Zirconium-magnesium-aluminum material, method for preparing same, and use thereof

Abstract

The application discloses a zirconium-magnesium-aluminum material and a preparation method and application thereof. x Mg y Al z (PO4) m ; wherein, x+z=1.5, y=1, and m=(4x+2y+3z) / 3. The zirconium-magnesium-aluminum material can improve the PID resistance of EVA resin, and further improve the service life of a photovoltaic module.

Description

Technical Field

[0001] This invention relates to a zirconium-magnesium-aluminum material, its preparation method, and its application. Background Technology

[0002] The lifespan of photovoltaic (PV) modules determines their operating costs. Potential-induced degradation (PID) and other issues can lead to power degradation exceeding 50%. EVA resin, a new material made from ethylene-vinyl acetate copolymer, is a commonly used encapsulation material in solar cell production. Its resistance to PID directly determines the product quality and lifespan of PV modules. Therefore, improving the PID resistance of EVA resin, thereby extending the lifespan of PV modules, is a pressing issue that needs to be addressed.

[0003] Chinese invention patent CN108034372A discloses a method for preparing an EVA encapsulation material resistant to potential-induced degradation (PID). This patent enhances the anti-PID performance of EVA by reducing the VA content, decreasing the acetic acid content, and adding a sodium ion-absorbing complex. However, free acetate ions still act as conductive ions, accelerating battery corrosion. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the defects of poor anti-PID performance of EVA resin and short service life of photovoltaic modules in the prior art, and to provide a zirconium magnesium aluminum material, its preparation method and application.

[0005] The technical problem to be solved by the present invention is achieved through the following technical solution.

[0006] This invention provides a zirconium-magnesium-aluminum material, the raw material composition of which includes zirconium, magnesium, aluminum and phosphate, and its structural formula is Zr. x Mg y Al z (PO4) m Where x+z=1.5, y=1, m=(4x+2y+3z) / 3.

[0007] This invention also provides a method for preparing zirconium-magnesium-aluminum material, which includes the following steps:

[0008] Add phosphoric acid solution to a mixed nitrate solution to form Zr. x Mg y Al z (PO4) m Adjust the pH to 3-4 and carry out the aging reaction;

[0009] The mixed nitrate solution contains zirconium ions, magnesium ions, aluminum ions, and nitrate ions; the sum of the concentrations of zirconium ions and aluminum ions in the mixed nitrate solution is 1.5 mol / L.

[0010] Wherein, x, y, z and m satisfy x+z=1.5, y=1, m=(4x+2y+3z) / 3.

[0011] In this invention, the concentration of magnesium ions in the mixed nitrate solution can be 0.5-2 mol / L, for example, 1 mol / L. When the magnesium ion concentration exceeds 2.3 mol / L, the magnesium ions will precipitate as magnesium nitrate.

[0012] In this invention, the concentration of the phosphoric acid solution can be 1-3 mol / L, for example, 2 mol / L.

[0013] In this invention, after adding the phosphoric acid solution, the mixture is generally stirred thoroughly.

[0014] In this invention, pH adjustment is generally achieved by adding a buffer solution dropwise; the buffer solution is, for example, a sodium hydroxide-sodium bicarbonate buffer solution.

[0015] In this invention, preferably, the pH is, for example, 3, 3.5, 3.7 or 4.

[0016] In this invention, the aging reaction temperature can be 75-85°C, for example, 80°C.

[0017] In this invention, the aging reaction time can be 8-10 hours, for example, 9 hours or 10 hours.

[0018] In this invention, after the aging reaction is completed, filtration is generally performed to obtain a precipitate. Preferably, the precipitate needs to be washed, dried and calcined.

[0019] The washing process is generally carried out by vacuum filtration.

[0020] The washing process typically involves using deionized water.

[0021] The washing process typically continues until the washing solution becomes neutral.

[0022] The drying process is generally carried out using a vacuum oven.

[0023] The drying time can be 4-5 hours.

[0024] Preferably, the moisture content after drying is ≤1%.

[0025] The roasting temperature can be 450-550℃, for example, 500℃.

[0026] The roasting time can be 20-30 hours, for example, 25 hours, 28 hours or 30 hours.

[0027] The present invention also provides a zirconium-magnesium-aluminum material prepared by the preparation method described above.

[0028] The present invention also provides an encapsulating film, the raw material composition of which comprises zirconium magnesium aluminum material as described above.

[0029] In some preferred embodiments of the present invention, the encapsulating film comprises zirconium magnesium aluminum material, EVA resin, tert-butyl peroxyisopropyl carbonate and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] as described above.

[0030] In some preferred embodiments of the present invention, the encapsulating film comprises the following components by weight fraction:

[0031] 0.2 parts of zirconium-magnesium-aluminum material;

[0032] 98.8 parts of EVA resin;

[0033] 0.5 parts of tert-butyl peroxide;

[0034] 0.5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid].

[0035] In this invention, preferably, the method for preparing the encapsulating film includes premixing the raw material composition, melt extrusion, casting into a film, cooling, slitting, and winding.

[0036] The present invention also provides an application of the encapsulating film described above in photovoltaic modules.

[0037] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0038] The reagents and raw materials used in this invention are all commercially available.

[0039] The positive and progressive effects of this invention are as follows: This invention provides a zirconium-magnesium-aluminum material, its preparation method and application. The encapsulating film made from the obtained zirconium-magnesium-aluminum material can improve the anti-PID performance of EVA resin, thereby improving the service life of photovoltaic modules. Attached Figure Description

[0040] Figure 1 The image shown is a scanning electron microscope (SEM) image of the zirconium-magnesium-aluminum material obtained in Example 1. Detailed Implementation

[0041] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0042] Example 1

[0043] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0044] (1) Prepare a mixed solution of zirconium, magnesium, and aluminum nitrates and maintain a concentration of c. 镁 =1 mol / L, c 锆 =1 mol / L, c 铝 =0.5mol / L;

[0045] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0046] (3) The pH of the solution was brought to 3 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 8 hours, and the precipitate was obtained by filtration.

[0047] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0048] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 20 hours.

[0049] The scanning electron microscope image of the zirconium-magnesium-aluminum material obtained in Example 1 is shown below. Figure 1 As shown.

[0050] Example 2

[0051] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0052] (1) Prepare a mixed solution of zirconium, magnesium, and aluminum nitrates and maintain a concentration of c. 镁 =1 mol / L, c 锆 =0.2mol / L, c 铝 =1.3 mol / L;

[0053] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0054] (3) The pH of the solution was adjusted to 3.7 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 9 hours, and the precipitate was obtained by filtration.

[0055] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0056] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 30 hours.

[0057] Example 3

[0058] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0059] (1) Prepare a mixed solution of zirconium and magnesium nitrates and maintain a concentration of c. 镁 =1 mol / L, c 锆 =1.5mol / L;

[0060] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0061] (3) The pH of the solution was adjusted to 3.5 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 10 hours, and the precipitate was obtained by filtration.

[0062] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0063] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 25 hours.

[0064] Example 4

[0065] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0066] (1) Prepare a mixed solution of zirconium and aluminum nitrates and maintain a concentration of c. 镁 =1 mol / L, c 铝 =1.5mol / L;

[0067] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0068] (3) The pH of the solution was brought to 4 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 9 hours, and the precipitate was obtained by filtration.

[0069] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0070] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 28 hours.

[0071] Comparative Example 1

[0072] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0073] (1) Prepare a mixed solution of zirconium, magnesium, and aluminum nitrates and maintain a concentration of c. 镁 =1 mol / L, c 锆 =1 mol / L, c 铝 =1 mol / L;

[0074] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0075] (3) The pH of the solution was brought to 3 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 8 hours, and the precipitate was obtained by filtration.

[0076] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0077] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 20 hours.

[0078] Comparative Example 2

[0079] A zirconium-magnesium-aluminum material, the preparation method of which includes the following steps:

[0080] (1) Prepare a mixed solution of zirconium, magnesium, and aluminum nitrates and maintain a concentration of c. 镁 =1 mol / L, c 锆 =1 mol / L, c 铝 =0.5mol / L;

[0081] (2) Then add 2 mol / L phosphoric acid solution and stir thoroughly;

[0082] (3) The pH of the solution was brought to 5 by adding sodium hydroxide-sodium bicarbonate buffer solution, heated to 80°C and aged for 8 hours, and the precipitate was obtained by filtration.

[0083] (4) The precipitate was filtered and washed with deionized water until neutral. It was then dried in a vacuum oven for 4-5 hours until the moisture content was ≤1%.

[0084] (5) The zirconium-magnesium-aluminum material was obtained by calcining at 500℃ for 20 hours.

[0085] Example 1

[0086] The encapsulating film is composed of the following substances: 0.2 parts of the zirconium-magnesium-aluminum material prepared in Examples 1-4 and Comparative Examples 1-2; 98.8 parts of EVA resin as the resin matrix; 0.5 parts of tert-butyl peroxyisopropyl carbonate; and 0.5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The above-mentioned raw material composition for the encapsulating film is premixed, melt-extruded, cast into a film, cooled, slit, and wound to prepare the encapsulating film. The light transmittance and power attenuation rate of the film are then tested.

[0087] The rolled-up film was cut to the size of the solar photovoltaic module, and stacked in the structural order of glass / EVA film / cell / ordinary EVA film / backsheet. Vacuum was then applied and laminated at 145°C for 5 minutes and 12 minutes to obtain the photovoltaic module. PID experiments were then conducted on the photovoltaic module.

[0088] The transmittance was tested using a UV-Vis-NIR spectrophotometer. The film thickness was 0.45 mm. The transmittance was measured according to GB / T 2410-2008.

[0089] The photovoltaic module PID test was conducted according to IEC TS 62804-1:2015, with the test conditions tightened to 85℃, 85%RH, and an external negative 1500V constant DC voltage. After 192 hours, the power attenuation of the photovoltaic module before and after the PID test was measured, and the test results of the encapsulation material were obtained in Table 1.

[0090] Table 1

[0091]

[0092] According to the data in Table 1, the encapsulating film made from the zirconium magnesium aluminum material of the present invention can be used to prepare photovoltaic modules with a power attenuation rate of no more than 2.05%, which greatly improves the anti-PID performance compared with photovoltaic modules made from pure EVA film.

[0093] The only difference between Comparative Example 1 and Example 1 is that the concentration of aluminum ions in Comparative Example 1 is 1 mol / L, making the sum of the concentrations of aluminum ions and zirconium ions 2 mol / L instead of 1.5 mol / L. As a result, Comparative Example 1 exhibits lower light transmittance and reduced resistance to PID compared to Example 1. Therefore, it can be seen that the sum of the concentrations of aluminum ions and zirconium ions affects both light transmittance and PID resistance.

[0094] The only difference between Comparative Example 2 and Example 1 is that Comparative Example 2 had a pH of 5, instead of the range of 3-4. This resulted in a decrease in transmittance and PID resistance in Comparative Example 2 compared to Example 1. Therefore, the adjusted pH level affects both transmittance and PID resistance.

Claims

1. An encapsulating film, characterized in that, Its raw material composition includes zirconium-magnesium-aluminum material, which satisfies the following conditions a and b; a. The raw material composition of the zirconium magnesium aluminum material includes zirconium, magnesium, aluminum and phosphoric acid, and the structural formula of the zirconium magnesium aluminum material is Zr x Mg y Al z (PO4) m ; wherein x+z=1.5, y=1, m=(4x+2y+3z) / 3; b. The preparation method of the zirconium-magnesium-aluminum material includes the following steps: To the mixed nitrate solution, phosphoric acid solution is added to form Zr x Mg y Al z (PO4) m , adjust pH to 3-4, and perform aging reaction; The mixed nitrate solution contains zirconium ions, magnesium ions, aluminum ions, and nitrate ions; the sum of the concentrations of zirconium ions and aluminum ions in the mixed nitrate solution is 1.5 mol / L. Wherein, x, y, z and m satisfy x+z=1.5, y=1, m=(4x+2y+3z) / 3.

2. The encapsulating film as described in claim 1, characterized in that, In condition b, the concentration of magnesium ions in the mixed nitrate solution is 0.5-2 mol / L; And / or, in condition b, the concentration of the phosphoric acid solution is 1-3 mol / L.

3. The encapsulating film as described in claim 1, characterized in that, In condition b, the concentration of magnesium ions in the mixed nitrate solution is 1 mol / L; and / or, in condition b, the concentration of the phosphoric acid solution is 2 mol / L.

4. The encapsulating film as described in claim 1, characterized in that, In condition b, after adding the phosphoric acid solution, the mixture is stirred. And / or, in condition b, the pH adjustment is performed by adding a buffer solution dropwise; And / or, in condition b, the pH is 3, 3.5, 3.7 or 4.

5. The encapsulating film as described in claim 4, characterized in that, In condition b, the buffer solution is a sodium hydroxide-sodium bicarbonate buffer solution.

6. The encapsulating film as described in claim 1, characterized in that, In condition b, the aging reaction temperature is 75-85℃; And / or, in condition b, the aging reaction time is 8-10 hours; And / or, in condition b, after the aging reaction is completed, filtration is performed to obtain the precipitated product.

7. The encapsulating film as described in claim 1, characterized in that, In condition b, the aging reaction temperature is 80°C; and / or, in condition b, the aging reaction time is 9 hours or 10 hours.

8. The encapsulating film as described in claim 6, characterized in that, The precipitated products need to be washed, dried and roasted.

9. The encapsulating film as described in claim 8, characterized in that, The washing process continues until the washing solution is neutral. And / or, the drying time is 4-5 hours; And / or, the moisture content after drying is ≤1%; And / or, the calcination temperature is 450-550°C; And / or, the roasting time is 20-30 hours.

10. The encapsulating film as described in claim 8, characterized in that, The roasting temperature is 500°C; and / or the roasting time is 25 hours, 28 hours, or 30 hours.

11. The application of an encapsulating film as described in any one of claims 1-10 in a photovoltaic module.

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