A green and efficient method for separating waste copper-indium-gallium-selenium solar thin film cells

Abstract

The present application relates to solid waste green recycling technology field, specifically to a kind of green efficient separation of waste copper indium gallium selenide solar thin film battery method, comprising: waste copper indium gallium selenide solar thin film battery is curled and fixed, then remove fixed, battery is cut into 2×2cm size square piece, put into beaker with deionized water and carry out ultrasonic;After a certain amount of deionized water is added in transient pressure difference separator, put into battery piece, open transient pressure difference separator when temperature, pressure reaches certain condition.The waste copper indium gallium selenide solar thin film battery separation product is obtained.The present application can be in short time to waste copper indium gallium selenide solar thin film battery efficient separation, so that CIGS layer is exposed, solves the problem of large energy consumption, pollution, CIGS layer leaching difficulty, valuable metal enrichment difficulty etc. in waste copper indium gallium selenide solar thin film battery recycling process, its process is green, efficient, simple and suitable for large-scale industrial application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid waste green recycling treatment, in particular to a method for green and efficient separation of waste and old copper-indium-gallium-selenium solar thin film battery. BACKGROUND

[0002] In recent years, the photovoltaic industry has developed rapidly. According to the latest version of the World Energy Statistics Yearbook released by the Energy Research Institute in 2023: solar and wind power generation continues to grow rapidly, setting a new record of 266 gigawatts. Solar power generation accounts for 72% (192 gigawatts) of the increase in power generation. Solar power generation increased by 25%, and renewable energy (excluding hydropower) met 84% of the net increase in power demand. As the main force of the transition from global fossil energy to new energy, the photovoltaic industry can basically maintain a compound growth rate of about 30% per year, and the market continues to rise. At present, crystalline silicon photovoltaic modules still dominate the photovoltaic market, but copper-indium-gallium-selenium solar thin film batteries have more application scenarios, higher photoelectric conversion efficiency, and lower cost preparation process, and other advantages, and the proportion in the photovoltaic market will become larger and larger, and the market share will eventually reach 50%. At that time, a large number of copper-indium-gallium-selenium solar thin film batteries will face retirement. At present, the focus of research is still on the preparation process and performance modification of copper-indium-gallium-selenium solar thin film batteries, and the research on the separation and recovery of copper-indium-gallium-selenium solar thin film batteries is relatively less. If copper-indium-gallium-selenium solar thin film batteries are not separated, it will cause the problem of difficult recovery. According to the existing separation and recovery methods, the separation method has the problems of long separation time, low separation efficiency, high energy consumption, etc., the recovery method has the disadvantages of high energy consumption and serious pollution in fire recovery, and the disadvantages of long leaching time, large reagent consumption and harmful waste liquid in wet recovery. Both fire recovery and wet recovery have the pain point that valuable metals are difficult to enrich.

[0003] In summary, there is an urgent need to develop a green and efficient method for separating waste and old copper-indium-gallium-selenium solar thin film batteries, which can not only solve the problems of long separation time, low separation efficiency, high energy consumption, etc. in the prior art, but also realize the enrichment of valuable metals, providing great convenience for subsequent recycling and utilization. SUMMARY

[0004] In view of the problems in the prior art, the present application provides a method for green and efficient separation of waste and old copper-indium-gallium-selenium solar thin film batteries, which aims to solve the problems of long separation time, low separation efficiency, high energy consumption, etc. in the prior art, and realize the enrichment of valuable metals, providing great convenience for subsequent recycling and utilization.

[0005] In order to achieve the above technical purpose and achieve the above technical effect, the present application is realized by the following technical scheme:

[0006] The application discloses a green and efficient method for separating waste copper indium gallium selenide solar thin film cells.

[0007] S1: winding and fixing the waste copper indium gallium selenide solar thin film cells according to a certain curvature, and keeping the winding state for a certain time;

[0008] S2: removing the fixing in step S1, and unfolding the thin film cells;

[0009] S3: observing the thin film cells unfolded in step S2, cutting the parts with gaps between the stainless steel substrates and upper structures into 2cm-sized cell pieces, and repeating steps S1-S3 for the parts without gaps; × 2cm-sized cell pieces, and repeating steps S1-S3 for the parts without gaps;

[0010] S4: placing the cell pieces into a beaker containing deionized water, placing the beaker in an ultrasonic instrument, and ultrasonically treating for a certain time;

[0011] S5: placing the cell pieces after ultrasonic treatment in step S4 into a transient pressure difference separator, and adding a certain amount of deionized water;

[0012] S6: starting the transient pressure difference separator when the temperature and pressure reach certain conditions;

[0013] S7: collecting the separation products including CIGS-PET layers, stainless steel substrates, EVA and PET, and performing vacuum drying treatment on the collected products.

[0014] Further, the winding curvature of the copper indium gallium selenide solar thin film cells in step S1 ranges from 4m to 50m -1 , and the winding state is kept for 30min.

[0015] Further, the winding curvature ranges from 20m to 50m -1 .

[0016] Further, the parts without gaps in step S3 repeat steps S1-S3, and the winding curvature and the time for keeping the winding state are consistent with those in the first implementation of step S1.

[0017] Further, the ultrasonic treatment time of the cell pieces in deionized water in step S4 is 10-60min.

[0018] Further, the ultrasonic treatment time ranges from 10min to 30min.

[0019] Further, the deionized water is 1-5ml.

[0020] Further, the deionized water is 1-5ml.

[0021] Further, the instantaneous pressure difference separator is opened when the pressure range is 3-6 MPa and the temperature is 100-300 DEG C.

[0022] Further, the instantaneous pressure difference separator is opened when the pressure range is 3-6 MPa and the temperature is 100-300 DEG C.

[0023] Further, the vacuum drying temperature in the step S7 is 50 DEG C, and the drying time is 30 min.

[0024] According to the technical solution, compared with the prior art, the application has the following advantages:

[0025] 1. The application realizes efficient separation of waste copper indium gallium selenium solar thin film battery through instantaneous pressure difference separation technology, and the separation products include CIGS-PET layer, stainless steel substrate, EVA and PET. Compared with the traditional separation method, the separation efficiency is significantly improved, the whole process is green and harmless, and no environmental burden is caused.

[0026] 2. The application realizes efficient separation of waste copper indium gallium selenium solar thin film battery through instantaneous pressure difference separation technology, which provides great convenience for subsequent recycling of valuable metals. The application exposes the GIGS layer, greatly shortens the wet leaching time, saves a large amount of chemical reagents, and reduces the harmful gas and carbon dioxide emissions generated by the separation of EVA and PET. Through the instantaneous pressure difference separation technology, the pollution to the atmosphere, water body and soil is greatly reduced, a new way for green separation and recycling of photovoltaic industry waste is provided, and it has far-reaching significance for environmental protection.

[0027] 3. The application realizes green and efficient separation of waste copper indium gallium selenium solar thin film battery, and the valuable metals such as copper, indium, gallium and selenium element in the battery are enriched, which provides high-quality raw materials for subsequent metal refining and recycling, reduces the demand for raw materials, alleviates the consumption pressure of natural resources, and also reduces the cost of material recycling, which is helpful to promote the sustainable development of upstream and downstream of photovoltaic industry chain.

[0028] 4. Compared with the traditional separation technology, the instantaneous pressure difference separation process has little physical damage to the thin film material, which means that more materials can be recycled and reused, greatly reducing material loss. This is particularly important for high-value copper indium gallium selenium solar thin film batteries, because the production cost of such materials is high. Through the technology, not only the material recycling efficiency can be effectively improved, but also the economic cost of the whole recycling process can be reduced, thereby bringing better economic benefits to enterprises.

[0029] Of course, any product implementing the application does not necessarily need to achieve all the advantages described above. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of 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.

[0031] Figure 1 This is a structural diagram of a waste copper indium gallium selenide thin-film battery.

[0032] Figure 2 SEM characterization of the structure of waste copper indium gallium selenide thin-film batteries;

[0033] Figure 3 This is a diagram showing the separation effect of Example 1;

[0034] Figure 4 This is a diagram showing the separation effect of Example 2;

[0035] Figure 5 This is a diagram showing the separation effect of Example 3;

[0036] Figure 6 This is a diagram showing the separation effect of Example 4;

[0037] Figure 7 This is a diagram showing the separation effect of Comparative Example 1;

[0038] Figure 8 This is a comparison diagram showing the separation effect of Example 2;

[0039] Figure 9 This is a comparison diagram showing the separation effect of Example 3;

[0040] Figure 10 This is a comparison diagram showing the separation effect of Example 4;

[0041] Figure 11 This is a schematic diagram of the overall process of the present invention. Detailed Implementation

[0042] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] Example 1

[0044] Waste copper indium gallium selenide (CIGS) thin-film solar cells were arranged according to a curvature of 20m. -1The film battery is unrolled after being curled and fixed for 30 min. The part of the substrate with a gap from the upper structure is cut into a 2x2 cm battery piece, and the part without a gap is repeated steps S1-S3, with the curling curvature and the time of keeping the curling state being consistent with the above.

[0045] The battery piece is placed in a beaker containing deionized water, and the beaker is placed in an ultrasonic instrument for ultrasonic treatment for 30 min. 5 ml of deionized water is added to the transient pressure difference separator, and the battery piece after ultrasonic treatment is placed in the transient pressure difference separator. The transient pressure difference separator is started when the pressure reaches 6 Mpa and the temperature displays 288℃, and the waste copper indium gallium selenium solar film battery separation products including CIGS-PET layer, stainless steel substrate, EVA between bonding substrate and PET, and PET of packaging substrate are collected (as shown in Figure 3 )。

[0046] The measured mass of the waste copper indium gallium selenium solar film battery 2x2 cm battery piece before separation is 0.2005 g, and the mass of the separation products CIGS-PET layer after separation is 0.0577 g, the mass of the stainless steel substrate is 0.0957 g, the mass of the EVA between the bonding substrate and the PET is 0.0195 g, and the mass of the PET of the packaging substrate is 0.0276 g. It is calculated that the stainless steel substrate, the EVA between the bonding substrate and the PET, and the PET of the packaging substrate account for 71.2% of the mass of the whole battery piece, which effectively enriches the valuable metals and selenium elements in the battery piece, and achieves the purpose of exposing the CIGS layer, and the separation effect is shown in Figure 3 .

[0047] Example 2

[0048] The waste copper indium gallium selenium solar film battery is curled according to a curvature of 30 m -1 The film battery is unrolled after being curled and fixed for 30 min. The part of the substrate with a gap from the upper structure is cut into a 2x2 cm battery piece, and the part without a gap is repeated steps S1-S3, with the curling curvature and the time of keeping the curling state being consistent with the above.

[0049] The battery piece is placed in a beaker containing deionized water, and the beaker is placed in an ultrasonic instrument for ultrasonic treatment for 25 min. 4 ml of deionized water is added to the transient pressure difference separator, and the battery piece after ultrasonic treatment is placed in the transient pressure difference separator. The transient pressure difference separator is started when the pressure reaches 5 Mpa and the temperature displays 241℃, and the waste copper indium gallium selenium solar film battery separation products including CIGS-PET layer, stainless steel substrate, EVA between bonding substrate and PET, and PET of packaging substrate are collected (as shown in Figure 4 ).

[0050] The measured mass of the waste Cu-In-Ga-Se solar thin film battery 2x2cm before separation was 0.2018g, the mass of the separation product CIGS-PET layer after separation was 0.0573g, the mass of the stainless steel substrate was 0.0967g, the mass of the EVA between the bonding substrate and the PET was 0.0197g, and the mass of the PET of the encapsulation substrate was 0.0281g. The calculated mass of the stainless steel substrate, the EVA between the bonding substrate and the PET, and the PET of the encapsulation substrate accounted for 71.6% of the mass of the whole battery, which effectively enriched the valuable metals and selenium elements in the battery, and at the same time achieved the purpose of exposing the CIGS layer, and the separation effect is shown in Figure 4 .

[0051] Example 3

[0052] The waste Cu-In-Ga-Se solar thin film battery was rolled according to a curvature of 40m -1 After 30min of maintaining the rolled state, the fixing was removed, and the thin film battery was unfolded. The part of the substrate with a gap from the upper structure was cut into a 2x2cm battery, and the part without a gap was repeated steps S1-S3, and the rolling curvature and the time of maintaining the rolled state were consistent with the above.

[0053] The battery was placed in a beaker containing deionized water, and the beaker was placed in an ultrasonic instrument for 20min. 3ml of deionized water was added to the transient pressure difference separator, and the battery after ultrasonic treatment was placed in the transient pressure difference separator. When the pressure reached 4Mpa and the temperature was 218℃, the transient pressure difference separator was started, and the separation products of the waste Cu-In-Ga-Se solar thin film battery were collected, including: CIGS-PET layer, stainless steel substrate, EVA between bonding substrate and PET, and PET of encapsulation substrate (as Figure 5 ).

[0054] The measured mass of the waste Cu-In-Ga-Se solar thin film battery 2x2cm before separation was 0.2047g, the mass of the separation product CIGS-PET layer after separation was 0.0594g, the mass of the stainless steel substrate was 0.0970g, the mass of the EVA between the bonding substrate and the PET was 0.0196g, and the mass of the PET of the encapsulation substrate was 0.0287g. The calculated mass of the stainless steel substrate, the EVA between the bonding substrate and the PET, and the PET of the encapsulation substrate accounted for 71.0% of the mass of the whole battery, which effectively enriched the valuable metals and selenium elements in the battery, and at the same time achieved the purpose of exposing the CIGS layer, and the separation effect is shown in Figure 5 .

[0055] Example 4

[0056] The waste copper indium gallium selenide solar thin film battery is rolled according to a curvature of 50 m -1 After being rolled and fixed, the battery is kept in the rolled state for 30 min, then the fixing is removed and the battery is unfolded. The part of the substrate with a gap from the upper structure is cut into a 2x2 cm battery piece, and the part without a gap is repeated steps S1-S3, and the rolling curvature and the time of keeping the rolled state are consistent with the above.

[0057] The battery piece is placed in a beaker containing deionized water, and the beaker is placed in an ultrasonic instrument for 20 min. 2 ml of deionized water is added to the transient pressure difference separator, and the battery piece after ultrasonic treatment is placed in the transient pressure difference separator. When the pressure reaches 3 Mpa and the temperature display is 188℃, the transient pressure difference separator is started, and the waste copper indium gallium selenide solar thin film battery separation products including CIGS-PET layer, stainless steel substrate, EVA between bonding substrate and PET, and PET of packaging substrate are collected. Figure 6 ).

[0058] The measured mass of the waste copper indium gallium selenide solar thin film battery 2x2 cm battery piece before separation is 0.2032 g, and the mass of the separation product CIGS-PET layer after separation is 0.0582 g, the mass of the stainless steel substrate is 0.0968 g, the mass of the EVA between the bonding substrate and the PET is 0.0197 g, and the mass of the PET of the packaging substrate is 0.0285 g. It is calculated that the stainless steel substrate, the EVA between the bonding substrate and the PET, and the PET of the packaging substrate account for 71.3% of the mass of the whole battery piece, which effectively enriches the valuable metals and selenium elements in the battery piece, and at the same time realizes the purpose of exposing the CIGS layer, and the separation effect is shown in Figure 6 .

[0059] Comparative Example 1

[0060] This comparative example provides a green and efficient method for separating waste copper indium gallium selenide solar thin film batteries, which is the same as Example 1 except that the rolling curvature in step S1 is 18 m -1 When the curvature is less than the preferred parameter range, the CIGS-PET layer is separated from the stainless steel substrate, the PET on the back of the stainless steel substrate falls off, but the EVA is still bonded to the stainless steel substrate and cannot be separated, and the separation effect is shown in Figure 7 .

[0061] Comparative Example 2

[0062] This comparative example provides a green and efficient method for separating waste copper indium gallium selenide (CIGS) thin-film solar cells. The method is identical to that of Example 1, except that the ultrasonic time in step S4 is 8 minutes. When the ultrasonic time is less than the preferred parameter range, the CIGS-PET layer separates from the stainless steel substrate, and the PET encapsulation on the back of the stainless steel substrate detaches. However, the EVA remains adhered to the stainless steel substrate and fails to separate. There is a tendency for EVA to separate from the stainless steel substrate, but complete separation is not achieved, and some of the solar cells remain on the stainless steel substrate. The separation effect is as follows: Figure 8 As shown.

[0063] Comparative Example 3

[0064] This comparative example provides a green and efficient method for separating waste copper indium gallium selenide (CIGS) thin-film solar cells. The method is identical to Example 1 except for step S5, which involves adding 0.5 ml of deionized water. When the amount of deionized water added is less than the preferred parameter range, the CIGS-PET layer separates from the stainless steel substrate, and the PET encapsulation on the back of the stainless steel substrate detaches. However, the EVA remains adhered to the stainless steel substrate and fails to separate. There is a tendency for EVA to separate from the stainless steel substrate, but complete separation is not achieved. The separation effect is stronger than in Comparative Example 2, and some of the solar cells remain on the stainless steel substrate. The separation effect is as follows: Figure 9 As shown.

[0065] Comparative Example 4

[0066] This comparative example provides a green and efficient method for separating waste copper indium gallium selenide (CIGS) thin-film solar cells. Except for step S6 where the pressure is 2.5 MPa, the method is identical to that of Example 1. When the pressure is less than the preferred parameter range, the CIGS-PET layer edge lifts and fails to separate from the stainless steel substrate. After shearing off the lifted portion, the PET encapsulated on the back of the stainless steel substrate does not detach, and the EVA remains adhered to the stainless steel substrate and fails to separate. The separation effect is as follows: Figure 10 As shown.

[0067] It should also be noted that when the experimental parameters are greater than the preferred parameter range, the separation products can be completely separated, but the energy consumed in the whole process is greater. Therefore, it is appropriate to separate waste copper indium gallium selenide solar thin-film batteries within the given preferred parameter range.

[0068] In summary, this invention proposes a green and efficient method for separating waste copper indium gallium selenide (CIGS) solar thin-film batteries. This method can separate waste CIGS solar thin-film batteries in a green and efficient manner, exposing the CIGS layer. It solves the problems of high energy consumption, high pollution, difficulty in leaching the CIGS layer, and difficulty in enriching valuable metals in the recycling process of waste CIGS solar thin-film batteries. The process is green, efficient, simple, and suitable for large-scale industrial applications.

[0069] The preferred embodiments of the application disclosed above are only to facilitate the elucidation of the application. The preferred embodiments do not describe all the details of the application and limit the application to the specific embodiments described. Obviously, many modifications and variations can be made in light of the teachings above. The description is chosen and described in order to best explain the principles of the application and its practical application to thereby enable others skilled in the art to best utilize the application and get the best results from the application. The application is only limited by the claims and their full scope and equivalents.

Claims

1. A method for efficiently separating waste copper indium gallium selenide solar thin film cells, characterized in that, The method comprises the following steps: S1: winding and fixing the waste copper indium gallium selenide solar thin film battery according to a certain curvature and keeping the winding state for a certain time; S2: removing the fixing in step S1 and unfolding the thin film battery; S3: observing the thin film battery unfolded in step S2, cutting the part with a gap between the stainless steel substrate and the upper structure into a 2´2 cm size battery piece, and repeating steps S1-S3 for the part without the gap; S4: placing the battery piece into a beaker containing deionized water, placing the beaker in an ultrasonic instrument, and ultrasonicating for a certain time; S5: placing the battery piece after ultrasonicating in step S4 into a flash pressure difference separator and adding a certain amount of deionized water; S6: running the flash pressure difference separator and opening the flash pressure difference separator when the temperature and pressure reach a certain condition; S7: collecting the separation products including CIGS-PET layer, stainless steel substrate, EVA, and PET, and performing vacuum drying treatment on the collected products; The curling curvature range of the copper-indium-gallium-selenium solar thin film battery in the step S1 is 4-50m -1 , the curling state is maintained for 30min, and the curvature range is 20-50m -1 ; In step S3, the part without the gap is repeated with steps S1-S3, and the winding curvature and the time of keeping the winding state are consistent with the first implementation of step S1; In step S4, the ultrasonicating time of the battery piece in the deionized water is 10-60 min; In step S5, 1-10 ml of deionized water is first added to the flash pressure difference separator, and then the battery piece is placed; In step S6, the pressure range of the flash pressure difference separator is 1-10 Mpa, and the flash pressure difference separator is opened when the temperature reaches 100-350℃.

2. The method of green and efficient separation of copper indium gallium selenide solar thin film cells as claimed in claim 1, wherein: In step S7, the vacuum drying temperature is 50℃, and the drying time is 30 min.

3. The method according to any one of claims 1-2 for use in the separation of copper indium gallium selenide solar thin film battery layers.

Images