Lead adsorption material, preparation method thereof and application of lead adsorption material in perovskite photoelectric device packaging

Abstract

The invention discloses a lead adsorption material, a preparation method thereof and application of the lead adsorption material in perovskite photoelectric device packaging, and belongs to the technical field of perovskite photoelectric device packaging. Two novel lead ion adsorption materials are prepared by taking 2-phosphonic-1, 2, 4-tricarboxylic acid butane or 2, 3-dimercaptosuccinic acid matched with polyvinyl alcohol and glycerol as raw materials. The prepared lead adsorption material is suitable for various situations needing to control lead release, for example, lead leakage in a perovskite photoelectric device is controlled, one of the two lead adsorption materials is integrated into a traditional packaging layer of the device to form a composite packaging layer, the impact strength and the waterproof and anti-oxidation capacity of the photoelectric device are enhanced by utilizing the traditional packaging layer, and the photoelectric device is prevented from being damaged. According to the perovskite photoelectric device, toxic lead in the damaged photoelectric device is prevented from being exposed to the environment through the lead adsorption layer made of the lead adsorption material, the lead adsorption layer still has excellent lead adsorption capacity after long-term temperature circulation, the service life of the perovskite photoelectric device can be effectively prolonged, the stability of the perovskite photoelectric device can be effectively improved, and potential pollution of the perovskite photoelectric device to the environment is reduced.

Description

Technical Field

[0001] This invention belongs to the field of perovskite optoelectronic device packaging technology, specifically relating to a lead adsorption material and its preparation method and application in perovskite optoelectronic device packaging. Background Technology

[0002] Metal halide perovskite materials, with their unique optoelectronic properties, have become an ideal choice for high-efficiency, low-cost optoelectronic devices, and related technological research continues to deepen. However, current devices still face technological bottlenecks, with lead being a key issue. As an essential component for achieving high efficiency and stability, lead's high toxicity and non-biodegradable nature make it prone to bioaccumulation through the food chain, harming the ecological environment and human health, and seriously hindering commercialization.

[0003] Most current lead removal methods are mainly aimed at a single type of optoelectronic device (i.e., rigid perovskite solar cells), and require adjustment of key components by means of doping precursor solutions or modifying interfaces, and introduction of new processes (such as spin coating). These changes not only make the device structure and fabrication process more complex, but also increase production costs. Summary of the Invention

[0004] To address the environmental toxicity and pollution risks of lead in perovskite optoelectronic devices, this invention proposes a lead adsorbent material, its preparation method, and its application in the encapsulation of perovskite optoelectronic devices. This lead adsorbent material is suitable for various situations requiring controlled lead release, such as controlling lead leakage in perovskite optoelectronic devices. By integrating this lead adsorbent material into the conventional encapsulation layer of the device to form a composite encapsulation layer, the conventional encapsulation layer enhances the impact resistance and waterproof / oxidation protection of the optoelectronic device, while the lead adsorbent layer prevents toxic lead from damaged optoelectronic devices from being exposed to the environment. This effectively improves the lifespan and stability of perovskite optoelectronic devices and reduces their potential environmental pollution.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] One of the technical solutions of the present invention is to provide a lead adsorption material, the raw materials of which include: lead adsorption additive material, polyvinyl alcohol (PVA) and glycerol; the lead adsorption additive material is 2-phosphono-1,2,4-tricarboxylate butane (PBTCA) or 2,3-dimercaptosuccinic acid (DMSA).

[0007] Polyvinyl alcohol has good film-forming properties and light transmittance, which enables the prepared film to be well applied to perovskite solar cells. Glycerol, as a plasticizer, improves the flexibility and low-temperature resistance of the film. After PBTCA is modified into PVA, the phosphoric acid contained in its molecule and the ester group generated by the reaction with PVA have a strong coordination ability for lead, which endows the film with good lead adsorption capacity.

[0008] Preferably, the ratio of 2-phosphono-1,2,4-tricarboxylic acid butane, polyvinyl alcohol and glycerol is 4 mL:3.75 g:0.5 mL; and the ratio of 2,3-dimercaptosuccinic acid, polyvinyl alcohol and glycerol is 0.15 g:3.75 g:0.5 mL.

[0009] The second technical solution of the present invention provides a method for preparing the above-mentioned lead adsorbent material, comprising the following steps: dissolving polyvinyl alcohol in water, adding lead adsorbent additive material and stirring evenly to obtain a mixed solution 1, continuing to add glycerol, stirring evenly to obtain a mixed solution 2, and obtaining the lead adsorbent material after the mixed solution 2 is solidified.

[0010] Preferably, the polyvinyl alcohol is heated during dissolution to increase the dissolution rate.

[0011] Preferably, the curing step includes: first treating the mixed solution 2 with ultraviolet ozone, and then drying it to constant weight to complete the curing.

[0012] More preferably, the ultraviolet ozone treatment is performed using an ultraviolet ozone cleaner.

[0013] More preferably, the drying temperature is 50°C.

[0014] The third technical solution of the present invention provides an application of the above-mentioned lead adsorption material in the packaging of perovskite optoelectronic devices.

[0015] Preferably, the specific steps of packaging the perovskite optoelectronic device include: superimposing the lead adsorption material with the conventional packaging layer of the perovskite optoelectronic device to obtain a composite packaging layer; tightly attaching the conventional packaging layer side of the composite packaging layer to the upper and lower sides of the perovskite optoelectronic device; and then performing edge packaging to complete the packaging of the perovskite optoelectronic device.

[0016] More preferably, the method for preparing the composite encapsulation layer includes: constructing the conventional encapsulation layer on a substrate, then coating the conventional encapsulation layer with a slurry containing lead adsorbent material, and obtaining the composite encapsulation layer after drying and curing.

[0017] Optionally, the materials of the conventional encapsulation layer include, but are not limited to, ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE), polyvinyl fluoride composite film (TPT), glass, epoxy resin, polydimethylsiloxane (PDMS), or silicone rubber.

[0018] The beneficial technical effects of the present invention are as follows:

[0019] This invention utilizes 2-phosphono-1,2,4-tricarboxylate butane or 2,3-dimercaptosuccinic acid, polyvinyl alcohol, and glycerol as raw materials to prepare two novel lead ion adsorbent materials. The prepared lead adsorbent materials are suitable for various situations requiring controlled lead release, such as controlling lead leakage in perovskite optoelectronic devices. By integrating one of the two lead adsorbent materials into the conventional encapsulation layer of the device to form a composite encapsulation layer, the conventional encapsulation layer enhances the impact resistance and waterproof / oxidation protection of the optoelectronic device, while the lead adsorbent layer prevents toxic lead from damaged optoelectronic devices from being exposed to the environment. This effectively improves the lifespan and stability of perovskite optoelectronic devices and reduces their potential environmental pollution.

[0020] The manufacturing process provided by this invention is simple and low-cost. It is not only applicable to rigid perovskite optoelectronic devices, but also to lead leakage prevention of flexible perovskite optoelectronic devices. Furthermore, it can maintain a high lead adsorption rate even after alternating hot and cold cycling experiments. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a schematic diagram of the encapsulation of a perovskite solar cell in this invention.

[0023] Figure 2 This is a schematic diagram of temperature changes in the temperature cycling experiment of this invention.

[0024] Figure 3 The results show the long-term operational stability test results of the pin-type rigid device obtained in Embodiment 2 and Comparative Example 1 of this invention.

[0025] Figure 4 The results show the long-term operational stability test results of the nip-type rigid device obtained in Embodiment 2 and Comparative Example 1 of this invention.

[0026] Figure 5 The results show the long-term operational stability test results of the pin-type flexible devices obtained in Embodiment 2 and Comparative Example 1 of this invention.

[0027] Figure 6 The results show the long-term operational stability test results of the pin-type rigid device obtained in Example 4 and Comparative Example 1 of this invention.

[0028] Figure 7The results show the long-term operational stability test results of the nip-type rigid device obtained in Example 4 and Comparative Example 1 of this invention.

[0029] Figure 8 The results show the long-term operational stability test results of the pin-type flexible devices obtained in Example 4 and Comparative Example 1 of this invention. Detailed Implementation

[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0031] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0032] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0033] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention.

[0034] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0035] The embodiments and comparative examples of this invention all use silicone sealant as an example. The perovskite solar cells in the embodiments and comparative examples of this invention have an area of ​​2.5 × 2.5 cm. 2 The packaging structure diagram is as follows: Figure 1 As shown (the top and bottom sides of the perovskite solar cell are tightly bonded to the lead adsorption coating applied to the perovskite solar cell, and sealant is applied around the device to achieve edge encapsulation). Both nip and pin types of perovskite solar cell devices were used to test the versatility of the adsorption coating. This included a pin-type rigid device with the structure: ITO / 4PADCB / FA. 0.98 MA 0.02 PbI3 / LiF / C 60 / BCP / Ag; nip-type rigid device, structure: ITO / SnO2 / FA 0.98 MA 0.02 PbI3 / oF-PEAI / Spiro-OMeTAD / MoO3 / Ag, and pin-type flexible devices with the structure: PEN / ITO / 4PADCB / FA 0.98 MA 0.02 PbI3 / LiF / C 60 / BCP / Ag.

[0036] In this embodiment of the invention, the equipment used for "ultraviolet ozone treatment" is an ultraviolet ozone cleaner, specifically model UC100-SE from Jiangsu Leibo Scientific Instruments Co., Ltd.

[0037] Example 1

[0038] 1. Add 3.75g of polyvinyl alcohol to 15mL of deionized water and heat to dissolve at 90℃ to obtain a polyvinyl alcohol aqueous solution.

[0039] 2. Add 4 mL of PBTCA solution (50 wt%) to the polyvinyl alcohol aqueous solution obtained in step 1, heat and stir until homogeneous. The heating temperature is 90 °C to obtain mixed solution 1.

[0040] 3. Add 0.5 mL of glycerol to the mixed solution 1 obtained in step 2 and stir well. Let it stand to remove bubbles to obtain mixed solution 2.

[0041] 4. After cleaning and drying the encapsulation material (PDMS with a thickness of 0.5 mm), lay it flat on the glass substrate. After UV ozone treatment for 10 min, apply the mixed solution 2 obtained in step 3 to the encapsulation material with a coating thickness of 0.62 mm. Place it in a drying oven and heat it at 50°C until the weight no longer changes (i.e., dry to constant weight) to obtain the composite encapsulation layer.

[0042] 5. Remove the composite encapsulation layer (i.e. lead adsorption coating) obtained in step 4 from the glass substrate and transfer it to the perovskite solar cell. Then, perform edge encapsulation on the perovskite optoelectronic device (the top and bottom sides of the perovskite solar cell are tightly bonded to the composite encapsulation layer, the PDMS side is bonded to the perovskite solar cell, and sealant is applied around the device to complete the edge encapsulation).

[0043] Example 2 (The only difference from Example 1 is that the coating thickness of the mixed solution 2 in step 3 is 0.70 mm)

[0044] 1. Add 3.75g of polyvinyl alcohol to 15mL of deionized water and heat to dissolve at 90℃ to obtain a polyvinyl alcohol aqueous solution.

[0045] 2. Add 4 mL of PBTCA solution (50 wt%) to the polyvinyl alcohol aqueous solution obtained in step 1, heat and stir until homogeneous. The heating temperature is 90 °C to obtain mixed solution 1.

[0046] 3. Add 0.5 mL of glycerol to the mixed solution 1 obtained in step 2 and stir well. Let it stand to remove bubbles to obtain mixed solution 2.

[0047] 4. After cleaning and drying the encapsulation material (PDMS with a thickness of 0.5 mm), lay it flat on the glass substrate. After UV ozone treatment for 10 min, apply the mixed solution 2 obtained in step 3 to the encapsulation material with a coating thickness of 0.70 mm. Place it in a drying oven and heat it at 50°C until the weight no longer changes (i.e., dry to constant weight) to obtain the composite encapsulation layer.

[0048] 5. Remove the composite encapsulation layer (i.e. lead adsorption coating) obtained in step 4 from the glass substrate and transfer it to the perovskite solar cell. Then, perform edge encapsulation on the perovskite optoelectronic device (the top and bottom sides of the perovskite solar cell are tightly bonded to the composite encapsulation layer, the PDMS side is bonded to the perovskite solar cell, and sealant is applied around the device to complete the edge encapsulation).

[0049] Example 3 (The only difference from Example 1 is that the coating thickness of the mixed solution 2 in step 3 is 0.785 mm)

[0050] 1. Add 3.75g of polyvinyl alcohol to 15mL of deionized water and heat to dissolve at 90℃ to obtain a polyvinyl alcohol aqueous solution.

[0051] 2. Add 4 mL of PBTCA solution (50 wt%) to the polyvinyl alcohol aqueous solution obtained in step 1, heat and stir until homogeneous. The heating temperature is 90 °C to obtain mixed solution 1.

[0052] 3. Add 0.5 mL of glycerol to the mixed solution 1 obtained in step 2 and stir well. Let it stand to remove bubbles to obtain mixed solution 2.

[0053] 4. After cleaning and drying the encapsulation material (PDMS with a thickness of 0.5 mm), lay it flat on the glass substrate. After UV ozone treatment for 10 min, apply the mixed solution 2 obtained in step 3 to the encapsulation material with a coating thickness of 0.785 mm. Place it in a drying oven and heat it at 50°C until the weight no longer changes (i.e., dry to constant weight) to obtain the composite encapsulation layer.

[0054] 5. Remove the composite encapsulation layer (i.e. lead adsorption coating) obtained in step 4 from the glass substrate and transfer it to the perovskite solar cell. Then, perform edge encapsulation on the perovskite optoelectronic device (the top and bottom sides of the perovskite solar cell are tightly bonded to the composite encapsulation layer, the PDMS side is bonded to the perovskite solar cell, and sealant is applied around the device to complete the edge encapsulation).

[0055] Example 4

[0056] 1. Add 3.75g of polyvinyl alcohol to 15mL of deionized water and heat to dissolve at 90℃ to obtain a polyvinyl alcohol aqueous solution.

[0057] 2. Add 0.15g of DMSA to the polyvinyl alcohol aqueous solution obtained in step 1, heat and stir until homogeneous. The heating temperature is 90℃ to obtain mixed solution 1.

[0058] 3. Add 0.5 mL of glycerol to the mixed solution 1 obtained in step 2 and stir well. Let it stand to remove bubbles to obtain mixed solution 2.

[0059] 4. After cleaning and drying the encapsulation material (PDMS with a thickness of 0.5 mm), lay it flat on the glass substrate. After UV ozone treatment for 10 min, apply the mixed solution 2 obtained in step 3 to the encapsulation material with a coating thickness of 0.70 mm. Place it in a drying oven and heat it at 50°C until the weight no longer changes (i.e., dry to constant weight) to obtain the composite encapsulation layer.

[0060] 5. Remove the composite encapsulation layer (i.e. lead adsorption coating) obtained in step 4 from the glass substrate and transfer it to the perovskite solar cell. Then, perform edge encapsulation on the perovskite optoelectronic device (the top and bottom sides of the perovskite solar cell are tightly bonded to the composite encapsulation layer, the PDMS side is bonded to the perovskite solar cell, and sealant is applied around the device to complete the edge encapsulation).

[0061] Comparative Example 1

[0062] Compared to Example 1, the encapsulation layer material is only PDMS. After transferring 0.5 mm PDMS to the top and bottom sides of the perovskite solar cell, sealant is applied around the edges for edge encapsulation.

[0063] To test lead leakage of the encapsulated device under worst-case conditions, a falling ball test was used to simulate severe weather such as hail. After physical impact, the encapsulation layer was cut with a knife to obtain a damaged perovskite solar cell encapsulated device. The damaged device was used to simulate rainfall and water immersion tests.

[0064] Drop ball test: A 400g solid steel ball was dropped 20cm above the packaged structure device, causing the battery to shatter.

[0065] Simulated rainfall experiment: The damaged device was placed in a funnel at a 20° angle. Deionized water was dripped above the device at a rate of 31.25 L / h for 1.5 hours. The contaminated water at the bottom of the funnel was collected, and the lead ion concentration in the water was tested. To simulate a harsh natural environment, tests were conducted at pH 4.2 and pH 4.2 with the presence of Ca. 2+ Mg 2+ Lead leakage rate in a water droplet experiment under competitive ion (2 ppm) conditions.

[0066] Immersion test: The damaged device was placed in 50 mL of deionized water, and the lead ion concentration in the polluted water was measured. To simulate a harsh natural environment, tests were conducted at pH 4.2 and pH 4.2 with the presence of Ca. 2+ Mg 2+ Lead leakage rate in immersion experiments under competitive ion (2 ppm) conditions.

[0067] Temperature cycling experiment: The packaged pin-type flexible and rigid devices are placed in a temperature cycling device. The temperature cycling diagram is shown below. Figure 2 As shown, each cycle lasts three hours. After 160 cycles, the packaged device is destroyed (using the same method as above), and the resulting damaged device is subjected to a water immersion test.

[0068] The amount of lead leakage was determined by measuring the concentration of lead ions in contaminated water during simulated rainfall and immersion experiments using a Shimadzu AA-7800 atomic absorption spectrometer.

[0069] The power conversion efficiency (PCE) of the packaged perovskite solar cell device was determined using a Keithley 2400 spectrometer under nitrogen-filled glove box conditions and with a light intensity of 100 mW·cm⁻¹. -2 The AM1.5G light source simulates sunlight, and the effective area of ​​the active layer is 0.0625 cm². 2 .

[0070] The results of the lead leakage tests are shown in Tables 1 to 6.

[0071] The long-term operational stability test results of the coatings encapsulated with different perovskite solar cells in Example 2 and Comparative Example 1 are shown below. Figures 3-5 .

[0072] The long-term operational stability test results of the coatings encapsulated with different perovskite solar cells in Example 4 and Comparative Example 1 are shown in the figure. Figures 6-8 .

[0073] Table 1. Photoelectric conversion efficiency (PCE) of NIP and pin-type rigid devices before and after packaging.

[0074]

[0075] Table 2 Lead leakage of NIP type rigid-fragmented devices in immersion tests

[0076]

[0077] Table 3 Lead leakage of pin-type rigid broken packaged devices in immersion tests

[0078]

[0079] Table 4. Lead leakage of pin-type flexible and rigid damaged packages in immersion tests after 160 temperature cycles.

[0080]

[0081] Table 5. Lead leakage of pin-type flexible and rigid damaged packages in immersion tests after 80 temperature cycles.

[0082]

[0083] Table 6 Lead leakage of NIP and pin-type rigid-fragmented devices in simulated rainfall experiments.

[0084]

[0085] From Tables 1 to 6 and Figures 3-8 It is known that the new coating of the present invention has good compatibility, while retaining the advantages of the original encapsulation material and reducing the risk of lead leakage after device damage. The film still has good lead adsorption capacity after temperature cycling, and improves the stability of the battery on the basis of the PDMS layer. Low-pollution and high-stability perovskite solar cells can be obtained without increasing the device fabrication steps.

[0086] In summary, this invention provides two lead-adsorption coatings based on modified polyvinyl alcohol (PVA). These two coatings can be combined with conventional encapsulation materials for perovskite solar cells to construct a universally applicable functional encapsulation system for lead adsorption. A lead-adsorption coating precursor solution is obtained by functionalizing PVA with a modifier, and then a highly uniform coating is formed on the surface of the encapsulation material via a blade coating method. This coating exhibits excellent optical transmittance and efficient lead adsorption performance. Experiments show that the lead leakage of damaged perovskite solar devices encapsulated with this coating is significantly reduced, and the coating itself has no negative impact on cell performance. Therefore, applying this type of functionalized encapsulation material to perovskite solar cells can effectively achieve stable encapsulation with low lead leakage rates.

[0087] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A lead adsorbent material, characterized by, The raw materials include: lead adsorption additive material, polyvinyl alcohol and glycerol; the lead adsorption additive material is 2-phosphono-1,2,4-tricarboxylic acid butane or 2,3-dimercaptosuccinic acid.

2. The lead adsorbent material of claim 1, wherein, The ratio of 2-phosphono-1,2,4-tricarboxylic acid butane, polyvinyl alcohol, and glycerol is 4 mL:3.75 g:0.5 mL; the ratio of 2,3-dimercaptosuccinic acid, polyvinyl alcohol, and glycerol is 0.15 g:3.75 g:0.5 mL.

3. A method for preparing the lead adsorbent material according to claim 1 or 2, characterized in that, The process includes the following steps: dissolving polyvinyl alcohol in water, adding lead adsorbent additive material and stirring until homogeneous to obtain mixed solution 1, continuing to add glycerol and stirring until homogeneous to obtain mixed solution 2, and then curing mixed solution 2 to obtain the lead adsorbent material.

4. The method for preparing the lead adsorbent material according to claim 3, characterized in that, The polyvinyl alcohol is heated during dissolution.

5. The method for preparing the lead adsorbent material according to claim 3, characterized in that, The curing steps include: first, treating the mixed solution 2 with ultraviolet ozone, and then drying it to a constant weight to complete the curing.

6. The application of the lead adsorbent material according to claim 1 or 2 in the packaging of perovskite optoelectronic devices.

7. The application according to claim 6, characterized in that, The specific steps for packaging the perovskite optoelectronic device include: superimposing the lead adsorption material with the traditional packaging layer of the perovskite optoelectronic device to obtain a composite packaging layer; tightly attaching the traditional packaging layer side of the composite packaging layer to the upper and lower sides of the perovskite optoelectronic device; and then performing edge packaging to complete the packaging of the perovskite optoelectronic device.

8. The application according to claim 7, characterized in that, The preparation steps of the composite encapsulation layer include: constructing the conventional encapsulation layer on a substrate, then coating the conventional encapsulation layer with a slurry containing lead adsorbent material, and obtaining the composite encapsulation layer after drying and curing.

9. The application according to claim 7, characterized in that, The materials of the conventional encapsulation layer include ethylene-vinyl acetate copolymer, ethylene-octene copolymer, polyvinyl fluoride composite film, glass, epoxy resin, polydimethylsiloxane, or silicone rubber.

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