CN108913902A - A kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly - Google Patents
A kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly Download PDFInfo
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- CN108913902A CN108913902A CN201810783695.3A CN201810783695A CN108913902A CN 108913902 A CN108913902 A CN 108913902A CN 201810783695 A CN201810783695 A CN 201810783695A CN 108913902 A CN108913902 A CN 108913902A
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- solar cell
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- thinfilm solar
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011084 recovery Methods 0.000 title claims abstract description 30
- 239000010409 thin film Substances 0.000 title claims abstract description 29
- 238000001704 evaporation Methods 0.000 title claims abstract description 26
- 230000008020 evaporation Effects 0.000 title claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 22
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052714 tellurium Inorganic materials 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 11
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910004613 CdTe Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of laser evaporation recovery and treatment methods of Thinfilm solar cell assembly, it be the Thinfilm solar cell assembly that will be scrapped back-panel glass and conductive electrode withdraw from after obtain the glass substrate with photovoltaic film layer, with the photovoltaic film layer on laser irradiation at short distance glass substrate, to it, all evaporation obtains complete glass substrate, and the evaporant of photovoltaic film layer then enters in solid powder collecting chamber, most leaches the synthetical recovery for realizing valuable metal in photovoltaic film layer through hydrometallurgical processes afterwards.The method of the present invention removes that photovoltaic film layer, the process of valuable metal solids is very short in collection photovoltaics film layer, speed is fast；The rate of recovery of valuable metal is high, and working environment is good, and it is high that glass substrate damages small reuse ratio；Mechanical automation technique can be used completely, and working environment is good, it is ensured that product chain whole process is environmental-friendly, improves the material recovery rate and recovering effect of Thinfilm solar cell assembly, improves resource utilization.
Description
Technical field
The present invention relates to a kind of laser evaporation recovery and treatment methods of Thinfilm solar cell assembly, belong to thin film solar
Battery component recovery technology field.
Background technique
It peters out in traditional energy, when environmental problem is aggravated year by year, new energy has been increasingly becoming various countries' energy strategy
Mainstream, wherein film photovoltaic industry is in new energy in occupation of critical role.Thin-film solar cells, it is with semiconductor
Material is the direct conversion that medium realizes light and electricity, when sunlight is irradiated to solar panel, in no machine driving and dirt
In the case where metachromia by-product, solar energy can be directly changed into electric energy.
At present on photovoltaic market, cadmium telluride diaphragm solar battery devotes photovoltaic power generation extensively.However, cadmium telluride is too
Positive energy battery is because containing dissipated metal tellurium and cadmium, therefore, carries out innoxious synthesis to cadmium telluride diaphragm solar battery component and returns
It is necessary to receive processing.Byproduct after the recovery processing of such solar cell module includes glass plate, electric wire, valuable dilute scattered gold
Belong to tellurium, cadmium, molybdenum etc., cycling and reutilization can be achieved.The recycling rate of waterused of resource is improved by recovery process.
Copper-indium-galliun-selenium film solar cell (CIGS) due to using your dilute element and the toxic element Cd such as In, Ga, Se,
If dealing with the problems such as being likely to result in waste and environmental pollution improperly.The most importantly reserves of In and limits throughput, are followed
The value that ring utilizes is just abnormal great.It therefore, need to be to using the longevity in order to guarantee the sustainable development of CIGS solar cell material
It orders overdue battery and carries out appropriate recovery processing.
Currently, the recycling of above two film battery assembly compared with frequently with method be wet process after the direct Mechanical Crushing of mould group
It leaches, is separated by solid-liquid separation, valuable metal is recycled from solution.Technique equipment investment early period is less, and technique is also relatively simple, but works
Environment is relatively poor.The cullet slag utility value of generation is small, throws aside stacking and environmental protection pressure is larger.
Summary of the invention
In view of this, the present invention provides a kind of recovery and treatment method of Thinfilm solar cell assembly, valuable metal is returned
High income, working environment is good, and backboard and base plate glass are reusable, and comprehensive utilization ratio is high, improves thin-film solar cells
The material recovery rate and recovering effect of component.
In order to solve the above technical problems, technical solution of the present invention provides a kind of laser of Thinfilm solar cell assembly
Evaporate recovery and treatment method, it is characterised in that：Include the following steps：
(1) laser evaporation photovoltaic film layer：The back-panel glass for the Thinfilm solar cell assembly scrapped and conductive electrode are withdrawn from
The glass substrate with photovoltaic film layer is obtained afterwards, with the photovoltaic film layer on laser irradiation device irradiation at short distance glass substrate to photovoltaic
All evaporation obtains complete glass substrate to film layer；The laser irradiation device includes laser irradiation device, negative-pressure air duct, gas-solid point
From device, solid powder collecting chamber and negative pressure centrifugal blower, laser irradiation device built in negative-pressure air duct arrival end, outlet end and gas-solid divide
It is connected from device, the gas vent of the gas-solid separator connects negative pressure centrifugal blower, and the material outlet of the gas-solid separator connects
Connect solid powder collecting chamber；
Gas-solid separator is efficiently to collect the solids in air-flow and isolated apparatus, the solid material of collection exist
It is periodically discharged into storage bin under gravity, the gas after separation then with the equipment of outlet discharge, is existing common apparatus, belongs to
The prior art；
(2) valuable metal in dissolution recycling photovoltaic film layer：Step (1) solid powder is collected indoor powder to collect out
The valuable metal in photovoltaic film layer is obtained to be operated to can be recycled according to existing hydrometallurgical processes process.
Hydrometallurgy is existing a kind of common method of extracting metals, it mainly includes the following steps：1. by raw material
Useful component is transferred to solution, that is, leaches；2. solvent for metallurgy and gold that leaching solution is separated with residue, while will be become entrained in residue
Belong to ion-cleaning recycling；3. the purification and enrichment of solution are leached, frequently with ion exchange and solvent extraction technology or other chemistry
Intermediate processing；4. extracting metal or compound from scavenging solution.Modern hydrometallurgy almost covers all in addition to steel
Metal smelting, its whole smelting process of some metals belong to hydrometallurgy, but most of is that mineral decompose, extraction and removal of impurities use
Wet processing is finally reduced into metal and is completed using pyrometallurgical smelting or powder metallurgy.Typical hydrometallurgy have tungsten, molybdenum, tantalum,
Niobium, cobalt, nickel, rare earth, uranium, thorium, bismuth, tin, copper, lead, zinc, titanium, manganese, vanadium, Au Ag Pt Pd, indium, ruthenium, osmium, iridium, germanium, gallium etc..
The method of the present invention is suitble to handle cadmium telluride diaphragm solar battery and copper-indium-galliun-selenium film solar cell, for tellurium
The concrete operations of cadmium Thinfilm solar cell assembly, above-mentioned steps (2) are：Step (1) solid powder is collected into indoor powder
End, which collects out, to be put into Strong oxdiative acid solution Oxidation Leaching and forms leachate, and leachate is obtained by extraction through N235 extractant
Extraction raffinate and organic phase, organic phase obtain strip liquor and back extraction organic phase after ammonium hydroxide is stripped, and strip liquor concentration and evaporation obtains secondary molybdenum
Sour ammonium；Vulcanized sodium is added in raffinate and sodium hydroxide solution, sedimentation filtration obtain molten containing cadmium, copper, the sediment of tin and alkalinity
Liquid, in alkaline solution plus acid for adjusting pH value is settled out tellurium dioxide.
Further, the Strong oxdiative acid solution is the mixed solution of hydrogen peroxide and sulfuric acid.
Further, the volume ratio of the hydrogen peroxide and sulfuric acid is for (1~3) ︰ 10.
Further, the mass ratio that step (1) solid powder collects indoor powder and Strong oxdiative acid solution is
Strong oxdiative Suan Rong Ye ︰ powder=(1~8) ︰ 1.
Further, the leachate extraction is extracted using four-stage counter-current, and organic phase back extraction is stripped using three-level.
Further, the back extraction organic phase returns is extracted in leachate.
Further, the mass ratio of the raffinate, vulcanized sodium and sodium hydroxide solution is 3 ︰, 1 ︰ 0.5.
Further, the pH value that the alkaline solution acid adding is adjusted is 5~6.
Further, it is configured to tellurium alkaline electrolyte after the purified processing of tellurium dioxide that the alkaline solution is settled out,
It is obtained metallic tellurium (4N) through tellurium alkaline electrolysis is recyclable, it is high-purity that metallic tellurium (4N) is achieved with photovoltaic grade 5N through vacuum distillation again
Tellurium.
The basic structure of cadmium telluride diaphragm solar battery component is：Base plate glass+transparency conducting layer+CdS layer+CdTe layer
+ back electrode layer+conductive adhesive tape+sealing joint strip+cover-plate glass.Wherein, photovoltaic film layer includes transparency conducting layer, CdS layer, CdTe layer
And back electrode layer, FTO transparency conducting layer are made of fluorine-doped tin oxide film, back electrode layer be by molybdenum target through magnetron sputtering plating and
At, therefore the valuable metal of photovoltaic film layer includes tin, cadmium, tellurium, copper, molybdenum etc..
Copper indium gallium selenide (CIGS) thin-film solar cells have multi-layer film structure, including metal gate-shaped electrode, antireflective coating,
Window layer (ZnO), transition zone (CdS), light absorbing layer (CIGS), metal back electrode (Mo), glass substrate etc..Absorbed layer CIGS
(chemical formula CuInGaSe2) compound semiconductor with yellow copper structure that is made of four kinds of elements, it is hull cell
Critical material.Wherein, photovoltaic film layer includes antireflective coating, Window layer, transition zone, light absorbing layer and metal back electrode, therefore, light
The organic metal for lying prostrate film layer includes zinc, cadmium, copper, indium, gallium, selenium, molybdenum etc..
The valuable metal in photovoltaic film layer is recycled, needs to be divided photovoltaic film layer and base plate glass and cover-plate glass
From it is all wet-leaching after Mechanical Crushing at present that but due to the effect of sealant, glass plate, which is difficult completely to separate, but the technique
The cullet slag disposed largely is difficult to by generating.
The present invention uses laser direct irradiation photovoltaic film layer, photovoltaic film layer is transferred energy in moment, to make photovoltaic
Film layer is rapidly heated steam raising, and evaporant enters in the negative pressure straw above laser irradiation device with air-flow fast transfer, most
After be deposited in solid powder collecting chamber.
Therefore, compared with Conventional processing methods, the present invention uses the technique of laser irradiation photovoltaic film layer, removes photovoltaic film
Layer, the process of valuable metal solids is very short in collection photovoltaics film layer, speed is fast；The rate of recovery of valuable metal is high, building ring
Border is good, and it is high that glass substrate damages small reuse ratio；Mechanical automation technique can be used completely, and working environment is good, it is ensured that produces
Product chain whole process is environmental-friendly, improves the material recovery rate and recovering effect of Thinfilm solar cell assembly, improves resource benefit
With rate.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the present invention；
Fig. 2 is the structural schematic diagram of laser irradiation device of the present invention；
Fig. 3 is the flow diagram of present invention recycling cadmium telluride diaphragm solar battery component.
Marginal data：
1, laser irradiation device；2, negative-pressure air duct；3, gas-solid separator；4, solid powder collecting chamber；5, negative pressure centrifugal blower；
6, the glass substrate with photovoltaic film layer.
Specific embodiment
It is with reference to the accompanying drawing and specific real in order to make those skilled in the art more fully understand technical solution of the present invention
Applying example, the present invention is described in further detail.
Referring to Fig. 1, a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly provided by the invention, including
Following steps：
(1) laser evaporation photovoltaic film layer：The back-panel glass for the Thinfilm solar cell assembly scrapped and conductive electrode are withdrawn from
The glass substrate 6 with photovoltaic film layer is obtained afterwards, with the photovoltaic film layer on laser irradiation device irradiation at short distance glass substrate to light
All evaporation obtains complete glass substrate to volt film layer；Referring to fig. 2, the laser irradiation device includes laser irradiation device 1, negative pressure
Air hose 2, gas-solid separator 3, solid powder collecting chamber 4 and negative pressure centrifugal blower 5, laser irradiation built in 2 arrival end of negative-pressure air duct
Device 1, outlet end are connect with gas-solid separator 3, and the gas vent of the gas-solid separator 3 connects negative pressure centrifugal blower 5, the gas
The material outlet of solid separator 3 connects solid powder collecting chamber 4；Photovoltaic film layer is rapidly heated steam raising upon laser irradiation,
Evaporant is rapidly introduced into the negative-pressure air duct 2 of 1 top of laser irradiation device with air-flow, is most deposited on afterwards through gas-solid separator 3 solid
It is to be processed in body powder collection chamber 4.
(2) valuable metal in dissolution recycling photovoltaic film layer：Step (1) solid powder is collected indoor powder to collect out
The valuable metal in photovoltaic film layer is obtained to be operated to can be recycled according to existing hydrometallurgical processes process.
The present invention is further detailed for recycling cadmium telluride diaphragm solar battery component below.
Referring to Fig. 3, a kind of laser evaporation recovery and treatment method of cadmium telluride diaphragm solar battery component, including following step
Suddenly：
(1) laser evaporation photovoltaic film layer：By the back-panel glass and conduction of the cadmium telluride diaphragm solar battery component scrapped
Pole obtains the glass substrate with photovoltaic film layer after withdrawing from, with the photovoltaic film on laser irradiation device irradiation at short distance glass substrate
Layer, photovoltaic film layer are rapidly heated steam raising upon laser irradiation, and evaporant is rapidly introduced into 1 top of laser irradiation device with air-flow
Negative-pressure air duct 2 in, be most deposited on afterwards through gas-solid separator 3 to be processed in solid powder collecting chamber 4.
(2) step (1) solid powder is collected indoor powder and collects out to be put into aoxidize in Strong oxdiative acid solution and soaked
Leachate is formed out, and raffinate and organic phase is obtained by extraction through N235 extractant in leachate, and organic phase obtains after ammonium hydroxide is stripped
Strip liquor and back extraction organic phase, strip liquor concentration and evaporation obtain ammonium paramolybdate；Vulcanized sodium is added in raffinate and sodium hydroxide is molten
Liquid, sedimentation filtration obtain containing cadmium, copper, tin sediment and alkaline solution, in alkaline solution plus acid for adjusting pH value is settled out dioxy
Change tellurium.
Above-mentioned Strong oxdiative acid solution is the mixed solution of hydrogen peroxide and sulfuric acid.
The volume ratio of hydrogen peroxide and sulfuric acid is for (1~3) ︰ 10.
Solid powder collect indoor powder and Strong oxdiative acid solution mass ratio be the molten liquid ︰ powder of Strong oxdiative acid=
(1~8) ︰ 1.
Above-mentioned leachate extraction is extracted using four-stage counter-current, and organic phase back extraction is stripped using three-level.
Above-mentioned back extraction organic phase returns to be extracted in leachate.
The mass ratio of above-mentioned raffinate, vulcanized sodium and sodium hydroxide solution is 3 ︰, 1 ︰ 0.5.
The pH value that above-mentioned alkaline solution acid adding is adjusted is 5~6.
It is configured to tellurium alkaline electrolyte after the purified processing of the tellurium dioxide that above-mentioned alkaline solution is settled out, through tellurium alkaline electro
Solution is recyclable to be obtained metallic tellurium (4N), and metallic tellurium (4N) is achieved with photovoltaic grade 5N high purity tellurium through vacuum distillation again.
Compared with Conventional processing methods, the present invention uses the technique of laser irradiation photovoltaic film layer, and removing photovoltaic film layer is collected
The process of valuable metal solids is very short in photovoltaic film layer, speed is fast；The rate of recovery of valuable metal is high, and working environment is good, glass
The small reuse ratio of glass substrate damage is high；Mechanical automation technique can be used completely, and working environment is good, it is ensured that product chain is whole
It is environmental-friendly, the material recovery rate and recovering effect of Thinfilm solar cell assembly are improved, is improved resource utilization.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly, it is characterised in that：Include the following steps：
(1) laser evaporation photovoltaic film layer：After the back-panel glass for the Thinfilm solar cell assembly scrapped and conductive electrode are withdrawn from
To the glass substrate with photovoltaic film layer, with the photovoltaic film layer on laser irradiation device irradiation at short distance glass substrate to photovoltaic film layer
All evaporation obtains complete glass substrate；The laser irradiation device includes laser irradiation device, negative-pressure air duct, gas solid separation
Device, solid powder collecting chamber and negative pressure centrifugal blower, laser irradiation device built in negative-pressure air duct arrival end, outlet end and gas solid separation
Device connection, the gas vent of the gas-solid separator connect negative pressure centrifugal blower, the material outlet connection of the gas-solid separator
Solid powder collecting chamber；
(2) valuable metal in dissolution recycling photovoltaic film layer：The indoor powder of step (1) solid powder collection is collected out and is pressed
It is operated to can be recycled according to existing hydrometallurgical processes process and obtains the valuable metal in photovoltaic film layer.
2. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 1, feature
It is：For cadmium telluride diaphragm solar battery component, the concrete operations of the step (2) are：Step (1) solid powder is received
Collect indoor powder and collect out and be put into Strong oxdiative acid solution Oxidation Leaching and form leachate, leachate is through N235 extractant
Raffinate and organic phase is obtained by extraction, organic phase obtains strip liquor and back extraction organic phase after ammonium hydroxide is stripped, and strip liquor concentration is steamed
Hair obtains ammonium paramolybdate；Vulcanized sodium is added in raffinate and sodium hydroxide solution, sedimentation filtration obtain the precipitating containing cadmium, copper, tin
Object and alkaline solution, in alkaline solution plus acid for adjusting pH value is settled out tellurium dioxide.
3. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：The Strong oxdiative acid solution is the mixed solution of hydrogen peroxide and sulfuric acid.
4. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 3, feature
It is：The volume ratio of the hydrogen peroxide and sulfuric acid is for (1~3) ︰ 10.
5. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：It is that Strong oxdiative acidity is molten that step (1) solid powder, which collects indoor powder and the mass ratio of Strong oxdiative acid solution,
Ye ︰ powder=(1~8) ︰ 1.
6. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：The leachate extraction is extracted using four-stage counter-current, and organic phase back extraction is stripped using three-level.
7. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：The back extraction organic phase returns to be extracted in leachate.
8. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：The mass ratio of the raffinate, vulcanized sodium and sodium hydroxide solution is 3 ︰, 1 ︰ 0.5.
9. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 2, feature
It is：The pH value that the alkaline solution acid adding is adjusted is 5~6.
10. a kind of laser evaporation recovery and treatment method of Thinfilm solar cell assembly according to claim 1, feature
It is：It is configured to tellurium alkaline electrolyte after the purified processing of the tellurium dioxide that the alkaline solution is settled out, through tellurium alkaline electrolysis
Obtain metallic tellurium.
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| CN113564361A (en) * | 2021-05-19 | 2021-10-29 | 兰州有色冶金设计研究院有限公司 | Pyrogenic treatment and recovery process of cadmium telluride thin-film solar cell |
| CN115503330A (en) * | 2022-06-27 | 2022-12-23 | 合复新材料科技(无锡)有限公司 | Interface separation and recovery method of EVA-Si laminating layer of solar backboard |
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Application publication date: 20181130 |