CN107687018A - A kind of method of sensitization solar battery light anode MAT'L recycling - Google Patents
A kind of method of sensitization solar battery light anode MAT'L recycling Download PDFInfo
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- CN107687018A CN107687018A CN201710612396.9A CN201710612396A CN107687018A CN 107687018 A CN107687018 A CN 107687018A CN 201710612396 A CN201710612396 A CN 201710612396A CN 107687018 A CN107687018 A CN 107687018A
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- light anode
- photosensitizer
- solar battery
- sensitization solar
- conductive substrates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/12—Etching of semiconducting materials
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Abstract
The invention discloses a kind of method of sensitization solar battery light anode MAT'L recycling, recycles photosensitizer, nano semiconductor material and electrically conducting transparent base material used in film sensitization solar battery light anode.To avoid photosensitizer from being denatured, photosensitizer and semiconductor film UF membrane are made by electrolysis；To avoid damage to the conductive layer of conductive substrates, light anode after being electrolysed by acid soak makes Nanometer Semiconductor Films be separated with conductive substrates, handled again by a series of decontamination deionization, the higher photosensitizer of recovery value, the semi-conducting material for preparing nano thin-film and conductive substrates these three materials.
Description
Technical field
The invention belongs to the crossing domain of chemistry and material, refers to a kind of recovery sensitization solar battery light anode material
The method of material.
Background technology
World today's energy scarcity, natural resources are increasingly exhausted, environmental pollution is on the rise；It is sustainable development, recyclable
Using with the green theme as era development.In order to solve energy problem, scientific circles research and develop new energy energetically
The utilization in source, wherein solar energy turns into the focus of research, various new in addition to the silicon solar cell for having formd industrialization
Type thin-film solar cells also shows good prospect, but utilization of most of these solar cells to material is all one
Secondary property, the serious waste more than to material, while environment can also be polluted.
The manufacture craft of novel thin film sensitization solar battery is all similar.Typically contain the electrically conducting transparent as substrate
Material, Nanometer Semiconductor Films and conduct photosensitizer as electric transmission and absorption photosensitizer produce photoelectric light
Sensitizer.The material for doing substrate is usually to deposit Fluorin doped SnO2Electro-conductive glass, conductive plastics, special metal material.System
The material of standby nano thin-film has titanium dioxide, zinc oxide, SnO2Deng metal-oxide semiconductor (MOS).Photosensitizer has inorganic and organic
Two major classes, inorganic photosensitizer are mainly the rutheniums such as N3, N719（Ru）It is metal multi-pyridine ligand, metalloporphyrin, phthalocyanine dye；
Organic photosensitive agent is mainly indoles, Coumarins dyestuff.The preparation of light anode is typically all that nano semiconductor material sinks
Product such as deposits Fluorin doped SnO in electrically conducting transparent substrate2Electro-conductive glass, conductive plastic film etc., formed one layer of Nano semiconductor
Film.Nowadays either in scientific research still in the product of the thin-film solar cells used, the use of light anode
All it is disposable, is just discarded after used.This not only results in the pollution of environment, and is the significant wastage to material.
But light anode is by its special structure that it really can only disposably be used, but for material used in light anode but
It can be reused by some technological means.
It is complicated to prepare the electrically conducting transparent substrate preparation technology of light anode, material price costliness.Sensitizer is with ruthenium system photosensitizer
The electricity conversion highest of agent；Ruthenium element is rare element, and reserves are less on the earth, expensive.And some inorganic light
Sensitizer also has pollution to environment.And the semi-conducting material in conductive substrates is deposited on, need consumption a large amount of in its production process
The energy and rare mineral matter.By be currently in that the laboratory research stage studied be all small area thin film solar electricity
Pond, it is disposable not bring too big economic loss and environmental hazard also, therefore also not it has been proposed that to light anode material
Recovery.But large area conductive substrates and semiconductor film material are needed to use if large-scale application.The solar battery longevity
Life is usually 15 years or so.Reach the performance of its light anode conductive substrates of the solar battery of useful life and semi-conducting material simultaneously
Do not change, still can be used for producing new light anode by recycling both materials.It is not only among these
Recycling to resource, the generation of industrial waste is reduced, while also contain huge economic benefit.
The content of the invention
For the broad scale research of nowadays sensitization solar battery, the difference of its electricity conversion and conventional solar cell
Away from less and less, the recycling problem of material will be faced when it is in large-scale application.
The invention provides a kind of method for the MAT'L recycling that solar cell is prepared to light anode, pass through electrolysis
Method makes photosensitizer be come off from light anode.Light anode semi-conducting material and conductive substrates are divided by the method for acid soak again
From the method for recycling each several part material.Photosensitizer is set to be separated with Nanometer Semiconductor Films discarded light anode electrolysis,
Then the Nanometer Semiconductor Films that immersion makes to deposit thereon in acid solution are separated so as to recycle these three materials.
A kind of method of sensitization solar battery light anode MAT'L recycling, it is characterised in that comprise the following steps：
（1）The sensitization solar battery for being up to useful life is disassembled, the light anode of cleaning performance failure；
（2）Negative voltage electrolysis desorption is added to separate photosensitizer from light anode；
（3）Acid soak is through step（1）Light anode separation Nanometer Semiconductor Films and conductive substrates after processing.
A kind of method of sensitization solar battery light anode MAT'L recycling in further detail below the step of：
（1）First used light anode is put into absolute ethyl alcohol to soak 5 minutes and rinsed one time with absolute ethyl alcohol again, air conditionses
Lower drying, then make photosensitizer come off by being electrolysed desorption, takes out light anode after photosensitizer is completely fallen off, spend from
Sub- water is rinsed, then the electrolyte rotation after electrolysis is evaporated, and extracts photosensitizer therefrom；
（2）Step will be passed through（1）The light anode of processing cleans up in deionized water, the light anode after cleaning is put into low dense
Soaked in degree acid solution.24 hours will be incubated at 60 degrees Celsius and then light is taken out from acid solution immersed with the low concentration acid solution of light anode
Anode.By the light anode of taking-up, ultrasound makes film be separated with conductive substrates in 10 minutes in deionized water；
（3）By step（2）The nano semiconductor material of gained is soaked 5 minutes in absolute ethyl alcohol, and 10 points are cleaned with deionized water
Clock, filtering drying recovery nano semiconductor material.Simultaneously to step（2）The conductive substrates of gained are ultrasonic 20 points in deionized water
Clock, then clean conductive substrates twice with cleanser, rinsed well with deionized water, be put into absolute ethyl alcohol and soak 5 minutes, taken out
Rinsed repeatedly with deionized water 2 times, drying recovery conductive substrates.
Nanometer Semiconductor Films are made to be separated with conductive substrates by acid soak.
The temperature of acid soak is 60 degrees Celsius, and the time of immersion is 24 hours.
Collect the photosensitizer, photosensitive according to used in different sensitization solar batteries its light anode for preparing light anode
It is the inorganic photosensitizer such as metal multi-pyridine ligand, metalloporphyrin, phthalocyanine dye that agent, which has ruthenium (Ru), and organic synthesis dye
The organic photosensitive agent such as material and natural organic dye.
Collect the Nanometer Semiconductor Films material being deposited in light anode electrically conducting transparent substrate；Prepare Nanometer Semiconductor Films
Material have nano-TiO2、ZnO、ZnO2、SnO2Deng nano-metal-oxide and Nano-meter SiO_22Deng nonmetal oxide.
The electrically conducting transparent base material for preparing light anode is collected, conductive substrates have deposition Fluorin doped SnO2Electro-conductive glass
(FTO), the TCO coated glasses transparent conductor material such as surface depositing indium-tin-oxide transparent conductive semiconductor film (ITO) and
Other particulate metal good conductor materials.
According to the variety classes of light anode, prepare the semi-conducting material of nano thin-film and the difference of conductive substrates and select not
Same acid solution.Acid solution has strong acid in dust technology, dilute sulfuric acid, watery hydrochloric acid etc., and the weak acid such as acetic acid, carbonic acid.
It is an advantage of the invention that：Recycle photosensitizer, nanometer used in film sensitization solar battery light anode
Semi-conducting material and electrically conducting transparent base material.To avoid photosensitizer from being denatured, photosensitizer and semiconductor film are made by electrolysis
UF membrane；To avoid damage to the conductive layer of conductive substrates, the light anode after being electrolysed by acid soak makes Nanometer Semiconductor Films
Separate with conductive substrates, then handled by a series of decontamination deionization, the higher photosensitizer of recovery value, prepare nanometer thin
These three materials of the semi-conducting material and conductive substrates of film.
Embodiment
Instantiation is as follows：Recovery is using N719 dyestuffs as photosensitizer, nano-TiO2Semi-conducting material is as film material
Material, surface deposition Fluorin doped SnO2Light anode material of the electro-conductive glass as the DSSC of conductive substrates.
Step is as follows；
（1）Reclaim N719；The N719 DSSCs for being first up to useful life are taken apart, by the light anode of failure
Rinsed with high-purity deionized water, be put into absolute ethyl alcohol and soak 5 minutes afterwards, being put into air-dry in fume hood is evaporated completely ethanol
Entirely, then add negative voltage electrolysis N719 is come off in the acetonitrile solution of 0.1mol/l tetrabutyl ammonium hexafluorophosphate, work as N719
Light anode is taken out after completely falling off, with deionized water rinsing, then N719 is extracted from electrolyte.
（2）Separate surface deposition Fluorin doped SnO2Electro-conductive glass and nano-TiO2 By recovered photosensitizer excessively
It is coated with nano-TiO2Deposition Fluorin doped SnO2Electro-conductive glass flushed three times with deionized water be put into absolute ethyl alcohol soak 5 points
Clock, then rinsed well with deionized water.Take 1mol/L dust technologies to be put into container, light anode is put into wherein, container is close
Envelope.It is put into thermostatic drying chamber, temperature is transferred to 60 degree, is incubated 24 hours.After taking-up container after temperature drops to room temperature,
Light anode is taken out in fume hood and is put into ultrasound 10 minutes in deionized water, separates film and conductive substrates, deposition fluorine is taken out and mixes
Miscellaneous SnO2Electro-conductive glass cleaning.
3rd, recovery deposition Fluorin doped SnO2Electro-conductive glass and nano-TiO2Film；Reclaim nano-TiO2Film
Deposition Fluorin doped SnO will have been separated2Electro-conductive glass acid liquor filtering after, will filter gained nano-TiO2It is put into high-purity
Soak 10 minutes and filters in degree deionized water, after soak 5 minutes and refilters in absolute ethyl alcohol, by the nano-TiO obtained by filtering2
Thermostatic drying chamber drying is put into, reclaims nano-TiO2。Reclaim surface deposition Fluorin doped SnO2Electro-conductive glass；After separation
Deposit Fluorin doped SnO2Electro-conductive glass be put into supersonic cleaning machine in deionized water ultrasound 20 minutes.Cleaned repeatedly with cleanser
Deposit Fluorin doped SnO2Twice of electro-conductive glass, rinsed well with deionized water.It is put into absolute ethyl alcohol and soaks 5 minutes, takes out
Rinsed repeatedly with high-purity deionized water.By the deposition Fluorin doped SnO after cleaning2Electro-conductive glass be put into thermostatic drying chamber baking
It is dry, recovery deposition Fluorin doped SnO2Electro-conductive glass.
1st, photosensitizer is reclaimed；The solar cell for being first up to useful life is taken apart, and the light anode of failure is put into
Soak in absolute ethyl alcohol 5 minutes and rinsed one time with absolute ethyl alcohol again, be put into fume hood and air-dry, then by adding negative voltage to light anode
Electrolysis makes photosensitizer come off, and takes out light anode after photosensitizer is completely fallen off pending, then electrolyte rotation is evaporated
Photosensitizer is extracted from electrolyte.
2nd, light anode conductive substrates and Nanometer Semiconductor Films are separated；Light anode after photosensitizer is come off go from
It is put into low concentration acid solution and soaks after being cleaned up in sub- water.Low concentration acid immersed with light anode is put into 60 degree of insulating box
Insulation is taken out for 24 hours.By the light anode of taking-up, ultrasound makes film be separated with conductive substrates in 10 minutes in deionized water.
3rd, nano semiconductor material and conductive substrates are reclaimed.Reclaim nano semiconductor material
It after the acid liquor filtering for having separated conductive substrates, will soak 5 minutes and filter in absolute ethyl alcohol, the nanometer half of gained will be filtered
Conductor material is put into high-purity deionized water to soak 10 minutes and filtered, and the nano semiconductor material for filtering gained is put into constant temperature
Drying box is dried, and reclaims nano semiconductor material.
Reclaim conductive substrates；Conductive substrates are put into ultrasound 20 minutes in supersonic cleaning machine, then it is repeatedly clear with cleanser
Wash conductive substrates twice, rinsed well with deionized water, be put into absolute ethyl alcohol and soak 5 minutes, taking-up with deionized water repeatedly
Rinse 2 times.Thermostatic drying chamber drying is finally putting into, reclaims conductive substrates.
Claims (8)
- A kind of 1. method of sensitization solar battery light anode MAT'L recycling, it is characterised in that comprise the following steps：（1）The sensitization solar battery for being up to useful life is disassembled, the light anode of cleaning performance failure；（2）Negative voltage electrolysis desorption is added to separate photosensitizer from light anode；（3）Acid soak is through step（1）Light anode separation Nanometer Semiconductor Films and conductive substrates after processing.
- 2. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, including, below More specifically step：（1）First used light anode is put into absolute ethyl alcohol to soak 5 minutes and rinsed one time with absolute ethyl alcohol again, air conditionses Lower drying, then make photosensitizer come off by being electrolysed desorption, takes out light anode after photosensitizer is completely fallen off, spend from Sub- water is rinsed, then the electrolyte rotation after electrolysis is evaporated, and extracts photosensitizer therefrom；（2）Step will be passed through（1）The light anode of processing cleans up in deionized water, the light anode after cleaning is put into low dense Soaked in degree acid solution；24 hours will be incubated at 60 degrees Celsius and then light is taken out from acid solution immersed with the low concentration acid solution of light anode Anode；By the light anode of taking-up, ultrasound makes film be separated with conductive substrates in 10 minutes in deionized water；（3）By step（2）The nano semiconductor material of gained is soaked 5 minutes in absolute ethyl alcohol, and 10 points are cleaned with deionized water Clock, filtering drying recovery nano semiconductor material；Simultaneously to step（2）The conductive substrates of gained are ultrasonic 20 points in deionized water Clock, then clean conductive substrates twice with cleanser, rinsed well with deionized water, be put into absolute ethyl alcohol and soak 5 minutes, taken out Rinsed repeatedly with deionized water 2 times, drying recovery conductive substrates.
- 3. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：Nanometer Semiconductor Films are made to be separated with conductive substrates by acid soak.
- 4. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：The temperature of acid soak is 60 degrees Celsius, and the time of immersion is 24 hours.
- 5. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：Collect the photosensitizer for preparing light anode, the photosensitizer according to used in different sensitization solar batteries its light anode It is the inorganic photosensitizer such as metal multi-pyridine ligand, metalloporphyrin, phthalocyanine dye to have ruthenium (Ru), and organic synthetic dye and The organic photosensitive agent such as natural organic dye.
- 6. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：Collect the Nanometer Semiconductor Films material being deposited in light anode electrically conducting transparent substrate；Prepare the material of Nanometer Semiconductor Films Material has nano-TiO2、ZnO、ZnO2、SnO2Deng nano-metal-oxide and Nano-meter SiO_22Deng nonmetal oxide.
- 7. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：The electrically conducting transparent base material for preparing light anode is collected, conductive substrates have deposition Fluorin doped SnO2Electro-conductive glass (FTO), The TCO coated glasses transparent conductor materials such as surface depositing indium-tin-oxide transparent conductive semiconductor film (ITO) and other spies Different metal good conductor material.
- 8. a kind of method of sensitization solar battery light anode MAT'L recycling according to claim 1, its feature exist In：According to the variety classes of light anode, prepare the semi-conducting material of nano thin-film and the difference of conductive substrates and select different Acid solution；Acid solution has strong acid in dust technology, dilute sulfuric acid, watery hydrochloric acid etc., and the weak acid such as acetic acid, carbonic acid.
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Cited By (2)
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| CN110797464A (en) * | 2019-11-07 | 2020-02-14 | 重庆文理学院 | Method for recycling transparent conductive electrode of organic solar cell |
| CN112713326A (en) * | 2019-10-25 | 2021-04-27 | 辉能科技股份有限公司 | Method for recovering original phase of oxide solid electrolyte, method for manufacturing lithium battery and green battery thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112713326A (en) * | 2019-10-25 | 2021-04-27 | 辉能科技股份有限公司 | Method for recovering original phase of oxide solid electrolyte, method for manufacturing lithium battery and green battery thereof |
| US11575158B2 (en) * | 2019-10-25 | 2023-02-07 | Prologium Technology Co., Ltd. | Recycling method for oxide-based solid electrolyte with original phase, method of fabricating lithium battery and green battery thereof |
| CN112713326B (en) * | 2019-10-25 | 2023-11-24 | 辉能科技股份有限公司 | Primary phase recovery method of oxide solid electrolyte, manufacturing method of lithium battery and green environment-friendly battery thereof |
| CN110797464A (en) * | 2019-11-07 | 2020-02-14 | 重庆文理学院 | Method for recycling transparent conductive electrode of organic solar cell |
| CN110797464B (en) * | 2019-11-07 | 2022-04-01 | 重庆文理学院 | Method for recycling transparent conductive electrode of organic solar cell |
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Application publication date: 20180213 |