CN109786561A - A kind of technique with perovskite active layer in amine liquefaction perovskite method recycling and reusing perovskite device - Google Patents
A kind of technique with perovskite active layer in amine liquefaction perovskite method recycling and reusing perovskite device Download PDFInfo
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- CN109786561A CN109786561A CN201910059471.2A CN201910059471A CN109786561A CN 109786561 A CN109786561 A CN 109786561A CN 201910059471 A CN201910059471 A CN 201910059471A CN 109786561 A CN109786561 A CN 109786561A
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Abstract
The invention discloses a kind of techniques with perovskite active layer in amine liquefaction perovskite method recycling and reusing perovskite device, including perovskite active layer in recycling and reusing perovskite device, evaporation amine obtains perovskite material after the recycling and reusing method (substrate is used to prepare solar cell device or other again) of gained substrate, the waste liquid initial gross separation generated, can further apply in the preparation of new round device.Technique of the present invention has low temperature, low power consuming, to the simple and effective recycling and reusing of calcium titanium ore bed.It the invention can avoid the potential threat caused by environment and health of human body, may be implemented to recycle to the abundant of resource and again, there is potential good economic benefit, the functionization of cheap perovskite solar cell can be pushed further into.
Description
Technical field
The present invention relates to the preparation of perovskite device and resource reclaim reutilization technology fields, in particular to a kind of to use amine liquid
The technique for changing perovskite active layer in perovskite method recycling and reusing perovskite device.
Background technique
Energy problem is the problem of mankind must face, fossil energy, if petroleum, natural gas, coal are non-renewable energy
Source, these energy can exhaust eventually, therefore greatly develop renewable energy and replace non-renewable energy resources to be only selection with comprehensive.
Solar energy is a kind of nexhaustible renewable energy, it is contemplated that from now, to the year two thousand thirty, photovoltaic power generation will account for the whole world, and newly power generation is held
The nearly one third of amount.Based on monte-Carlo model (Monte Carlo model), scientist has found the calcium titanium in cost at present
Thin-film solar cells cost based on mine is well below other kinds of solar battery.Therefore, perovskite replaces silicon
Preparing solar battery has more possibilities.
In view of by lead be based on perovskite material there is good photoelectric characteristic to be not easy to replace, but the poison of lead
Property and other metallic elements rare characteristic, a large amount of perovskite solar batteries that manufacture will certainly generate a large amount of lead bearing wastes, and
These wastes are directly discharged to will cause serious soil and pollution of waterhead and the wasting of resources in environment.Considered back based on this
It receives and perovskite material is recycled just to be particularly important.
For in the recycling and treatment process of current organic inorganic hybridization perovskite solar battery use dimethyl formyl
Amine (N, N-Dimethylformamide, DMF) or dimethyl sulfoxide (Dimethyl sulfoxide, DMSO) etc. are highly polar to be had
Solvent, these solvent boiling points are high, at high cost, treatment process highly energy-consuming, to each functional layer low separation efficiency.For current calcium titanium
The recycling and reusing of mine solar battery and the highly energy-consuming for the treatment of process, to each functional layer low separation efficiency, in order to avoid environment
Pollute and realize recycling for resource, spy proposes molten using low-boiling point gas or liquid amine solution based on low temperature (room temperature)
Solve perovskite.Recycling and reusing perovskite solar battery simultaneously realizes substrate, organic inorganic hybridization perovskite, organic function layer,
The recycling technique of the heavy metals such as inorganic functional layer and silver/gold and noble metal back electrode material.
Summary of the invention
Based on this, the present invention provides a kind of with calcium titanium in amine liquefaction perovskite method recycling and reusing perovskite device
The technique of mine active layer, the technique can not only re-use transparent conducting glass (such as FTO, ITO) or transparent conducting glass/oxygen
Compound substrate, and recycling and reusing organic inorganic hybridization perovskite, organic function layer, inorganic functional layer and silver/gold etc.
Heavy metal and noble metal back electrode material, while the double effects of the feature of environmental protection Yu resource-effective property are realized, there is potential warp
Ji benefit, is expected to further decrease the manufacturing cost of perovskite solar battery and cost recovery period, to promote perovskite
Solar cell becomes real clean energy resource and contributes for the development of human society.
Technical scheme is as follows:
A kind of technique with perovskite active layer in amine liquefaction perovskite method recycling and reusing perovskite device, specific steps
It is as follows:
Step (1), the cleaning step of perovskite device:, can using chain types amines such as low boiling point methylamine or ethamine to device processing
It also may be dipped in the amines such as ethamine with being placed in methylamine gas environment, processing is impregnated repeatedly, perovskite material is dissolved, without
Other function layer can be dissolved.
Step (2) substrate cleaning: to (1) resulting substrate with continuing to be handled repeatedly with amines such as methylamine or ethamine, is steamed
Surface solvent is sent out, recycling and reusing utilizes substrate.
Step (3), substrate can be reused for preparing solar cell device: new using the above processing gained substrate preparation
Solar cell device.
Step (4), the waste liquid (the mix suspending object or precipitating of each functional layer composition) of generation and obtains back electrode metal
Material processing: after the filtering of waste liquid obtained by step (1), suspended matter or precipitating are separated from waste liquid.
Step (5), the further utilization to recycling perovskite waste liquid: step (4) filtered waste liquid is according to amine used
Boiling point selects suitable heating temperature heating evaporation to be more than amine, this step obtains perovskite, is recycling and reusing lead committed step,
Solution containing perovskite is isolated after amine liquefaction calcium titanium ore bed, is returned after room temperature or according to amine boiling point appropriate heating abjection amine
It receives and recycles solid perovskite material, perovskite material can be used to prepare new round device, and equally can weight after amine recycling
It is multiple to utilize.
Preferably, amine used in the present invention includes the chain types amine such as methylamine, ethamine, propylamine.
Preferably, the perovskite device refers mainly to the solar battery based on perovskite, secondly refers to LED and field-effect
The device architecture of transistor etc., solar battery and LED have ITO(FTO and flexible conductive film) glass/electronics or hole function
Modifying interface other function layer is added in layer/calcium titanium ore bed/hole or electronic work ergosphere/back electrode or its mutation, such as each interlayer.
Preferably, the liquefaction refers to that perovskite encounters amine and can liquefy, and the present invention is this property that perovskite liquefies
It applies in recycling and reusing perovskite device.
Preferably, the amine liquefaction perovskite part refers to that perovskite can be liquefied by amine by perovskite amine environment.
Preferably, the amine liquefaction recycling and reusing perovskite device refers to the calcium titanium that perovskite device is put into amine
In mine environment, the perovskite on perovskite device can be liquefied and be detached from substrate, and waste liquid is further separated to reach back after disengaging
Receive the purpose for recycling perovskite active layer.
Preferably, the perovskite refers to that perovskite has AMX3General formula, central metal cation M and anion X-shaped at
It is coordinated octahedral structure, A is present in octahedral interstice, plays balance BX3The effect of anionic charge, M be metal Ge, Sn, Pb,
Any one of Cu, Mn, Sb, Bi or two kinds or more, any one of X Cl, Br, I or two kinds or more are common
There is CH3NH3PbI3、NH2CH=NH2PbI3。
Preferably, step (5) utilizes the chemical equation RNH of gained filtrate3MX3 ·nRNH2→RNH3MX3 +
nRNH2↑ (R is organic chain type group in formula, and X is halogen, M is metallic element) obtain perovskite, prepares new one with this
Take turns device.
Beneficial effects of the present invention are as follows: 1) present invention recycles again the device of organic inorganic hybridization perovskite solar cell
It is maximized using processing with technological effect is recycled, energy simple and practical ground recycling and reusing includes organic function layer and inorganic functional
Layer；2) present invention still is able to reuse to each functional layer of recycling；3) present invention is using chains such as low boiling point methylamine or ethamine
Formula amine can volatilize to device processing, low boiling point amine at very low temperatures, therefore can recycle practical, maximized realization
Harmless treatment waste product.
Detailed description of the invention
Fig. 1 is perovskite solar cell device basic structure schematic diagram.
Fig. 2 is the recycling and reusing detailed step schematic diagram of perovskite solar cell device.
Fig. 3 be ethanol amine to before the preliminary cleaning treatment of device, packaging, obtained ultraviolet-visible is inhaled after processing
Receive spectrum schematic diagram.
Specific embodiment
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be readily apparent from understanding, tie now
The present invention is described in further detail for conjunction specific embodiment and attached drawing.These attached drawings are simplified schematic diagram, only with
Illustration illustrates basic structure of the invention, therefore it only shows the composition relevant to the invention.
Embodiment 1
Fig. 2 is referred to, the present embodiment uses ethanolamine treatment ITO/ perovskite/PCBM/ encapsulated layer.
Specifically, structure involved by the present embodiment is that ITO electro-conductive glass size is 25mm × 25mm, and PCBM is uniform
It is coated on perovskite surface, encapsulated layer area 15mm × 15m.
Fig. 3 is referred to, the device prepared is placed in ethanol amine, the non-encapsulated layer covering on after 1s it can be found that surface
Part be dissolved and be detached from substrate, throwing off encapsulated layer perovskite is dissolved rapidly, and preliminary cleaning is to obtain transparent conducting glass
The mixed solution and suspended matter of ITO and each functional layer chemical constituent of device, further to the thorough cleaning of substrate to prepare new one
The device of wheel.
Embodiment 2
Fig. 2 is referred to, the present embodiment uses the device of methylamine recycling and reusing classics planar heterojunction structure perovskite solar cell
Part.
Referring to Figure 1, the device architecture of planar heterojunction structure perovskite solar cell is discarded involved in the present embodiment
It is ITO/ nickel oxide/perovskite/PCBM/ aluminium electrode, ITO electro-conductive glass size is 25mm × 25mm, distributed six above
A area is the device of 3mm × 3mm.
Specifically, the device prepared is placed in closed methylamine environment, the perovskite quilt on after 1s it can be found that surface
It dissolves and is detached from substrate, methylamine cleans device tentatively to obtain transparent conducting glass/NiO and each functional layer chemical group of device
The mixed solution and suspended matter divided is further cleaned and is handled to prepare the device of a new round, back electrode energy to the thorough of substrate
Enough by filtering come recycling and reusing.
The foregoing is merely presently preferred embodiments of the present invention, and those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, protection scope of the present invention all should belong to.
Claims (8)
1. a kind of technique with perovskite active layer in amine liquefaction perovskite method recycling and reusing perovskite device, feature
It is, the specific steps are as follows:
Step (1), the cleaning step of perovskite device:, can using chain types amines such as low boiling point methylamine or ethamine to device processing
It also may be dipped in the amines such as ethamine with being placed in methylamine gas environment, processing is impregnated repeatedly；
Step (2), substrate cleaning: to (1) resulting substrate with continuing to be handled repeatedly with amines such as methylamine or ethamine, atimodometer
Face solvent, recycling and reusing utilize substrate；
Step (3), substrate can be reused for preparing solar cell device: new too using the above processing gained substrate preparation
Positive energy battery device；
Step (4), the waste liquid (the mix suspending object or precipitating of each functional layer composition) of generation and obtains back electrode metal material
Processing: after the filtering of waste liquid obtained by step (1), suspended matter or precipitating are separated from waste liquid；
Step (5), the further utilization to recycling perovskite waste liquid: step (4) filtered waste liquid is according to amine boiling point used
Select suitable heating temperature heating evaporation more than amine, this step obtains perovskite, isolates and contains after amine liquefaction calcium titanium ore bed
Perovskite solution, the recycling and reusing solid perovskite material after room temperature or according to amine boiling point appropriate heating abjection amine, calcium
Titanium ore material can be used to prepare new round device, and can equally reuse after amine recycling.
2. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 1
The technique of active layer, it is characterised in that: amine used in the present invention includes the chain types amine such as methylamine, ethamine, propylamine.
3. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 2
The technique of active layer, it is characterised in that: the perovskite device refers mainly to the solar battery based on perovskite, secondly refers to
The device architecture of LED and field effect transistor etc., solar battery and LED have ITO(FTO and flexible conductive film) glass/electricity
Modifying interface is added in son or hole functional layer/calcium titanium ore bed/hole or electronic work ergosphere/back electrode or its mutation, such as each interlayer
Etc. other functions layer.
4. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 3
The technique of active layer, it is characterised in that: the liquefaction refers to that perovskite encounters amine and can liquefy, and the present invention is that perovskite liquefies
This property is applied in recycling and reusing perovskite device.
5. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 4
The technique of active layer, it is characterised in that: the amine liquefaction perovskite part refers to that perovskite can quilt by perovskite amine environment
Amine liquefaction.
6. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 5
The technique of active layer, it is characterised in that: the amine liquefaction recycling and reusing perovskite device, which refers to, is put into perovskite device
In the perovskite environment of amine, the perovskite on perovskite device can be liquefied and be detached from substrate, and waste liquid further divides after disengaging
From to achieve the purpose that recycling and reusing perovskite active layer.
7. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 6
The technique of active layer, it is characterised in that: the perovskite refers to that perovskite has AMX3General formula, central metal cation M and yin
Ion X-shaped is present in octahedral interstice at coordination octahedral structure, A, plays balance BX3The effect of anionic charge, M are metal
Any one of Ge, Sn, Pb, Cu, Mn, Sb, Bi or two kinds or more, any one of X Cl, Br, I or two kinds and with
On, it common are CH3NH3PbI3、NH2CH=NH2PbI3。
8. a kind of perovskite in amine liquefaction perovskite method recycling and reusing perovskite device according to claim 7
The technique of active layer, it is characterised in that: step (5) utilizes the chemical equation RNH of gained filtrate3MX3 ·nRNH2→
RNH3MX3 + nRNH2↑ (R is organic chain type group in formula, and X is halogen, M is metallic element) obtains perovskite, with this
To prepare new round device.
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| CN112620310A (en) * | 2020-12-15 | 2021-04-09 | 深圳市惠能材料科技研发中心(有限合伙) | Non-invasive recovery and reuse method and application of read-out circuit substrate integrated with halogen perovskite material |
| CN113264838A (en) * | 2021-04-21 | 2021-08-17 | 北方民族大学 | Method for recovering perovskite from waste perovskite |
| CN114602956A (en) * | 2022-03-04 | 2022-06-10 | 湖南铱太科技有限公司 | Recovery and regeneration method universal for positive and negative perovskite solar cell |
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| CN114602956B (en) * | 2022-03-04 | 2022-12-09 | 湖南铱太科技有限公司 | Recovery and regeneration method universal for positive and negative perovskite solar cell |
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