CN116871299A - Recovery processing method of waste photovoltaic modules - Google Patents
Recovery processing method of waste photovoltaic modules Download PDFInfo
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- CN116871299A CN116871299A CN202310922977.8A CN202310922977A CN116871299A CN 116871299 A CN116871299 A CN 116871299A CN 202310922977 A CN202310922977 A CN 202310922977A CN 116871299 A CN116871299 A CN 116871299A
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- 239000002699 waste material Substances 0.000 title claims abstract description 92
- 238000011084 recovery Methods 0.000 title claims abstract description 52
- 238000003672 processing method Methods 0.000 title claims description 13
- 238000005530 etching Methods 0.000 claims abstract description 88
- 239000011521 glass Substances 0.000 claims abstract description 61
- 238000004140 cleaning Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000197 pyrolysis Methods 0.000 claims description 17
- 238000004064 recycling Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000002161 passivation Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000003486 chemical etching Methods 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B09B3/50—Destroying solid waste or transforming solid waste into something useful or harmless involving radiation, e.g. electro-magnetic waves
-
- 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
-
- 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
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a recovery treatment method of a waste photovoltaic module, which belongs to the field of solid waste recovery treatment, and comprises the following steps: removing the frame and backboard materials of the waste photovoltaic module; performing laser cleaning on the removed waste photovoltaic module to obtain a glass plate and a solar cell chip; performing heat treatment on the glass plate and the solar cell chip, removing residual EVA materials on the surfaces of the glass plate and the solar cell chip, and completing recovery of the glass plate; and etching the solar cell chip subjected to heat treatment to complete silicon chip recovery. By the method provided by the invention, the loss of glass and silicon wafers in the recovery process is very low, the separation time is only 5-7 seconds, the recovery rate of the final glass can reach 100%, and the recovery efficiency of the silicon wafers can reach 99%.
Description
Technical Field
The invention relates to the technical field of solid waste recovery treatment, in particular to a recovery treatment method of a waste photovoltaic module.
Background
The existing waste photovoltaic module recovery in China has the problems of low added value of target products, relatively low backward recovery rate and slow recovery rate of part of recovery processes, little consideration of harmless treatment of harmful metals and substances and the like.
Current methods for photovoltaic module separation are mainly physical and chemical. Wherein, the physical method is divided into hot knife cutting and pyrolysis separation; the chemical method is classified into an organic solvent method and an acid solution etching method. However, these methods cannot solve the problem that the waste photovoltaic module chip is difficult to separate from the glass plate. More importantly, the method can cause damage to the photovoltaic module in the splitting process, and materials such as glass, silicon chips and backboard in the waste photovoltaic module cannot be completely separated.
Disclosure of Invention
Aiming at the technical problem that the high-integrity recovery of the waste photovoltaic module chip cannot be completed in the prior art, the invention provides a recovery processing method of the waste photovoltaic module, and each module in the waste photovoltaic module can be completely separated by adopting the method, and complete glass and silicon chips can be recovered.
In order to achieve the above purpose, the recovery processing method of the waste photovoltaic module provided by the invention comprises the following steps: performing laser cleaning on the removed waste photovoltaic module to obtain a glass plate and a solar cell chip; wherein, the laser cleaning includes: the laser cleaning device comprises a first laser cleaning and a second laser cleaning, wherein the laser scanning power adopted in the first laser cleaning is larger than that adopted in the second laser cleaning; the laser irradiation patterns at the time of the first laser cleaning and the second laser cleaning may be the same or different; performing heat treatment on the glass plate and the solar cell chip, removing residual EVA materials on the surfaces of the glass plate and the solar cell chip, and completing recovery of the glass plate; and etching the solar cell chip subjected to heat treatment to complete silicon chip recovery.
In an exemplary embodiment of the present invention, the laser cleaning of the removed waste photovoltaic module may include: performing first laser cleaning on the periphery of the removed waste photovoltaic module; and carrying out secondary laser cleaning on the surface of the dismantled waste photovoltaic module.
In one exemplary embodiment of the present invention, the laser irradiation pattern may be set as a linear laser pattern.
In one exemplary embodiment of the present invention, the laser irradiation pattern may be set as a thread laser pattern.
In one exemplary embodiment of the present invention, the laser shot pattern may be determined according to the laser scanning power.
In an exemplary embodiment of the present invention, the laser scanning time may be set to 5 to 7s.
In an exemplary embodiment of the present invention, the conditions of the heat treatment may include: the pyrolysis heating rate is 5-10 ℃/min, and the pyrolysis end temperature is 450-480 ℃.
In an exemplary embodiment of the present invention, the etching treatment on the solar cell chip after the heat treatment may include: immersing the solar cell chip subjected to heat treatment in alkaline solution for first etching to remove an aluminum back electrode of the solar cell chip; immersing the solar cell chip subjected to the first etching in an acid solution for performing the second etching to remove the silver electrode of the solar cell chip; immersing the solar cell chip subjected to the second etching in phosphoric acid solution for the third etching, and removing the passivation layer of the solar cell chip.
In an exemplary embodiment of the present invention, the first etching condition may include: the etching liquid is sodium hydroxide solution with the concentration of 1.5-2.5 mol/L, and the etching time is 6-7 minutes; the conditions of the second etching may include: the etching solution is nitric acid solution with the concentration of 55-65%, and the etching time is 9-11 minutes; the conditions of the third etching may include: phosphoric acid solution with concentration of 55-65% of etching solution
And etching the liquid for 12-14 minutes.
In an exemplary embodiment of the present invention, the recycling method may further include: and (3) carrying out electrolytic treatment on the etching liquid after the etching treatment, and recovering the metal aluminum and the metal silver.
Through the technical scheme provided by the invention, the invention has at least the following technical effects:
(1) According to the recovery processing method of the waste photovoltaic module, each module in the waste photovoltaic module is completely separated by adopting a laser cleaning and splitting method, and the complete silicon wafer and the glass plate which are not broken or cracked in a large scale are recovered, so that the recovery processing method has higher utilization value in subsequent silicon recovery;
(2) The waste photovoltaic module recovery processing method has very low loss on glass and silicon chips in the recovery process, the separation time is only 5-7 seconds, the recovery rate of the final glass can reach 100%, and the recovery efficiency of the silicon chips can reach 99%;
(3) The recovery treatment method of the waste photovoltaic module can also recover valuable metals in the waste photovoltaic module, the recovery rate of metal aluminum and silver can reach more than 90%, and the valuable metals cannot be lost in the treatment process;
(4) The method for recycling the waste photovoltaic modules belongs to green harmless recycling, does not use any organic solvent in the whole recycling process, does not have organic solvent pollution, and does not generate any toxic and harmful byproducts.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain, without limitation, the embodiments of the invention. In the drawings:
fig. 1 is a flowchart of a method for recycling waste photovoltaic modules according to an embodiment of the present invention.
Detailed Description
The following describes the detailed implementation of the embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
In the present invention, unless otherwise indicated, terms of orientation such as "upper, lower, top, bottom" are used generally with respect to the orientation shown in the drawings or with respect to the positional relationship of the various components with respect to one another in the vertical, vertical or gravitational directions. The "first," "second," etc. are merely for convenience of description and for convenience of distinction, and are not to be construed as indicating or implying relative importance.
In the prior art, when the waste photovoltaic module chip is separated from the glass plate in a hot knife cutting mode and the like, the chip and the glass plate are often damaged to different degrees, and the high integrity of the chip and the glass plate cannot be guaranteed.
Aiming at the technical problems, the invention provides a novel recovery processing method of waste photovoltaic modules, which is characterized in that each module in the waste photovoltaic modules is completely separated by a laser cleaning and splitting method, and complete glass and silicon wafers are recovered. In the process of treating the waste photovoltaic module, the method controls the degree of decomposing the module by regulating and controlling the laser irradiation power, time and irradiation pattern, so that a complete silicon wafer, a glass backboard and the like can be obtained, the secondary utilization of the recovered silicon wafer is realized, and the purpose of quickly and completely recovering the waste photovoltaic module is finally realized.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
Referring to fig. 1, an embodiment of the invention provides a method for recycling waste photovoltaic modules, which includes the following steps:
step S101: and removing the frame and backboard materials of the waste photovoltaic module.
Step S102: and carrying out laser cleaning on the dismantled waste photovoltaic module to obtain a glass plate and a solar cell chip.
Step S103: and carrying out heat treatment on the glass plate and the solar cell chip, and removing residual EVA materials (namely ethylene-vinyl acetate copolymer materials) on the surfaces of the glass plate and the solar cell chip to complete recovery of the glass plate.
Step S104: and etching the solar cell chip subjected to heat treatment to complete silicon chip recovery.
Further, in step S102, laser cleaning may be performed on the removed waste photovoltaic module multiple times, so as to gradually separate the waste photovoltaic module chip (i.e., the solar cell chip) from the glass plate. For example, the periphery of the removed waste photovoltaic module can be subjected to first laser cleaning to realize preliminary separation of the waste photovoltaic module chip and the glass plate; and performing laser cleaning on the surface of the dismantled waste photovoltaic module for the second time to completely separate the waste photovoltaic module chip from the glass plate.
Preferably, the periphery of the removed waste photovoltaic module can be subjected to first laser cleaning by adopting first laser scanning power; and then adopting second laser scanning power to carry out second laser cleaning on the surface of the dismantled waste photovoltaic module. Wherein the first laser scanning power is greater than the second laser scanning power. The laser with larger scanning power has higher temperature, and the bonding degree between the waste photovoltaic module chip and the glass plate can be rapidly reduced by scanning the periphery of the waste photovoltaic module through the high-temperature laser. However, if laser with larger scanning power is continuously used for scanning, the high temperature generated by the laser is very likely to cause the breakage of the waste photovoltaic module chip and the glass plate. Therefore, when the laser cleaning is performed for the second time, the laser with smaller scanning power is used for scanning the surface of the waste photovoltaic module, so that the decomposition degree of the waste photovoltaic module chip and the glass plate is controlled, and the waste photovoltaic module chip and the glass plate are prevented from being damaged due to high temperature.
Further, the laser irradiation pattern at the time of the first laser cleaning and the laser irradiation pattern at the time of the second laser cleaning may be the same. The laser irradiation pattern is determined according to the laser scanning power.
For example, the laser irradiation pattern may be set as a linear laser pattern. The laser area generated by the linear laser pattern is smaller, but the laser temperature rise is also more severe. When the linear laser graph is adopted to perform local scanning on the position with larger bonding strength of the waste photovoltaic module chip and the glass plate, a better integral separation effect can be obtained.
Of course, the laser irradiation pattern may be set as a thread laser pattern. The laser area generated by the thread laser pattern is relatively large, but the laser temperature rise is also relatively mild. When the thread laser pattern is adopted to scan the whole waste photovoltaic module in a large range, the bonding force between the waste photovoltaic module chip and the glass plate can be destroyed, and the damage to the waste photovoltaic module chip and the glass plate caused by overhigh heat energy can be avoided.
Preferably, the laser irradiation pattern at the time of the first laser cleaning and the laser irradiation pattern at the time of the second laser cleaning may be different.
For example, when the periphery of the dismantled waste photovoltaic module is subjected to first laser cleaning by adopting first laser scanning power, setting a laser irradiation pattern as a thread laser pattern; and setting the laser irradiation pattern as a linear laser pattern when the surface of the dismantled waste photovoltaic module is subjected to laser cleaning for the second time by adopting the second laser scanning power. When the laser scanning power is higher and the scanning is performed in a thread mode, the laser area can be increased, and enough heating energy can be ensured to peel the periphery of the waste photovoltaic module; when the laser scanning power is lower and the laser scanning is performed in a linear mode, the waste photovoltaic module can be protected from damage, and a better local separation effect can be obtained. Further, the laser scanning time may be set to 5 to 7 seconds. Specifically, the laser scanning time may be set to 5s, 5.5s, 6s, 6.5s, 7s, or the like. If the laser scanning time is less than 5s, the contact time of the laser and the waste photovoltaic module is possibly too short, and the waste photovoltaic module chip and the glass plate cannot be completely stripped; if the laser scanning time is less than 7s, the contact time between the laser and the waste photovoltaic module is too long, so that the chip of the waste photovoltaic module and the glass plate are broken or cracked on a large scale.
Further, in step S103, the conditions of the heat treatment may include: the pyrolysis heating rate is 5-10 ℃/min, and the pyrolysis end temperature is 450-480 ℃. Specifically, the pyrolysis heating rate may be set to 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, and the pyrolysis end temperature may be set to 450 ℃, 460 ℃, 470 ℃ or 480 ℃.
Further, in step S104, the process of performing etching treatment on the solar cell chip after the heat treatment includes the following sub-steps.
Substep S1041: immersing the solar cell chip subjected to heat treatment in alkaline solution for first etching to remove the aluminum back electrode of the solar cell chip.
Illustratively, the conditions of the first etching may include: the etching liquid is sodium hydroxide solution with the concentration of 1.5-2.5 mol/L, and the etching time is 6-7 minutes.
Sub-step S1042: immersing the solar cell chip after the first etching in an acid solution for the second etching to remove the silver electrode of the solar cell chip.
Illustratively, the conditions of the second etching may include: the etching liquid is nitric acid solution with concentration of 55% -65%, and the etching time is 9-11 minutes.
Substep S1043: immersing the solar cell chip subjected to the second etching in phosphoric acid solution for the third etching, and removing the passivation layer of the solar cell chip.
Illustratively, the conditions for the third etching may include: the etching liquid is phosphoric acid solution with concentration of 55% -65%, and the etching time is 12-14 minutes.
Further, the recycling method may further include step S105: and (3) carrying out electrolytic treatment on the etching liquid after the etching treatment, and recovering the metal aluminum and the metal silver.
For a better understanding of the above-described exemplary embodiments of the present invention, they are further described below in conjunction with specific examples.
Example 1
A recovery processing method of waste photovoltaic modules is realized by the following steps.
Step (1): the recovered waste photovoltaic modules are sorted, cleaned and dedusted, classified according to the specification and the damage degree, and the photovoltaic module frame and the backboard materials are removed mechanically.
Step (2): and respectively placing the washed broken waste photovoltaic modules and the whole waste photovoltaic modules on a laser separation platform, then stripping the solar cell chip by using a laser cleaning machine, and finally respectively obtaining a glass plate and the solar cell chip.
Step (3): and removing residual EVA materials on the surfaces of the glass plate and the solar cell chip in a pyrolysis mode, cleaning and dedusting the glass plate after cooling, and completing a glass plate recovery procedure.
Step (4): and dissolving the metal electrode into etching solution by using an etching method to complete the silicon wafer recovery process.
Step (5): and extracting metal from the etched solution to complete the valuable metal recovery process.
Preferably, in the step (1), the damaged waste photovoltaic module and the complete waste photovoltaic module are respectively placed in two ultrasonic cleaners.
Preferably, in step (2), the laser cleaning apparatus employs a continuous laser cleaning machine of rated power 1500 w.
Preferably, in the step (2), the actual laser scanning power is 300w and 400w, which are sequentially scanned and separated. The periphery of the waste photovoltaic module is scanned by using 400w of laser scanning power, and then the surface of the waste photovoltaic module is scanned by using 300w of laser scanning power.
Preferably, in the step (2), a linear laser pattern is used when the actual laser scanning power is 300w, and a thread laser pattern is used when the actual laser scanning power is 400 w.
Preferably, in step (2), the laser scanning time is 5 to 7 seconds.
Preferably, in step (3), the pyrolysis temperature rise rate is 5 ℃/min and the end point temperature is 450 ℃.
Preferably, in the step (4), the chemical etching reagent of the aluminum back electrode of the solar cell chip is sodium hydroxide, the concentration of the etching solution is 2mol/L, and the etching time is 5 minutes. The chemical etching reagent of the silver electrode of the solar cell chip is nitric acid, the concentration of the etching solution is 60% nitric acid solution, and the etching time is 10 minutes. The chemical etching reagent of the passivation layer of the solar cell chip is phosphoric acid, the concentration of the etching solution is 60% of the concentration of phosphoric acid solution, and the etching time is 12 minutes.
After each chemical etching, the next step is carried out after washing with deionized water for 10 minutes.
Preferably, in step (5), silver and aluminum are purified by electrolysis, respectively.
By carrying out the method according to example 1, the complete recovery rate of the final glass plate and silicon wafer can reach more than 90%.
Example 2
A recovery processing method of waste photovoltaic modules is realized by the following steps.
Step (1): the recovered waste photovoltaic modules are sorted, cleaned and dedusted, classified according to the specification and the damage degree, and the photovoltaic module frame and the backboard materials are removed mechanically.
Step (2): and respectively placing the washed broken waste photovoltaic modules and the whole waste photovoltaic modules on a laser separation platform, then stripping the solar cell chip by using a laser cleaning machine, and finally respectively obtaining a glass plate and the solar cell chip. Wherein, the actual laser scanning power is 400w, the laser irradiation pattern is a linear laser pattern, and the laser scanning time is 5 seconds.
Step (3): and removing residual EVA materials on the surfaces of the glass plate and the solar cell chip in a pyrolysis mode, cleaning and dedusting the glass plate after cooling, and completing a glass plate recovery procedure. Wherein the pyrolysis heating rate is 10 ℃/min, and the end point temperature is 480 ℃.
Step (4): and dissolving the metal electrode into etching solution by using an etching method to complete the silicon wafer recovery process.
The chemical etching reagent of the aluminum back electrode of the solar cell chip is sodium hydroxide, the concentration of etching liquid is 2mol/L, and the etching time is 5 minutes. The chemical etching reagent of the silver electrode of the solar cell chip is nitric acid, the concentration of the etching solution is 60% nitric acid solution, and the etching time is 10 minutes. The chemical etching reagent of the passivation layer of the solar cell chip is phosphoric acid, the concentration of the etching solution is 60% of the concentration of phosphoric acid solution, and the etching time is 12 minutes.
The complete recovery of the final glass plate and silicon wafer was 40% to 50% by implementation according to the method of example 2.
Example 3
A recovery processing method of waste photovoltaic modules is realized by the following steps.
Step (1): the recovered waste photovoltaic modules are sorted, cleaned and dedusted, classified according to the specification and the damage degree, and the photovoltaic module frame and the backboard materials are removed mechanically.
Step (2): and respectively placing the washed broken waste photovoltaic modules and the whole waste photovoltaic modules on a laser separation platform, then stripping the solar cell chip by using a laser cleaning machine, and finally respectively obtaining a glass plate and the solar cell chip. Wherein, the actual laser scanning power is 300w, the laser irradiation pattern is a linear laser pattern, and the laser scanning time is 7 seconds.
Step (3): and removing residual EVA materials on the surfaces of the glass plate and the solar cell chip in a pyrolysis mode, cleaning and dedusting the glass plate after cooling, and completing a glass plate recovery procedure. Wherein the pyrolysis heating rate is 5 ℃/min, and the end point temperature is 460 ℃.
Step (4): and dissolving the metal electrode into etching solution by using an etching method to complete the silicon wafer recovery process.
The chemical etching reagent of the aluminum back electrode of the solar cell chip is sodium hydroxide, the concentration of etching liquid is 2mol/L, and the etching time is 5 minutes. The chemical etching reagent of the silver electrode of the solar cell chip is nitric acid, the concentration of the etching solution is 60% nitric acid solution, and the etching time is 10 minutes. The chemical etching reagent of the passivation layer of the solar cell chip is phosphoric acid, the concentration of the etching solution is 60% of the concentration of phosphoric acid solution, and the etching time is 12 minutes.
The complete recovery of the final glass plate and silicon wafer was 60% to 70% by implementation according to the method of example 3.
Example 4
A recovery processing method of waste photovoltaic modules is realized by the following steps.
Step (1): the recovered waste photovoltaic modules are sorted, cleaned and dedusted, classified according to the specification and the damage degree, and the photovoltaic module frame and the backboard materials are removed mechanically.
Step (2): and respectively placing the washed broken waste photovoltaic modules and the whole waste photovoltaic modules on a laser separation platform, then stripping the solar cell chip by using a laser cleaning machine, and finally respectively obtaining a glass plate and the solar cell chip. The actual laser scanning power is 500w, the laser irradiation pattern is a linear laser pattern, and the laser scanning time is 10 seconds.
Step (3): and removing residual EVA materials on the surfaces of the glass plate and the solar cell chip in a pyrolysis mode, cleaning and dedusting the glass plate after cooling, and completing a glass plate recovery procedure. Wherein the pyrolysis heating rate is 10 ℃/min, and the end point temperature is 480 ℃.
Step (4): and dissolving the metal electrode into etching solution by using an etching method to complete the silicon wafer recovery process.
The chemical etching reagent of the aluminum back electrode of the solar cell chip is sodium hydroxide, the concentration of etching liquid is 2mol/L, and the etching time is 5 minutes. The chemical etching reagent of the silver electrode of the solar cell chip is nitric acid, the concentration of the etching solution is 60% nitric acid solution, and the etching time is 10 minutes. The chemical etching reagent of the passivation layer of the solar cell chip is phosphoric acid, the concentration of the etching solution is 60% of the concentration of phosphoric acid solution, and the etching time is 12 minutes.
The complete recovery of the final glass plate and silicon wafer was only 20% by performing according to the method of example 4.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The recovery processing method of the waste photovoltaic module is characterized by comprising the following steps of:
performing laser cleaning on the removed waste photovoltaic module to obtain a glass plate and a solar cell chip; wherein, the laser cleaning includes: the laser cleaning device comprises a first laser cleaning and a second laser cleaning, wherein the laser scanning power adopted in the first laser cleaning is larger than that adopted in the second laser cleaning; the laser irradiation patterns in the first laser cleaning and the second laser cleaning are the same or different;
performing heat treatment on the glass plate and the solar cell chip, removing residual EVA materials on the surfaces of the glass plate and the solar cell chip, and completing recovery of the glass plate;
and etching the solar cell chip subjected to heat treatment to complete silicon chip recovery.
2. The method for recycling waste photovoltaic modules according to claim 1, wherein the laser cleaning of the removed waste photovoltaic modules comprises:
performing first laser cleaning on the periphery of the removed waste photovoltaic module;
and carrying out secondary laser cleaning on the surface of the dismantled waste photovoltaic module.
3. The method for recycling waste photovoltaic modules according to claim 1, wherein the laser irradiation pattern is set as a linear laser pattern.
4. The method for recycling waste photovoltaic modules according to claim 1, wherein the laser irradiation pattern is a screw laser pattern.
5. The method for recycling waste photovoltaic modules according to claim 1, wherein the laser irradiation pattern is determined based on the laser scanning power.
6. The method for recycling waste photovoltaic modules according to claim 1, wherein the laser scanning time is set to 5-7 s.
7. The method for recycling waste photovoltaic modules according to claim 1, wherein the heat treatment conditions include: the pyrolysis heating rate is 5-10 ℃/min, and the pyrolysis end temperature is 450-480 ℃.
8. The method for recycling waste photovoltaic modules according to claim 1, wherein the etching treatment of the solar cell chip after the heat treatment comprises:
immersing the solar cell chip subjected to heat treatment in alkaline solution for first etching to remove an aluminum back electrode of the solar cell chip;
immersing the solar cell chip subjected to the first etching in an acid solution for performing the second etching to remove the silver electrode of the solar cell chip;
immersing the solar cell chip subjected to the second etching in phosphoric acid solution for the third etching, and removing the passivation layer of the solar cell chip.
9. The method for recycling waste photovoltaic modules according to claim 1, wherein the conditions for the first etching include: the etching liquid is sodium hydroxide solution with the concentration of 1.5-2.5 mol/L, and the etching time is 6-7 minutes;
the conditions of the second etching include: the etching solution is nitric acid solution with the concentration of 55-65%, and the etching time is 9-11 minutes;
the conditions of the third etching include: the etching liquid is phosphoric acid solution with concentration of 55% -65%, and the etching time is 12-14 minutes.
10. The method for recycling waste photovoltaic modules according to claim 1, characterized in that the recycling method further comprises: and (3) carrying out electrolytic treatment on the etching liquid after the etching treatment, and recovering the metal aluminum and the metal silver.
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| CN117505407A (en) * | 2024-01-05 | 2024-02-06 | 国能龙源环保有限公司 | Method for removing organic matters in waste salt by utilizing laser |
| CN117505407B (en) * | 2024-01-05 | 2024-04-19 | 国能龙源环保有限公司 | Method for removing organic matters in waste salt by utilizing laser |
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