incorporating a specific red light-converting powder, selectively absorbs ultraviolet light in the solar spectrum and efficiently converts it into red light. This conversion significantly improves the light energy utilization of heterojunction (HJT) solar panels, thereby increasing the photoelectric conversion efficiency.

[0003] Currently, red light-conversion powders primarily include rare earth organic complexes and rare earth inorganic compounds. However, these two types of red light-conversion powders present the following challenges in film applications: Poor dispersion uniformity reduces film transmittance, impacting the module's absorption of long-wavelength light; Aggregation of the red light-conversion powder induces fluorescence quenching, reducing fluorescence quantum efficiency and weakening light conversion efficiency. This significantly impacts module power gain, hindering the practical application of red light-conversion films.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] One object of the present invention is to provide a highly dispersed red light-converting adhesive film to solve the technical problems of poor dispersion uniformity of red light-converting powder and low light-conversion efficiency in the red light-converting adhesive film in the prior art.

[0006] Another object of the present invention is to provide a method for preparing a highly dispersed red light transfer adhesive film.

[0007] Another object of the present invention is to provide a photovoltaic module comprising the above-mentioned high-dispersion red light-transfer adhesive film.

[0008] In order to achieve the above-mentioned object of the present invention, the first aspect of the present invention provides a highly dispersed red light-converting adhesive film, comprising an adhesive film body and red light-converting powder dispersed in the adhesive film body; in the red light-converting adhesive film, the mass fraction of the red light-converting powder is 0.005% to 1%;

[0009] The red light conversion powder is mainly prepared from europium chloride, 2-thenoyltrifluoroacetone and the compound shown in the following formula I in a molar ratio of 1: (2.5-3.5): (0.5-1.5);

[0010]

[0011] Wherein, R1 is selected from any one of alkylene groups having 2 to 8 carbon atoms; and R is selected from any one of methyl and ethyl groups.

[0012] In a specific embodiment of the present invention, the R1 is ethylene.

[0013] In a specific embodiment of the present invention, R is ethyl.

[0014] In a specific embodiment of the present invention, the preparation of the red light conversion powder includes:

[0015] (a) mixing a solution containing europium chloride and a solution containing 2-thenoyltrifluoroacetone, and stirring the mixture at 55-65° C. to react;

[0016] (b) Add a solution containing the compound of formula I to the material of step (a), stir and react at 55-65°C, cool to room temperature, and collect the precipitate.

[0017] In a specific embodiment of the present invention, the solvents used in the solution containing europium chloride, the solution containing 2-thenoyltrifluoroacetone, and the solution containing the compound represented by formula I are independently selected from any one of methanol and ethanol.

[0018] In a specific embodiment of the present invention, the concentration of the solution containing europium chloride is 0.3-0.5 mol / L; the concentration of the solution containing 2-thenoyltrifluoroacetone is 1-1.4 mol / L; the concentration of the solution containing the compound represented by formula I is 0.3-0.5 mol / L.

[0019] In a specific embodiment of the present invention, the adhesive film body comprises the following components by weight: 100 parts of a base resin, 0.5-1.5 parts of a crosslinking agent, 0.1-1 parts of a co-crosslinking agent, 0.1-0.5 parts of an antioxidant, 0.1-1 parts of a light stabilizer, and 0.3-1.5 parts of a coupling agent. Furthermore, the base resin comprises EVA resin or POE resin.

[0020] In a specific embodiment of the present invention, the thickness of the highly dispersed red light transfer adhesive film is 0.05 to 2 mm.

[0021] The second aspect of the present invention provides a method for preparing the highly dispersed red light-converting adhesive film of the first aspect, comprising the following steps: uniformly mixing the adhesive film body and the red light-converting powder in proportion, and extruding and casting the mixture into a film.

[0022] A third aspect of the present invention provides a photovoltaic module, comprising the high-dispersion red light-transfer adhesive film provided by the first aspect of the present invention.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention ensures the dispersibility of the red light conversion powder in the film by introducing an appropriate siloxane structure into the red light conversion powder. The light transmittance in the 280-380nm band is low, which can absorb more ultraviolet rays and convert them into red light. At the same time, the light transmittance in the 380-1100nm band is high, and the long-wave band is better utilized, significantly improving the component power. DETAILED DESCRIPTION

[0025] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0026] The first aspect of the present invention provides a highly dispersed red light-converting adhesive film, comprising an adhesive film body and red light-converting powder dispersed in the adhesive film body; in the red light-converting adhesive film, the mass fraction of the red light-converting powder is 0.005% to 1%;

[0027] The red light-converting powder is mainly prepared from europium chloride, 2-thenoyltrifluoroacetone and the compound shown in the following formula I in a molar ratio of 1:(2.5-3.5):(0.5-1.5);

[0028]

[0029] Wherein, R1 is selected from any one of alkylene groups having 2 to 8 carbon atoms; and R is selected from any one of methyl and ethyl groups.

[0030] The present invention ensures the dispersibility of the red light conversion powder in the film by introducing an appropriate siloxane structure into the red light conversion powder. The light transmittance in the 280-380nm band is low, which can absorb more ultraviolet rays and convert them into red light. At the same time, the light transmittance in the 380-1100nm band is high, and the long-wave band is better utilized, significantly improving the component power.

[0031] For example, in different embodiments, the mass fraction of the red light-conversion powder in the red light-conversion adhesive film can be 0.005%, 0.008%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, or a range consisting of any two thereof. When the amount of red light-conversion powder in the red light-conversion adhesive film is within the above range, the module power gain effect increases as the amount of red light-conversion powder increases. When the amount of red light-conversion powder is too low, the module power gain is not significant. When the amount of red light-conversion powder is too high, it leads to reduced long-wavelength transmission and powder aggregation, which in turn reduces the module's overall utilization of sunlight.

[0032] The red light-conversion powder of the present invention is prepared using europium chloride, 2-thenoyltrifluoroacetone, and the compound represented by Formula I. The europium chloride provides europium ions as luminescent centers, which coordinate with 2-thenoyltrifluoroacetone to form a chelate, enhancing ultraviolet absorption and energy transfer. The compound represented by Formula I fills the coordination sites of the europium ions, stabilizing the chelate structure and inhibiting non-radiative transitions. Furthermore, the -R1Si(OR)3 structure in the compound represented by Formula I significantly improves the dispersion uniformity and stability of the red light-conversion powder within the film. For example, in different embodiments, in the preparation of red light-converting powder, the molar ratio of europium chloride to 2-thenoyltrifluoroacetone can be 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5 or a range consisting of any two thereof; the molar ratio of europium chloride to the compound represented by formula I can be 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5 or a range consisting of any two thereof.

[0033] In a specific embodiment of the present invention, the red light conversion powder is mainly prepared from europium chloride, 2-thenoyltrifluoroacetone and the compound represented by formula I in a molar ratio of 1:3:1.

[0034] For example, the red light conversion powder of the present invention may have the following coordination structure:

[0035]

[0036] In a specific embodiment of the present invention, R1 is ethylene.

[0037] In a specific embodiment of the present invention, R is ethyl.

[0038] In a specific embodiment of the present invention, the specific structure of the compound represented by Formula I can be as follows:

[0039]

[0040] Through research, the present invention found that when R1 is ethylene and R is ethyl, the corresponding red light conversion powder has the best compatibility with the matrix resin of the film body, such as EVA resin, avoiding the problem of decreased effective light transmittance caused by local phase separation caused by the introduction of silicone, etc.

[0041] In a specific embodiment of the present invention, the preparation of red light conversion powder includes:

[0042] (a) mixing a solution containing europium chloride and a solution containing 2-thenoyltrifluoroacetone, and stirring the mixture at 55-65° C. to react;

[0043] (b) Add a solution containing the compound of formula I to the material of step (a), stir and react at 55-65°C, cool to room temperature, and collect the precipitate.

[0044] In a specific embodiment of the present invention, in step (a), the stirring reaction time is 20 to 40 min, such as 20 min, 25 min, 30 min, 35 min, 40 min or a range consisting of any two thereof; in step (b), the stirring reaction time is 1 to 3 h, such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h or a range consisting of any two thereof.

[0045] In a specific embodiment of the present invention, the solvents used in the solution containing europium chloride, the solution containing 2-thenoyltrifluoroacetone, and the solution containing the compound represented by formula I are independently selected from any one of methanol and ethanol.

[0046] In a specific embodiment of the present invention, the concentration of the solution containing europium chloride is 0.3-0.5 mol / L; the concentration of the solution containing 2-thenoyltrifluoroacetone is 1-1.4 mol / L; and the concentration of the solution containing the compound represented by formula I is 0.3-0.5 mol / L.

[0047] The synthetic route of the compound represented by the following formula I of the present invention can be referred to as follows:

[0048]

[0049] In the first step, compound A (4,7-dihydroxy-1,10-phenanthroline) can be mixed with a sodium hydroxide aqueous solution, stirred at 70-90° C. for 4-6 hours, cooled to precipitate a solid, and the collected solid is compound B; in the second step, compound B and compound C can be mixed in a solvent at a molar ratio of 1: (2-2.5), using N-ethyldimethylaminopyridinium bromide as a catalyst, reacting at 100-105° C. for 2-4 hours, cooling to room temperature, adding water, and then extracting with ethyl acetate. The organic phase is collected and the solvent is removed to obtain the compound represented by formula I.

[0050] Among them, N-ethyldimethylaminopyridine bromide can be obtained by commercial products or homemade methods. The present invention provides an optional preparation method: take 0.05 mol of dimethylaminopyridine, add 10 g of DMF and 10 g of deionized water, heat to 45°C, add 0.055 mol of bromoethane dropwise, and react for 20 hours; filter at 0-5°C to obtain crystals, namely N-ethyldimethylaminopyridine bromide; its structure is verified by nuclear magnetic resonance, and the nuclear magnetic resonance data are: 1H NMR (D2O or CDCl3): pyridine ring hydrogen: δ8.5-9.0 ppm (multiple peaks, 4H, pyridine ring -H); dimethylamino (-N(CH3)2): δ3.2-3.5 ppm (singlet, 6H); ethyl (-CH2CH3): δ3.0-3.2 ppm (quartet, 2H, -N + -CH2-), δ1.3-1.5ppm (triplet, 3H, -CH3). The reaction route is as follows:

[0051]

[0052] Compound C can be obtained from commercial products or by self-production. Compound C can be: 2-chloroethyltrimethoxysilane (CAS No.: 18157-21-6), 2-chloroethyltriethoxysilane (CAS No.: 18279-67-9), 3-chloropropyltrimethoxysilane (CAS No.: 2530-87-2), 3-chloropropyltriethoxysilane (CAS No.: 5089-70-3), etc. Self-production compound C takes 8-chlorooctyltrimethoxysilane as an example, and its synthesis method is as follows:

[0053] To 0.12 mol of trimethoxysilane, add 0.0001 mol of RuCl₃ (CAS No.: 14898-67-0). Heat to 80°C, then gradually add 0.1 mol of 8-chloro-1-octene dropwise. After cooling to room temperature, distill the mixture under reduced pressure at 120°C. The product is the product. 8-Chlorooctyltriethoxysilane was prepared using the same method as described above, except that an equal amount of triethoxysilane was used instead of trimethoxysilane. The corresponding structure was verified by NMR. The nuclear magnetic data of 8-chlorooctyltrimethoxysilane are: 1HNMR (CDCl3): Si-CH2-chain end: δ0.6-0.7ppm (triplet, 2H); -CHCl group: δ3.5-3.6ppm (triplet, 2H); methylene chain (-(CH2)6-): δ1.2-1.4ppm (multiplet, 12H); -OCH2CH3: δ3.7-3.8ppm (quartet, 6H), δ1.2ppm (triplet, 9H). The nuclear magnetic data of 8-chlorooctyltriethoxysilane are: 1H NMR (CDCl3 solvent): δ0.6-0.7ppm (t, 2H, Si-CH2-); δ1.2-1.4ppm (m, 12H, -(CH2)6-); δ1.5-1.6ppm (m, 2H, -CH2-CH2Cl); δ3.5-3.6ppm (t, 2H, -CH2Cl); δ3.7-3.8ppm (q, 6H, -OCH2-); δ1.2ppm (t, 9H, -OCH2CH3).

[0054] Specifically, when R1 is ethylene and R is methyl, the structure of the corresponding compound represented by Formula I is as follows:

[0055]

[0056] The synthesis method is as follows: 0.1 mol of compound A (4,7-dihydroxy-1,10-phenanthroline) was added to 200 mL of 15% sodium hydroxide aqueous solution, heated to 80°C with stirring, and reacted for 5 hours. The mixture was cooled to remove the precipitated solid, which was then filtered to obtain compound B. 0.1 mol of compound B and 0.23 mol of 2-chloroethyltrimethoxysilane were added to 200 mL of dimethylformamide (DMF), followed by the addition of 0.005 mol of N-ethyldimethylaminopyridinium bromide as a catalyst. The mixture was heated to 100°C for 3 hours, cooled to room temperature, and extracted with ethyl acetate (200 mL x 3). The organic phase was collected and the solvent removed to obtain the compound represented by Formula Ⅰ1. Structural characterization by nuclear magnetic resonance and mass spectrometry confirmed the compound to be the target product. Among them, the nuclear magnetic data of the compound represented by formula Ⅰ1 are: 1H NMR (CDCl3): phenanthroline ring No. 2 and No. 9: δ8.70-8.80ppm (d, 2H); phenanthroline ring No. 5 and No. 6: δ7.75-7.85ppm (s, 2H); phenanthroline ring No. 3 and No. 8: δ7.35-7.45ppm (d, 2H); -O-CH2-: δ4.20-4.30ppm (t, 4H); -OCH3: δ3.50-3.55ppm (s, 18H); -CH2-Si: δ1.90-2.00ppm (t, 4H).

[0057] When R1 is ethylene and R is ethyl, the structure of the corresponding compound represented by formula I is as follows:

[0058]

[0059] The synthesis method is as follows: Compound B was prepared according to the above method; 0.1 mol of Compound B and 0.23 mol of 2-chloroethyltriethoxysilane were added to 200 mL of DMF, followed by the addition of 0.005 mol of N-ethyldimethylaminopyridinium bromide as a catalyst. The reaction was heated to 100°C for 3 hours, cooled to room temperature, and 200 mL of water was added. Extraction was then performed with ethyl acetate (200 mL x 3). The organic phase was collected and the solvent removed to obtain the compound represented by Formula I2. Structural characterization by NMR and mass spectrometry confirmed the compound to be the target product. Among them, the nuclear magnetic data of the compound represented by formula I2 are: 1H NMR (CDCl3): phenanthroline ring No. 2 and No. 9: δ8.70-8.75ppm (d, 2H); phenanthroline ring No. 5 and No. 6: δ7.75-7.80ppm (s, 2H); phenanthroline ring No. 3 and No. 8: δ7.35-7.40ppm (d, 2H); —O—CH2—CH2—Si(α-CH2): δ4.20-4.30ppm(t, 4H); —O—CH2—CH2—Si(β-CH2): δ1.85-1.95ppm(t, 4H); Si—O—CH2—CH3(OCH2): δ3.75-3.85ppm(q, 12H); Si—O—CH2—CH3(CH3): δ1.15-1.25ppm(t, 18H).

[0060] When R1 is an octylene group and R is a methyl group, the structure of the compound represented by the corresponding formula I is as follows:

[0061]

[0062] The synthesis method is as follows: Compound B was prepared according to the above method; 0.1 mol of Compound B and 0.23 mol of 8-chlorooctyltrimethoxysilane were added to 200 mL of DMF, followed by the addition of 0.005 mol of N-ethyldimethylaminopyridinium bromide as a catalyst. The temperature was raised to 100°C for 3 hours, and then cooled to room temperature. 200 mL of water was added, followed by extraction with ethyl acetate (200 mL x 3). The organic phase was collected and the solvent removed to obtain the compound represented by Formula I3. Structural characterization by NMR and mass spectrometry confirmed the compound to be the target product. The NMR data of the compound represented by Formula I3 were: 1H NMR (CDCl3): phenanthroline rings 2 and 9: δ8.70–8.75 ppm (d, 2H); phenanthroline rings 5 ​​and 6: δ7.75–7.80 ppm (s, 2H); phenanthroline rings 3 and 8: δ7.35–7.40 ppm (d, 2H); —O—CH2—(CH2)7—Si(α-CH2): δ4.20–4.30 ppm (t, 4H); Si—OCH3: δ3.50–3.55 ppm (s, 18H); —O—CH2—CH2—(CH2)6—(β-CH2): δ1.55–1.65ppm (quintet, 4H); —(CH2)—CH2—Si(ω-1-CH2): δ1.40–1.50ppm (sextet, 4H); —(CH2)4—: δ1.25–1.35ppm(m, 16H); —(CH2)7—CH2—Si(ω-CH2): δ0.60–0.70ppm(t, 4H).

[0063] When R1 is octylene and R is ethyl, the structure of the compound represented by formula I is as follows:

[0064]

[0065] The synthesis method is as follows: Compound B was prepared according to the above method; 0.1 mol of Compound B and 0.23 mol of 8-chlorooctyltriethoxysilane were added to 200 mL of DMF, followed by the addition of 0.005 mol of N-ethyldimethylaminopyridinium bromide as a catalyst. The temperature was raised to 100°C for 3 hours, and then cooled to room temperature. 200 mL of water was added, followed by extraction with ethyl acetate (200 mL x 3). The organic phase was collected and the solvent removed to obtain the compound represented by Formula I4. Structural characterization by NMR and mass spectrometry confirmed the compound to be the target product. The NMR data of the compound represented by Formula I4 were: 1H NMR (CDCl3): phenanthroline rings No. 2 and 9: δ8.70–8.75 ppm (d, 2H); phenanthroline rings No. 5 and 6: δ7.75–7.80 ppm (s, 2H); phenanthroline rings No. 3 and 8: δ7.35–7.40 ppm (d, 2H); —O—CH2—(CH2)7—Si(α-CH2): δ4.20-4.30 ppm (t, 4H); Si—O—CH2—CH3(OCH2): δ3.75-3.85 ppm (q, 12H); —O—CH2—CH 2—(CH2)6—(β-CH2): δ1.55-1.65ppm (quintet, 4H);—(CH2)—CH2—Si(ω-1-CH2): δ1.40-1.50ppm (sextet, 4H);—(CH2)4—: δ1.25-1.35ppm (m, 16H); Si—O—CH2—CH3(CH3): δ1.15-1.25ppm (t, 18H);—(CH2)7—CH2—Si(ω-CH2): δ0.60-0.70ppm (t, 4H).

[0066] In a specific embodiment of the present invention, the adhesive film comprises the following components by weight: 100 parts of a base resin, 0.5-1.5 parts of a crosslinking agent, 0.1-1 parts of a co-crosslinking agent, 0.1-0.5 parts of an antioxidant, 0.1-1 parts of a light stabilizer, and 0.3-1.5 parts of a coupling agent. Furthermore, the base resin comprises EVA resin or POE resin.

[0067] The adhesive film body of the present invention may be the same as the adhesive film body conventionally used for red light transfer adhesive films. For example, in different embodiments, the amounts of the remaining components in the adhesive film body, by weight, relative to 100 parts of the base resin, may be as follows:

[0068] The amount of the cross-linking agent can be 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or a range consisting of any two thereof;

[0069] The amount of the auxiliary cross-linking agent can be 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part or a range consisting of any two thereof;

[0070] The amount of the antioxidant can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part or a range consisting of any two thereof;

[0071] The amount of the light stabilizer can be 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part or a range consisting of any two thereof;

[0072] The amount of the coupling agent can be 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or a range consisting of any two parts thereof.

[0073] Among them, the types of various auxiliary agents can be exemplified as follows, but are not limited thereto: the cross-linking agent is selected from at least one of peroxide cross-linking agents, for example, tert-butyl peroxycarbonate-2-ethylhexyl ester; the auxiliary cross-linking agent includes ethylene glycol dimethacrylate; the antioxidant includes any one or more of hindered phenol antioxidants and phosphite antioxidants; the light stabilizer includes 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; the coupling agent includes at least one of silane coupling agents, such as an epoxy-containing silane coupling agent, specifically γ-glycidyloxypropyltrimethoxysilane.

[0074] The second aspect of the present invention provides a method for preparing the highly dispersed red light-converting adhesive film of the first aspect, comprising the following steps: uniformly mixing the adhesive film body and the red light-converting powder in proportion, and extruding and casting the mixture into a film.

[0075] In a specific embodiment of the present invention, the extrusion casting temperature is 75-90°C. In actual operation, the uniform mixing operation can be performed in a mixer, and the extrusion casting film forming operation can be performed in a casting machine. Specifically, the extrusion casting temperature can be 75°C, 80°C, 85°C, 90°C, or a range of any two thereof. The specific extrusion casting temperature can be adjusted conventionally.

[0076] In a specific embodiment of the present invention, the thickness of the highly dispersed red optical transfer adhesive film is 0.05 to 2 mm, for example, it can be 0.05 mm, 0.1 mm, 0.3 mm, 0.5 mm, 0.8 mm, 1 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm or a range consisting of any two thereof.

[0077] A third aspect of the present invention provides a photovoltaic module, comprising the high-dispersion red light-transfer adhesive film provided by the first aspect of the present invention.

[0078] In a specific embodiment of the present invention, the photovoltaic module includes an HJT cell and glass, and a high-dispersion red light transfer adhesive film is attached between the HJT cell and the glass.

[0079] Some product information used in the specific implementation of the present invention may be as follows, which are conventional materials in this field, but are not limited to these: EVA resin: Sailbon V2825.

[0080] Example 1

[0081] This embodiment provides a highly dispersed red light transfer adhesive film and a preparation method thereof, wherein the highly dispersed red light transfer adhesive film includes the following components in parts by weight:

[0082] 100 parts of EVA resin, 0.8 parts of crosslinking agent tert-butyl peroxycarbonate-2-ethylhexyl ester, 0.5 parts of co-crosslinking agent ethylene glycol dimethacrylate, 0.4 parts of antioxidant tris(nonylphenyl) phosphite, 0.5 parts of light stabilizer 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1.2 parts of coupling agent γ-glycidyloxypropyltrimethoxysilane, and 0.01 parts of red light-converting powder.

[0083] The preparation method of red light-converting powder comprises:

[0084] Weigh 0.1 mol of europium chloride and dissolve it in 250 mL of methanol to obtain a europium chloride solution; weigh 0.3 mol of 2-thenoyltrifluoroacetone and dissolve it in 250 mL of methanol to obtain a 2-thenoyltrifluoroacetone solution; weigh 0.1 mol of the compound represented by formula Ⅰ1 and dissolve it in 250 mL of methanol to obtain a solution of the compound represented by formula Ⅰ1;

[0085] The 2-thiopheneyltrifluoroacetone solution was added dropwise to the europium chloride solution, and the mixture was stirred at 60°C for 30 minutes after the addition was completed; then the solution of the compound represented by formula Ⅰ1 was added, and the mixture was stirred at 60°C for 2 hours after the addition was completed; then the mixture was cooled to room temperature, the precipitate was precipitated, filtered and dried to obtain a red photoconversion powder.

[0086] The preparation method of the highly dispersed red light-transfer adhesive film of this embodiment includes the following steps: weighing each material in proportion, mixing them evenly in a mixer, and then putting them into a casting machine. At 80°C, the highly dispersed red light-transfer adhesive film with a thickness of 0.5 mm is formed by plasticizing, extruding, stretching, pulling, and winding.

[0087] Example 2

[0088] This embodiment refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the amount of red light-transfer powder in the highly dispersed red light-transfer adhesive film is different.

[0089] In this embodiment, the amount of red light conversion powder used is 0.5 parts by weight.

[0090] Example 3

[0091] This embodiment refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the amount of red light-transfer powder in the highly dispersed red light-transfer adhesive film is different.

[0092] In this embodiment, the amount of red light conversion powder used is 1 part by weight.

[0093] Example 4

[0094] This embodiment refers to the high-dispersion red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the red light-transfer powder in the high-dispersion red light-transfer adhesive film is different.

[0095] The preparation method of the red light conversion powder of this embodiment includes:

[0096] Weigh 0.1 mol of europium chloride and dissolve it in 250 mL of methanol to obtain a europium chloride solution; weigh 0.3 mol of 2-thenoyltrifluoroacetone and dissolve it in 250 mL of methanol to obtain a 2-thenoyltrifluoroacetone solution; weigh 0.1 mol of the compound represented by formula I2 and dissolve it in 250 mL of methanol to obtain a solution of the compound represented by formula I2;

[0097] The 2-thiopheneyltrifluoroacetone solution was added dropwise to the europium chloride solution, and the mixture was stirred at 60°C for 30 minutes after the addition was completed; then the solution of the compound represented by formula I2 was added, and the mixture was stirred at 60°C for 2 hours after the addition was completed; then the mixture was cooled to room temperature, the precipitate was precipitated, filtered and dried to obtain a red photoconversion powder.

[0098] Example 5

[0099] This embodiment refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 4, with the only difference being that the amount of red light-transfer powder in the highly dispersed red light-transfer adhesive film is different.

[0100] In this embodiment, the amount of red light conversion powder used is 0.5 parts by weight.

[0101] Example 6

[0102] This embodiment refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 5, with the only difference being that the amount of red light-transfer powder used in the highly dispersed red light-transfer adhesive film is different.

[0103] In this embodiment, the amount of red light conversion powder used is 1 part by weight.

[0104] Example 7

[0105] This embodiment refers to the high-dispersion red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the red light-transfer powder in the high-dispersion red light-transfer adhesive film is different.

[0106] The preparation method of the red light conversion powder of this embodiment includes:

[0107] Weigh 0.1 mol of europium chloride and dissolve it in 250 mL of methanol to obtain a europium chloride solution; weigh 0.3 mol of 2-thenoyltrifluoroacetone and dissolve it in 250 mL of methanol to obtain a 2-thenoyltrifluoroacetone solution; weigh 0.1 mol of the compound represented by formula I3 and dissolve it in 250 mL of methanol to obtain a solution of the compound represented by formula I3;

[0108] The 2-thiopheneyltrifluoroacetone solution was added dropwise to the europium chloride solution, and the mixture was stirred at 60°C for 30 minutes after the addition was completed; then the solution of the compound represented by formula I3 was added, and the mixture was stirred at 60°C for 2 hours after the addition was completed; then the mixture was cooled to room temperature, the precipitate was precipitated, filtered and dried to obtain a red photoconversion powder.

[0109] Example 8

[0110] This embodiment refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 7, with the only difference being that the amount of red light-transfer powder used in the highly dispersed red light-transfer adhesive film is different.

[0111] In this embodiment, the amount of red light conversion powder used is 1 part by weight.

[0112] Example 9

[0113] This embodiment refers to the high-dispersion red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the red light-transfer powder in the high-dispersion red light-transfer adhesive film is different.

[0114] The preparation method of the red light conversion powder of this embodiment includes:

[0115] Weigh 0.1 mol of europium chloride and dissolve it in 250 mL of methanol to obtain a europium chloride solution; weigh 0.3 mol of 2-thenoyltrifluoroacetone and dissolve it in 250 mL of methanol to obtain a 2-thenoyltrifluoroacetone solution; weigh 0.1 mol of the compound represented by formula I4 and dissolve it in 250 mL of methanol to obtain a solution of the compound represented by formula I4;

[0116] The 2-thiopheneyltrifluoroacetone solution was added dropwise to the europium chloride solution, and the mixture was stirred at 60°C for 30 minutes after the addition was completed; then the solution of the compound represented by formula I4 was added, and the mixture was stirred at 60°C for 2 hours after the addition was completed; then the mixture was cooled to room temperature, the precipitate was precipitated, filtered and dried to obtain a red photoconversion powder.

[0117] Example 10

[0118] This embodiment refers to the high-dispersion red light-transfer adhesive film and preparation method thereof of Example 9, with the only difference being that the amount of red light-transfer powder in the high-dispersion red light-transfer adhesive film is different.

[0119] In this embodiment, the amount of red light conversion powder used is 1 part by weight.

[0120] Comparative Example 1

[0121] Comparative Example 1 refers to the highly dispersed red light-transfer adhesive film and preparation method thereof of Example 1, with the only difference being that the red light-transfer powder in the red light-transfer adhesive film is different.

[0122] The preparation method of the red light-converting powder of Comparative Example 1 includes:

[0123] Weigh 0.1 mol of europium chloride and dissolve it in 250 mL of methanol to obtain a europium chloride solution; weigh 0.3 mol of 2-thenoyltrifluoroacetone and dissolve it in 250 mL of methanol to obtain a 2-thenoyltrifluoroacetone solution; weigh 0.1 mol of 1,10-phenanthroline and dissolve it in 250 mL of methanol to obtain a 1,10-phenanthroline solution;

[0124] The 2-thiopheneyltrifluoroacetone solution was added dropwise to the europium chloride solution, and the mixture was stirred at 60°C for 30 minutes. The 1,10-phenanthroline solution was then added, and the mixture was stirred at 60°C for 2 hours. The mixture was then cooled to room temperature, the precipitate was precipitated, and the solution was filtered and dried to obtain a red photoconversion powder.

[0125] Comparative Example 2

[0126] Comparative Example 2 refers to the red light-converting adhesive film and preparation method thereof of Comparative Example 1, with the only difference being that the amount of red light-converting powder in the red light-converting adhesive film is different.

[0127] In Comparative Example 2, the amount of the red light-converting powder used was 0.5 parts by weight.

[0128] Comparative Example 3

[0129] Comparative Example 3 refers to the red light-converting adhesive film and preparation method thereof of Comparative Example 1, with the only difference being that the amount of red light-converting powder in the red light-converting adhesive film is different.

[0130] In Comparative Example 3, the amount of the red light-converting powder used was 1 part by weight.

[0131] Comparative Example 4

[0132] Comparative Example 4 refers to the highly dispersed red photoconvertible adhesive film and its preparation method of Example 1, with the only difference being that no red photoconvertible powder is added in the preparation of the photoconvertible adhesive film.

[0133] Experimental example

[0134] To compare and illustrate the performance differences between the films of different Examples and Comparative Examples, the films of different Examples and Comparative Examples were fabricated into photovoltaic module samples for testing. Their light transmittance was tested, and the initial module power of the different photovoltaic modules was also tested in accordance with IEC 61215. The test results are shown in Table 1.

[0135] The photovoltaic module samples to be tested included upper glass, upper film, cells, lower film, and lower glass, all of which were double-glass modules. Both the upper and lower films were the films of the present invention, and the cells were 210-size HJT cells (66 cells), resulting in a 210-66 module.

[0136] Table 1 Performance test results of photovoltaic modules corresponding to different films

[0137]

[0138]

[0139] From the above test results, it can be seen that the present invention ensures the dispersion of red light conversion powder in the film by introducing an appropriate siloxane structure into the red light conversion powder, and the transmittance in the 280-380nm band is low, which can absorb more ultraviolet rays and convert them into red light; at the same time, the transmittance in the 380-1100nm band is high, and the long-wave band is better utilized, significantly improving the component power.

[0140] Further, according to Examples 1 to 6, when the same amount of red light conversion powder is added and R1 of the compound used in the red light conversion powder is ethylene, when R of the compound used in the red light conversion powder is ethyl, it is more helpful to improve the compatibility with the matrix resin and the initial power of the component is higher.

[0141] Further, Examples 1-6 show that, given the same amount of red light-converting powder added and the same ethylene group as the R1 compound, an ethyl group in the red light-converting powder compound significantly improves compatibility with the matrix resin, resulting in higher initial module power. Similarly, Examples 7-10 also show similar results.

[0142] Further, Examples 4-6 and 9-10 show that, given the same amount of red light-converting powder added and the same ethyl group in the compound used, an ethylene group in the compound used for red light-converting powder significantly improves compatibility with the matrix resin, resulting in higher initial module power. Similarly, a comparison of Examples 1-3 and 7-8 shows similar results.

[0143] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Highly dispersed red light transfer film, characterized by: The invention comprises a film body and red light conversion powder dispersed in the film body; in the red light conversion film, the mass fraction of the red light conversion powder is 0.005% to 1%; The red light conversion powder is mainly prepared from europium chloride, 2-thenoyltrifluoroacetone and the compound shown in the following formula I in a molar ratio of 1: (2.5-3.5): (0.5-1.5); Wherein, R1 is selected from any one of alkylene groups having 2 to 8 carbon atoms; and R is selected from any one of methyl and ethyl groups.

2. The highly dispersed red light transfer adhesive film according to claim 1, characterized in that: The R1 is ethylene.

3. The highly dispersed red light transfer adhesive film according to claim 1 or 2, characterized in that: The R is an ethyl group.

4. The highly dispersed red light transfer adhesive film according to claim 1, characterized in that: The preparation of the red light conversion powder comprises: (a) mixing a solution containing europium chloride and a solution containing 2-thenoyltrifluoroacetone, and stirring the mixture at 55-65° C. to react; (b) Add a solution containing the compound of formula I to the material of step (a), stir and react at 55-65°C, cool to room temperature, and collect the precipitate.

5. The highly dispersed red light transfer adhesive film according to claim 4, characterized in that: The solvents used in the solution containing europium chloride, the solution containing 2-thenoyltrifluoroacetone, and the solution containing the compound represented by formula I are independently selected from any one of methanol and ethanol.

6. The highly dispersed red light transfer adhesive film according to claim 4, characterized in that: Has at least one of the following characteristics: (1) The concentration of the europium chloride-containing solution is 0.3 to 0.5 mol / L; (2) The concentration of the solution containing 2-thenoyltrifluoroacetone is 1 to 1.4 mol / L; (3) The concentration of the solution containing the compound represented by formula I is 0.3 to 0.5 mol / L.

7. The highly dispersed red light transfer adhesive film according to claim 1, characterized in that: The adhesive film body comprises the following components in parts by weight: 100 parts of base resin, 0.5-1.5 parts of cross-linking agent, 0.1-1 parts of auxiliary cross-linking agent, 0.1-0.5 parts of antioxidant, 0.1-1 parts of light stabilizer and 0.3-1.5 parts of coupling agent; Preferably, the matrix resin includes EVA resin or POE resin.

8. The highly dispersed red light transfer adhesive film according to claim 1, characterized in that: The thickness of the highly dispersed red light transfer adhesive film is 0.05 to 2 mm.

9. The method for preparing a highly dispersed red light transfer adhesive film according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing the film main body and the red light-converting powder in proportion, and extruding and casting the mixture into a film.

10. A photovoltaic module, characterized in that: The invention comprises the highly dispersed red light transfer adhesive film according to any one of claims 1 to 8.

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