Non-polar thermally stable light conversion adhesive film and preparation method thereof

Abstract

The invention discloses a non-polar heat-stable light conversion adhesive film and a preparation method thereof. The preparation method comprises the following steps: dissolving alkane amine, alkane acid and a light conversion agent in a reaction solvent to obtain a mixed solution; adding a silane coupling agent into the mixed solution, stirring for a period of time at 45-55 DEG C, heating to 115-125 DEG C, keeping for a period of time, then adding POE resin, stirring and fully mixing at 95-105 DEG C, and then drying to obtain the non-polar heat-stable light conversion adhesive film. The light conversion adhesive film prepared by the invention can block the damage of ultraviolet photons to a photovoltaic cell, improve the stability of the cell, effectively utilize high-energy photons and improve the efficiency of a photovoltaic module, and has stability at a high temperature of 120 DEG C.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and particularly relates to a non-polar thermally stable light-converting film and a preparation method thereof. Background Art

[0002] Non-polar photovoltaic films represented by polyolefin (POE) have excellent water, vapor and ion barrier capabilities. Related prior art examples include the patent specification with publication number CN118359643A, etc. However, ultraviolet photons can easily penetrate through the POE film and cause damage to crystalline silicon photovoltaic cells.

[0003] Organic conjugated molecules represented by 9,10-diphenylanthracene (DPA) can effectively convert ultraviolet photons into visible photons and be utilized by photovoltaic cells. The inventor previously studied a light-converting film and its preparation method and application. Refer to the patent specification with publication number CN118206930A. The raw material composition of the light-converting film includes a matrix resin and a light-converting agent with a mass ratio of 1000 - 30000:1, and an optionally added softening agent; the matrix resin is EVA or POE; the light-converting agent is 9,10-diphenylanthracene and / or its derivatives. The preparation method of the light-converting film: Mix the matrix resin and the light-converting agent and heat to 80 - 150 °C and stir to fully disperse the light-converting agent in the matrix resin until the mixture is completely transparent and has no visible agglomerates to the naked eye, and then cool to obtain the light-converting film; or, dissolve the light-converting agent in the softening agent, then add the matrix resin, the matrix resin softens in the softening agent and is fully mixed with the light-converting agent, and then dry at 80 - 150 °C to remove part or all of the softening agent, and cool to obtain the light-converting film. The above patent technology adds a specific amount of the light-converting agent 9,10-diphenylanthracene and / or its derivatives on the basis of the EVA or POE film. The obtained light-converting film has a light conversion efficiency close to 100%, and can convert high-energy photons of 300 - 400 nm into low-energy photons near 452 nm.

[0004] However, the organic molecules 9,10-diphenylanthracene and its derivatives have low stability and cannot ensure the long-term operation of crystalline silicon photovoltaic cells. Summary of the Invention

[0005] In view of the above technical problems and deficiencies in the art, the present invention provides a non-polar thermally stable light-converting film and a preparation method thereof. According to the preparation method of the present invention, the light-converting agent in the light-converting film can be stabilized. The alkane amine and alkane acid in the technical solution of the present invention can provide a non-polar environment for silane and can be dispersed in POE.

[0006] The specific technical solution is as follows:

[0007] [1] A preparation method of a non-polar thermally stable light-converting film, comprising:

[0008] Dissolving an alkane amine, an alkane acid and a light conversion agent in a reaction solvent to obtain a mixed solution; the alkane amine comprises at least one of octylamine, dodecylamine, hexadecylamine, heptadecanylamine and octadecylamine; the alkane acid comprises at least one of octanoic acid, hexadecylamine, heptadecanylamine and octadecylamine;

[0009] Adding a silane coupling agent to the mixed solution, stirring for a period of time at 45-55° C. (e.g., 50° C.), heating to 115-125° C. (e.g., 120° C.), and maintaining for a period of time, then adding a POE resin at 95-105° C. (e.g., 100° C.), stirring and mixing thoroughly, and then drying to obtain the non-polar heat-stable light-converting adhesive film;

[0010] The silane coupling agent includes at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0011] In the preparation method of the present invention, due to the presence of water in the air and water that may be brought by the raw materials, when heated to 115-125°C, the silane coupling agent will be partially hydrolyzed to form nano-silicon dioxide, and its surface is composed of alkane amine, alkane acid and remaining silane coupling agent, which has non-polar characteristics, and the light conversion agent is embedded in the inside. Taking the silane coupling agent 3-aminopropyltriethoxysilane and the light conversion agent 9,10-diphenylanthracene as examples, the exemplary examples are as follows Figure 1 As shown, the silane coupling agent is hydrolyzed to encapsulate the light conversion agent.

[0012] In some embodiments, in the method for preparing the non-polar heat-stable light-converting adhesive film, the amount ratio of the light-converting agent, the alkane amine, the alkane acid and the silane coupling agent can be 0.1-10g:5-10mL:5-10mL:5-20mL, and can further be 1g:10mL:10mL:10mL.

[0013] In some embodiments, in the method for preparing the non-polar heat-stable light-converting adhesive film, the usage ratio of the light-converting agent to the reaction solvent can be 0.001-0.01 g:1 mL, and can further be 0.005 g:1 mL.

[0014] In some embodiments, in the method for preparing the non-polar heat-stable light-converting adhesive film, the reaction solvent may include at least one of octane, toluene, heptane, ether, tetrahydrofuran, ethyl acetate, methyl acetate, and acetone.

[0015] In some embodiments, in the method for preparing the non-polar heat-stable light-converting adhesive film, the reaction solvent is a non-polar solvent.

[0016] In some embodiments, in the method for preparing the non-polar heat-stable light-converting adhesive film, the mass ratio of the POE resin to the light-converting agent may be 1000 to 30000:1.

[0017] In some embodiments, for the preparation method of the non-polar thermally stable light-converting adhesive film, the light-converting agent may be 9,10-diphenylanthracene and its derivatives, and specifically, at least one of the compounds having the structure shown in the following formula (I) can be selected:

[0018]

[0019] In formula (I), R 1 and R 2 are each independently selected from H, C 1 -C 18 alkyl or C 1 -C 18 alkoxy group.

[0020] In some embodiments, for the preparation method of the non-polar thermally stable light-converting adhesive film, stir at 45-55 °C for 2-3 hours.

[0021] In some embodiments, for the preparation method of the non-polar thermally stable light-converting adhesive film, maintain at 115-125 °C for 5-10 minutes.

[0022] In some embodiments, for the preparation method of the non-polar thermally stable light-converting adhesive film, the drying temperature can be 80-120 °C.

[0023] [2] A non-polar thermally stable light-converting adhesive film prepared by the preparation method according to [1].

[0024] The light-converting adhesive film prepared by the present invention can block the damage of ultraviolet photons to the photovoltaic cell, improve the battery stability, effectively utilize high-energy photons, improve the efficiency of the photovoltaic module, and at the same time, has stability at a high temperature of 120 °C.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] The present invention mixes a light-converting agent such as 9,10-diphenylanthracene with stabilizers (silane coupling agent, alkane amine and alkane acid) to form a nano-silica coating structure, and the alkane amine and alkane acid provide a non-polar environment and are embedded in the POE adhesive film.

[0027] The light-converting adhesive film obtained by the present invention still has a light-converting efficiency of 97.5% after aging at 120 °C for 7 days, while the light-converting efficiency of the pure 9,10-diphenylanthracene embedded in the POE adhesive film is only 86.2% after aging. Description of the Drawings

[0028] Figure 1 For the exemplary nano-silica (DPA@SiO 2Schematic diagram of the structure, the light conversion agent is embedded inside the nano-silica, and the surface is composed of the remaining silane coupling agent, alkane amine and alkane acid, with non-polar characteristics.

[0029] Figure 2 This is the comparison data graph of the fluorescence quantum efficiency (PLQY) of the light conversion film before and after aging in Example 1 and Comparative Example 1 of the present invention.

[0030] Figure 3 For DPA@SiO in Example 1 2 Spectrum of the aged light conversion film with the embedded one, (a) excitation spectrum (PLE) and emission spectrum (PL), (b) original data graph of PLQY.

[0031] Figure 4 Spectrum of the aged light conversion film with DPA directly embedded in Comparative Example 1, (a) excitation spectrum (PLE) and emission spectrum (PL), (b) original data graph of PLQY. Detailed implementation manners

[0032] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention.

[0033] The operating methods without specific conditions noted in the following embodiments are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer.

[0034] In the following examples, the POE resin is POE 8411 of Dow Chemical Company, USA.

[0035] Example 1:

[0036] The preparation method of the non-polar thermally stable light conversion film includes the following steps:

[0037] 1) Take 4 mL of octane, 0.02 g of 9,10-diphenylanthracene, 0.2 mL of octylamine, and 0.2 mL of octanoic acid, and stir ultrasonically to dissolve completely.

[0038] 2) Add 0.2 mL of 3-aminopropyltrimethoxysilane, stir at 50 °C for 2 h, and anneal at 120 °C for 5 minutes.

[0039] 3) Add 20 g of the POE resin film masterbatch and mix well with the above liquid at 100 °C (stir vigorously with a glass rod).

[0040] 4) Dry at 80 - 120 °C to obtain the light conversion film.

[0041] See Figure 2 、 Figure 3, the fluorescence quantum efficiency of the light conversion film was tested to be 97.4%. After aging for 7 days at 120°C, the fluorescence quantum efficiency was 97.5%.

[0042] Comparative Example 1:

[0043] The preparation method of the light conversion film includes the following steps:

[0044] Stir 20 g of POE resin, 4 mL of octane, and 0.02 g of 9,10-diphenylanthracene at 120°C for 1 h until completely transparent and free of agglomerates, and then cool naturally to obtain the POE light conversion film. See Figure 2 , Figure 4 , the fluorescence quantum efficiency of the light conversion film was tested to be 97.4%. After aging for 7 days at 120°C, the fluorescence quantum efficiency was 86.2%.

[0045] Example 2:

[0046] The preparation method of the non-polar thermally stable light conversion film includes the following steps:

[0047] 1) 4 mL of octane, 0.02 g of 9,10-diphenylanthracene derivative A, 0.2 mL of octylamine, 0.2 mL of octanoic acid, and stir ultrasonically to dissolve completely. The structure of 9,10-diphenylanthracene derivative A is as follows:

[0048]

[0049] 2) Add 0.2 mL of 3-aminopropyltrimethoxysilane and stir at 50°C for 2 h, then anneal at 120°C for 5 minutes.

[0050] 3) Add 20 g of POE resin film masterbatch and mix well with the above liquid at 100°C (stir vigorously with a glass rod).

[0051] 4) Dry at 80 - 120°C to obtain the light conversion film.

[0052] The fluorescence quantum efficiency of the light conversion film was tested to be 95.2%. After aging for 7 days at 120°C, the fluorescence quantum efficiency was 95.0%.

[0053] Example 3:

[0054] The preparation method of the non-polar thermally stable light conversion film includes the following steps:

[0055] 1) 4 mL of octane, 0.02 g of 9,10-diphenylanthracene derivative B, 0.2 mL of octylamine, 0.2 mL of octanoic acid, and stir ultrasonically to dissolve completely. The structure of 9,10-diphenylanthracene derivative B is as follows:

[0056]

[0057] 2) 0.2 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 50 °C for 2 h and annealed at 120 °C for 5 minutes.

[0058] 3) 20 g of POE resin film masterbatch was added and thoroughly mixed with the above liquid at 100 °C (stirred vigorously with a glass rod).

[0059] 4) It was dried at 80 - 120 °C to obtain the light conversion film.

[0060] The fluorescence quantum efficiency of the light conversion film was tested to be 94.2%, and after aging for 7 days at 120 °C, the fluorescence quantum efficiency was 94.1%.

[0061] Example 4:

[0062] The preparation method of the non-polar thermally stable light conversion film includes the following steps:

[0063] 1) 4 mL of octane, 0.02 g of 9,10-diphenylanthracene, 0.2 mL of dodecylamine, and 0.2 mL of palmitic acid were ultrasonically stirred and completely dissolved.

[0064] 2) 0.2 mL of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 50 °C for 2 h and annealed at 120 °C for 5 minutes.

[0065] 3) 20 g of POE resin film masterbatch was added and thoroughly mixed with the above liquid at 100 °C (stirred vigorously with a glass rod).

[0066] 4) It was dried at 80 - 120 °C to obtain the light conversion film.

[0067] The fluorescence quantum efficiency of the light conversion film was tested to be 97.6%, and after aging for 7 days at 120 °C, the fluorescence quantum efficiency was 97.5%.

[0068] In each of the above examples, 3-aminopropyltrimethoxysilane hydrolyzes in an environment of alkane amine and alkane acid to form nano-SiO 2 , SiO 2 coordinates with amino and carboxyl groups and is wrapped by non-polar alkane groups. Thus, nano-DPA@SiO 2 has non-polarity.

[0069] As Figure 2 shown, for the light conversion film embedded with DPA@SiO 2 in Example 1, after aging for 7 days at 120 °C, the PLQY did not decrease. For the light conversion film of DPA in Comparative Example 1, the PLQY decreased significantly, indicating that the light conversion film embedded with DPA@SiO 2 has high thermal stability.

[0070] Figure 3 andFigure 4 are the original data spectra of PLE, PL, and PLQY of the light conversion film with DPA@SiO embedded in Example 1 and the light conversion film with DPA in Comparative Example 1 respectively. The PLE spectrum of the light conversion film with DPA@SiO 2 embedded shows multi-peak characteristics after aging, which is consistent with the PLE spectrum of DPA itself. The peaks of the PLE spectrum of the light conversion film with DPA in Comparative Example 1 decrease after aging, indicating that the structure of DPA has changed. 2 embedded shows multi-peak characteristics after aging, which is consistent with the PLE spectrum of DPA itself. The peaks of the PLE spectrum of the light conversion film with DPA in Comparative Example 1 decrease after aging, indicating that the structure of DPA has changed.

[0071] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

Claims

1. A method for preparing a non-polar heat-stable light-converting adhesive film, characterized in that: include: Dissolving an alkane amine, an alkane acid and a light conversion agent in a reaction solvent to obtain a mixed solution; the alkane amine comprises at least one of octylamine, dodecylamine, hexadecylamine, heptadecanylamine and octadecylamine; the alkane acid comprises at least one of octanoic acid, hexadecylamine, heptadecanylamine and octadecylamine; Adding a silane coupling agent to the mixed solution, stirring at 45-55° C. for a period of time, heating to 115-125° C. and maintaining for a period of time, then adding a POE resin at 95-105° C. and stirring to mix thoroughly, and then drying to obtain the non-polar heat-stable light-converting adhesive film; The silane coupling agent includes at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

2. The preparation method according to claim 1, characterized in that: The usage ratio of the light conversion agent, the alkane amine, the alkane acid and the silane coupling agent is 0.1-10 g: 5-10 mL: 5-10 mL: 5-20 mL, further 1 g: 10 mL: 10 mL: 10 mL.

3. The preparation method according to claim 1 or 2, characterized in that: The usage ratio of the light conversion agent to the reaction solvent is 0.001-0.01 g:1 mL, further 0.005 g:1 mL.

4. The preparation method according to claim 1, characterized in that: The reaction solvent includes at least one of octane, toluene, heptane, ether, tetrahydrofuran, ethyl acetate, methyl acetate, and acetone; or, The reaction solvent is a non-polar solvent.

5. The preparation method according to claim 1, characterized in that: The mass ratio of the POE resin to the light conversion agent is 1000 to 30000:

1.

6. The preparation method according to claim 1, characterized in that: The light conversion agent is 9,10-diphenylanthracene and its derivatives, selected from at least one of the compounds having the structure shown in the following formula (I): In formula (I), R1 and R2 are independently selected from H, C1 to C 18 Alkyl or C1~C 18 Alkoxy.

7. The preparation method according to claim 1, characterized in that: Stir at 45-55°C for 2-3 hours.

8. The preparation method according to claim 1, characterized in that: Maintain at 115-125°C for 5-10 minutes.

9. The preparation method according to claim 1, characterized in that: The drying temperature is 80-120°C.

10. The non-polar heat-stable light-converting adhesive film prepared according to the preparation method according to any one of claims 1 to 9.

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