CN111957715A - Process for recycling waste crystalline silicon solar cell modules - Google Patents
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- CN111957715A CN111957715A CN202010717748.9A CN202010717748A CN111957715A CN 111957715 A CN111957715 A CN 111957715A CN 202010717748 A CN202010717748 A CN 202010717748A CN 111957715 A CN111957715 A CN 111957715A
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- crystalline silicon
- silicon solar
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- waste crystalline
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- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 30
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 30
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 38
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000005341 toughened glass Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention provides a process for recycling waste crystalline silicon solar cell modules, and belongs to the technical field of crystalline silicon materials. After the waste crystalline silicon solar cell is cut, processing EVA (ethylene-vinyl acetate copolymer) adhesive by a thermal decomposition method to realize successful splitting of each part of the assembly; the recovery process can keep the original performance of each part of the crystalline silicon solar module, has the characteristics of low energy consumption, strong processing capability, high recovery rate and the like, realizes the high-efficiency recovery and utilization of each part of the waste crystalline silicon solar cell module to the maximum extent, and can be used for processing the waste crystalline silicon solar module materials in a large scale.
Description
Technical Field
The invention belongs to the technical field of crystalline silicon materials, relates to a waste crystalline silicon solar cell, and particularly relates to a process for recycling a waste crystalline silicon solar cell component.
Background
The use of fossil energy in large quantities emits large quantities of sulfide and nitride, which can cause environmental pollution such as acid rain. Meanwhile, greenhouse gases such as carbon dioxide and the like are also discharged along with the emission of the greenhouse gases, so that the global climate is influenced. The traditional fossil energy faces the problems of high pollution and exhaustion, and the vigorous development of renewable energy has very important significance to our country. Solar energy is an inexhaustible clean renewable energy source and is widely concerned by the industry. With the rapid development of the global solar power generation market in recent years, the growth rate of the yield of solar cells is basically maintained at 30-40%. Among them, the crystalline silicon solar cell in the field of solar photovoltaic power generation is widely used due to its advantages of high power generation efficiency, convenience for later maintenance, and the like. It is predicted that global solar cells will continue to grow at a rate of about 25% by the year 2030. The installed solar cell capacity will increase from 0.5 GW in the early 21 st century to 300 GW in 2030 s.
The service life of most photovoltaic modules is 25 years, and after 2020 years, the first solar photovoltaic power stations built in China are updated and upgraded greatly. If the waste photovoltaic module is discarded at will, certain damage can be caused to the environment, and the original design purpose of clean energy is violated. Secondly, also can produce unqualified defective products in the production of photovoltaic module, increase the running cost of enterprise. How to recycle and treat the waste components to reduce the damage to the environment is a direction of attention, which does not violate the development aim of green clean energy. The waste solar cell components contain materials such as silicon, silver, copper, aluminum, glass, plastics and the like. The waste photovoltaic module comprises 70% of glass, 10% of aluminum, 10% of adhesive sealant, 5% of silicon and 5% of the other components. The parts with recycling value in the crystalline silicon solar cell comprise silicon, an aluminum frame, tempered glass, silver, copper, aluminum and other metals. The waste crystalline silicon solar cell has great resource recycling value. Meanwhile, the waste crystalline silicon solar cells contain heavy metals such as tin and lead, and are harmful to the environment and human bodies due to random treatment. From the perspective of law, economy and environment, the recovery of the waste photovoltaic module has important practical significance and scientific research value.
EVA is a transparent material used to encapsulate crystalline silicon solar cell modules and to serve as an adhesive between the layers of the panel. The EVA plays a role of "take-up and take-down" in the crystalline silicon solar module, which maintains the structure of the crystalline silicon solar module. If the EVA is disposed, the crystalline silicon solar energy component can be easily disassembled into different parts. Therefore, the EVA treatment becomes a key technology for treating the waste photovoltaic module.
Disclosure of Invention
The invention provides a process for recycling waste crystalline silicon solar cell modules, which removes EVA (ethylene-vinyl acetate copolymer) adhesive films in the cell modules by a thermal decomposition method to realize successful separation of all parts in the modules.
The technical scheme adopted by the invention is as follows: a process for recycling waste crystalline silicon solar cell modules specifically comprises the following steps:
s1, cutting waste crystalline silicon solar cells into blocks, soaking the blocks in absolute ethyl alcohol for 1 hour, removing impurities on the surfaces of the blocks, and airing the blocks for later use;
s2, placing the waste crystalline silicon assembly in a crucible at 400-600 ℃, treating for 30-40min, decomposing EVA (ethylene vinyl acetate) adhesive in the battery assembly to realize the disassembly of the assembly, and recovering materials of all parts of the assembly.
Preferably, in S1, the waste crystalline silicon solar cells are cut into blocks with a width of 3 cm × 3 cm.
The performance of the waste crystalline silicon solar cell module material recovered by the thermal decomposition method is tested.
FIG. 1 is a thermogravimetric diagram of a waste crystalline silicon solar cell module;
as can be seen from fig. 1, the thermogravimetric variation of the waste crystalline silicon solar modules; the weight loss rate of the first stage is about 18.3 percent from 221.5 ℃ to 360 ℃; the second stage is carried out at 360-412.4 ℃, the sample is rapidly thermally decomposed at the stage, and the weight loss rate at the stage is about 42 percent; at 412.4 ℃, the weight loss rate of the waste crystalline silicon solar cell module material sample reaches 61%.
FIG. 2 is a thermogravimetric graph of a waste crystalline silicon solar module treated at 350 ℃, 400 ℃ and 600 ℃ for 30 minutes;
the thermogravimetric analysis of the assembly after 350 ℃ treatment proves that 350 ℃ is not enough to completely decompose EVA on the assembly, so that the thermogravimetric diagram also shows three weight loss stages. This conclusion is consistent with the thermogram of an untreated as-received spent crystalline silicon solar cell module. The first stage occurs at 258.7-330 ℃, and the weight loss rate is about 26.38%; the second stage is about 330-370 ℃ and the weight loss rate is-11.96%; the third stage is about 370-412.5 deg.C, and the weight loss rate of the sample is about 48.5%. Since the cell is manufactured by subjecting the panel to a lamination and curing process, first heating the crystalline silicon photovoltaic panel to a temperature above the melting point of EVA (72 ℃) in vacuum to melt the EVA and distribute the sealant uniformly, and then subjecting the panel to a standard curing EVA treatment at 150 ℃ for 60 minutes or to a rapid cure for 10 minutes, the sealant will undergo a cross-linking process, thereby changing its physical properties, encapsulating the solar cell, and protecting it from moisture and electrical insulation. The reliability of the photovoltaic system is also ensured throughout the life cycle and a durable strong adhesion is achieved between each layer of the panel. While it is difficult to see the thermal weight loss peaks when the thermal decomposition temperature is increased to 400 ℃ and 600 ℃. The test proves that most of EVA of the photovoltaic waste module can be removed at the high temperature of 400 ℃ and 600 ℃.
FIG. 3 is a scanning electron microscope image of a waste crystalline silicon solar module which is untreated and treated at 350 ℃ and 400 ℃ for 30 minutes;
the middle white stripe structure, which is the grid line of the crystalline silicon solar cell, can be clearly seen in fig. 3. Because the grid line of the waste photovoltaic cell piece which is coated with the EVA and is not processed is smooth and flat. It can be seen that the obvious EVA laminate structure covers the surface of the grid line. After the waste battery assembly is heated at 350 ℃, the EVA laminated structure on the grid line can be seen to be damaged, and the silver grid line formed by silk-screen printing is exposed below the EVA laminated structure. But a large number of continuous EVA layer structures can be seen on the silver grid line due to insufficient heating temperature. The waste battery component heated at 400 ℃ can show that the EVA laminated structure on the surface of the silver grid line after high-temperature thermal decomposition disappears, and uneven metal particles formed by screen printing appear on the surface of the silver grid line. Through the observation of a scanning electron microscope, the EVA on the waste photovoltaic module can be clearly and visually seen to have an obvious treatment effect by the thermal decomposition method. After the combination of the thermogravimetric analysis in the previous period, the optimal temperature for obtaining the EVA heat treatment in the waste assembly is 400 ℃. And the high-temperature thermal decomposition has little influence on the structures of other substances in the photovoltaic waste assembly. The recovery of other parts of the photovoltaic waste assembly is not influenced.
As can be seen from fig. 4a, after the waste crystalline silicon solar modules are firstly cut, even though the toughened glass at the outermost layer is broken, the waste crystalline silicon solar modules cannot be successfully separated by hands. After cutting, the silicon solar module is placed in a crucible and heated at 400 ℃ for 30 minutes, and the parts of the silicon solar module are completely separated (figure 4 b). The thermal decomposition temperature of the EVA is about 400 ℃, and the EVA in the waste component can be completely decomposed at the temperature. Finally, the separated materials are sorted (fig. 4 c), so that the separation of the toughened glass, the silicon wafer and the grid line can be realized, and further the next resource recovery and reutilization of each part of the assembly can be completed.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, after the waste crystalline silicon solar cell is cut, the EVA (ethylene-vinyl acetate copolymer) adhesive is treated by a thermal decomposition method to realize the successful splitting of each part of the component; the recovery process can keep the original performance of each part of the crystalline silicon solar module, has the characteristics of low energy consumption, strong processing capacity, high recovery rate and the like, and realizes the efficient recovery and utilization of materials of each part of the waste crystalline silicon solar module to the maximum extent. The process for treating the waste crystalline silicon solar modules by the thermal decomposition method can be used for treating the waste crystalline silicon solar modules in a large batch.
Drawings
FIG. 1 is a thermogravimetric diagram of a waste crystalline silicon solar cell module;
FIG. 2 is a thermogravimetric diagram of a waste crystalline silicon solar module treated at 350 ℃, 400 ℃ and 600 ℃ for 30 minutes;
FIG. 3 is a scanning electron microscope image of a waste crystalline silicon solar module which is untreated and is treated at 350 ℃ and 400 ℃ for 30 minutes;
FIG. 4 is a photograph showing the appearance of the used photovoltaic module before and after the 350 ℃ thermal decomposition process.
Detailed Description
The process for treating EVA in the waste crystalline silicon solar cell module by the thermal decomposition method is further explained by the specific example;
example 1
A process for recycling waste crystalline silicon solar cell modules specifically comprises the following steps:
s1, cutting a waste crystalline silicon solar cell module (3 cm multiplied by 3 cm), soaking in absolute ethyl alcohol for 1 hour to remove part of surface impurities, and drying for later use;
s2, then placing the waste crystalline silicon solar cell modules in a crucible, and treating for 30 minutes at 350 ℃; and when the decomposition of the EVA part is detected, the waste crystalline silicon solar cell module can not be completely separated, all parts of the module are still adhered together, and the disassembly is difficult.
Example 2
A process for recycling waste crystalline silicon solar cell modules specifically comprises the following steps:
s1, cutting a waste crystalline silicon solar cell module (3 cm multiplied by 3 cm), soaking in absolute ethyl alcohol for 1 hour to remove part of surface impurities, and drying for later use;
s2, then placing the waste crystalline silicon solar cell modules in a crucible, and treating for 30 minutes at 400 ℃; and when the EVA is completely decomposed, the waste crystalline silicon solar cell modules can be completely separated, and all parts of the modules have good performances and can be recycled.
Example 3
A process for recycling waste crystalline silicon solar cell modules specifically comprises the following steps:
s1, cutting a waste crystalline silicon solar cell module (3 cm multiplied by 3 cm), soaking in absolute ethyl alcohol for 1 hour to remove part of surface impurities, and drying for later use;
s2, then placing the waste crystalline silicon solar cell modules in a crucible, and treating for 30 minutes at 600 ℃; the EVA is detected to be decomposed, the waste crystalline silicon solar cell module is observed to be completely separated, all parts of the module are good in performance, but electric energy loss caused by high temperature is large, and the crystal silicon and the grid lines are wrapped and covered after the toughened glass is heated, melted and cooled at high temperature, so that the recycling efficiency of the crystal silicon and the grid lines is low.
Claims (2)
1. A process for recycling waste crystalline silicon solar cell modules is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, cutting waste crystalline silicon solar cells into blocks, soaking the blocks in absolute ethyl alcohol for 1 hour, removing impurities on the surfaces of the blocks, and airing the blocks for later use;
s2, placing the waste crystalline silicon assembly in a crucible, treating for 30-40min at the temperature of 400-600 ℃, decomposing the EVA adhesive in the battery assembly to realize the disassembly of the assembly, and recovering materials of all parts of the assembly.
2. The process for recycling waste crystalline silicon solar cell modules as claimed in claim 1, wherein the process comprises the following steps: in S1, the waste crystalline silicon solar cells are cut into blocks with a width of 3 cm × 3 cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010717748.9A CN111957715A (en) | 2020-07-23 | 2020-07-23 | Process for recycling waste crystalline silicon solar cell modules |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010717748.9A CN111957715A (en) | 2020-07-23 | 2020-07-23 | Process for recycling waste crystalline silicon solar cell modules |
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| CN111957715A true CN111957715A (en) | 2020-11-20 |
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| CN202010717748.9A Pending CN111957715A (en) | 2020-07-23 | 2020-07-23 | Process for recycling waste crystalline silicon solar cell modules |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618859A (en) * | 2022-02-28 | 2022-06-14 | 武汉大学 | Method for recycling waste crystalline silicon solar panel |
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2020
- 2020-07-23 CN CN202010717748.9A patent/CN111957715A/en active Pending
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| CN114618859A (en) * | 2022-02-28 | 2022-06-14 | 武汉大学 | Method for recycling waste crystalline silicon solar panel |
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