CN109950406A - A kind of perovskite battery and preparation method thereof with graphene barrier layer - Google Patents
A kind of perovskite battery and preparation method thereof with graphene barrier layer Download PDFInfo
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Classifications
-
- 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
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a kind of perovskite batteries with graphene barrier layer, it include: perovskite cell matrix, the perovskite cell matrix is equipped with composite film layer, the composite film layer is equipped with the gold electrode being used cooperatively, and the perovskite cell matrix is realized by composite film layer and the gold electrode to be conducted；The perovskite cell matrix includes: electron transfer layer, perovskite absorbed layer and hole transmission layer, wherein the composite film layer successively includes: the first p-type graphene film, N-type perovskite thin film and the second p-type graphene film from the bottom up.The water oxygen stability of perovskite battery of the present invention is good, and thermal stability is high, and method is easy to operate and plasticity is strong, improve the stability of perovskite solar battery, extend perovskite solar battery service life, increases photoelectric conversion efficiency, meet actual operation requirements.
Description
Technical field
The present invention relates to a kind of perovskite battery and preparation method thereof with graphene barrier layer, belongs to thin film solar
Battery technology field.
Background technique
Graphene be as six side of carbon atom it is tightly packed made of honeycomb two-dimensional material, less than 1 nanometer of thickness.Carbon
The π orbital electron cloud of atom can form a closely knit, localization electric field in the hexagon gap of graphene, which does not permit
Perhaps the hole that any substance passes through graphene.In addition, being formed by between hexagon according to the atomic structure of graphene by carbon atom
Gap only allows radius to be that the atom of 0.032nm size passes through, and size atom more the smallest than radius (hydrogen: 0.079nm) is also small, root
According to principles above, graphene can stop passing through for any atom and molecule, therefore it is with unique impermeability.In addition, by
In noble metal nano compound particle, in fields such as optics, electricity and biology, all there is potential application prospects, so to gold
The research for belonging to nano-complex particle becomes the previous very noticeable research field of mesh, the high thermal conductivity of nano silver composite material
Property and electric conductivity and higher surface-active and catalytic performance, pay close attention to nano silver composite material widely in recent years.
Organic-inorganic hybrid material CH3NH3PbX3It is a kind of at low cost, easy film forming, narrow band gap, photo absorption performance for perovskite structure
Well, the bipolar semiconductor material for the features such as carrier mobility is high, in recent years, since the excellent photoelectricity of perovskite material is special
Property, become the research emphasis in photovoltaic material field.It is referred to as calcium titanium using thin-film solar cells prepared by this kind of material
Mine type solar battery.Determine perovskite battery performance the key technical indexes be battery incident photon-to-electron conversion efficiency and battery it is steady
It is qualitative.Efficiency of solar cell based on perovskite material rises to current 22.1% from 3.8% in 2009.With calcium titanium
The stability of the continuous improvement of the photoelectric conversion efficiency of mine battery, battery becomes critical issue urgently to be solved.
In the prior art, on the one hand, perovskite material is very sensitive to moisture and oxygen, and it is irreversible to be easy chance water oxygen generation
It decomposes；On the other hand, there is also thermal stability problems for perovskite device, and be the main reason for heat fade top layer electrode (including
Gold electrode) can at a lower temperature (75 DEG C) harmful doping is carried out to perovskite material by charge transport layer, to make
Battery efficiency decays rapidly in a very short period of time.In order to improve the water oxygen stability of perovskite device, traditional technology is using ring
Oxygen resin is packaged, and the encapsulating material of this hard not only will affect the stability of calcium titanium ore bed, and can seriously affect flexibility
The flexibility of device.In order to improve perovskite device thermal stability and water oxygen stability, the usually top electrode in perovskite battery
One layer of inert metal (such as: Cr, Ni etc.) or organic insulating material (such as: PMMA, PC etc.) are inserted between charge transport layer, due to
Metal all has diffusivity, and inert metal is very limited to the raising of thermal stability, and the thickness of organic insulating material is to device
Photoelectric properties influence is very big, needs strict control, this greatly increases the difficulty of device preparation.For this reason, it may be necessary to design corresponding skill
Art scheme, which is given, to be solved.
Summary of the invention
The present invention be directed to the shortcomings of the prior art, provide a kind of perovskite battery with graphene barrier layer and
The water oxygen stability of preparation method, perovskite battery is good, and thermal stability is high, and method is easy to operate and plasticity is strong, improves
The stability of perovskite solar battery extends perovskite solar battery service life, increases photoelectric conversion efficiency, meets real
Border requirement.
To solve the above problems, the technical solution used in the present invention is as follows:
A kind of perovskite battery with graphene barrier layer, comprising: transparent guide glass and setting are in transparent guide glass
Perovskite cell matrix on glass, the perovskite cell matrix are equipped with composite film layer, and the composite film layer is equipped with
The gold electrode being used cooperatively, the perovskite cell matrix is realized by composite film layer and the gold electrode to be conducted；
The perovskite cell matrix includes: electron transfer layer, perovskite absorbed layer and hole transmission layer, wherein described
Composite film layer successively includes: that the first p-type graphene film, N-type perovskite thin film and the second p-type graphene are thin from the bottom up
Film.
As an improvement of the above technical solution, the gold electrode is setting on the second p-type graphene film, and the gold
It is covered on electrode by PDMS.
Specifically, the perovskite battery preparation method with graphene barrier layer includes:
Step (1): being sequentially prepared electron transfer layer, perovskite absorbed layer and hole transmission layer on substrate after cleaning,
Obtain perovskite cell matrix；
Step (2): gold electrode is evaporated on the composite film layer of the containing graphene of CVD method preparation, PDMS is bonded in gold
On electrode, barrier layer matrix is obtained, barrier layer matrix is then immersed in removal composite film layer growth substrate in etching liquid, is obtained
To the composite film layer for being covered with PDMS and gold electrode；
The first p-type graphene film side in composite film layer is fitted in the sky of perovskite cell matrix by step (3)
In the transport layer of cave, then removes the PDMS in composite film layer on the second p-type graphene film and stop to get to graphene
The perovskite battery of layer.
As an improvement of the above technical solution, in step (1), substrate is successively ultrasonic in acetone, isopropanol and ethyl alcohol
It cleans each 5 minutes, then passes to inert gas and dry up the substrate after being cleaned；The substrate be indium tin oxide-coated glass or
Fluorine-doped tin oxide electro-conductive glass.
As an improvement of the above technical solution, in step (1), the material of electron transfer layer uses TiO2、ZnO、SnO2、
Nb2O5、In2O3、Zn2SnO4、PC60BM、PC70BM and C60One or more of；The preparation of electron transfer layer is using precipitating, rotation
Painting, blade coating, silk-screen printing, atomic layer deposition or physical vaporous deposition.
As an improvement of the above technical solution, in step (1), the material of the perovskite absorbed layer is ABX3Perovskite is brilliant
Body, wherein A is CH3NH3 +、H2N-CH=NH2 +、C3H11SN3 2+, Cs or (CH3)4N+, B Pb, Ge or Sn；X is Cl, Br or I.
As an improvement of the above technical solution, the material of the hole transmission layer uses Spiro-OMeTAD, PEDOT:
PSS, NiO, P3HT, PTAA or CuSCN.
As an improvement of the above technical solution, in step (2), gold electrode with a thickness of 75-95nm, PDMS with a thickness of
0.25-0.45mm；The composite film layer of containing graphene is the single-layer or multi-layer graphite that copper or nickel substrate are grown in by CVD method
Alkene；Etching liquid is FeCl3Or (NH4)2S2O8。
As an improvement of the above technical solution, in step 3, composite film layer and/or perovskite cell matrix are heated to
70-85 DEG C, the first p-type graphene film of progress is bonded with hole transmission layer；It is smoked that solvent is carried out to fitting part after fitting
It steams and/or solvent anneal processing, solvent for use is chlorobenzene or toluene；In addition, the separation of PDMS layer and gold electrode is at 85-95 DEG C
At a temperature of carry out.
Compared with prior art, implementation result of the invention is as follows by the present invention:
The present invention is that the uniqueness based on graphene is impervious, combines the special construction for forming PNP to make graphene, perovskite
It is introduced into perovskite battery for barrier layer, compared with the perovskite battery of traditional structure, both can effectively stop golden under high temperature
Belonging to the water oxygen that harmful diffusion of the electrode to calcium titanium ore bed can effectively prevent in air again and entering calcium titanium ore bed prevents calcium titanium ore bed
It decomposes, to substantially increase the water oxygen stability and thermal stability of perovskite battery, there is weight to perovskite battery industryization
The practical value and directive significance wanted.
The method of the invention is improved using the graphene of two-dimensional material, perovskite in conjunction with the special construction for forming PNP
Perovskite thin film battery thermal stability and water oxygen stability, then graphene transfer is realized by wet process, it is real using low temperature thermal-adhering
The combination of existing graphene and hole transmission layer, solvent is stifling and/or solvent anneal processing can be such that graphene and hole transmission layer pastes
That closes is more preferable, and this method is easy to operate, and the battery containing graphene of favorable repeatability and preparation can solve perovskite electricity simultaneously
The problem of pond thermal stability and water oxygen stability difference.
Detailed description of the invention
Fig. 1 is the perovskite battery structure schematic diagram of the present invention with graphene barrier layer；
Fig. 2 is that the perovskite battery and traditional perovskite battery thermal stability in embodiment with graphene barrier layer compare
Figure；
Fig. 3 is the perovskite battery and traditional perovskite cell water oxidative stability pair in embodiment with graphene barrier layer
Than figure；
Fig. 4 is that the perovskite battery and traditional perovskite battery in embodiment with graphene barrier layer are placed in air
Calcium titanium ore bed XRD diagram after 48 hours.
Specific embodiment
Illustrate the contents of the present invention below in conjunction with specific embodiments.
It is as shown in Figures 1 to 4: embodiment: the perovskite battery with graphene barrier layer, comprising: transparent guide glass 1
With the perovskite cell matrix 2 being arranged on transparent guide glass 1, perovskite cell matrix 2 is equipped with composite film layer 3, multiple
It closes film layer 3 and is equipped with the gold electrode 4 being used cooperatively, perovskite cell matrix 2 is realized by composite film layer 3 and gold electrode 4
Conduction；Perovskite cell matrix 2 includes: electron transfer layer 21, perovskite absorbed layer 22 and hole transmission layer 23, composite film layer
3 successively include: the first p-type graphene film 31, N-type perovskite thin film 32 and the second p-type graphene film 33 from the bottom up；Its
In, gold electrode 4 is that setting is covered with PDMS on the second p-type graphene film 33, and on gold electrode 4.The present invention is based on graphite
The uniqueness of alkene is impervious, combines the special construction for forming PNP to introduce perovskite battery as barrier layer graphene, perovskite
In, compared with the perovskite battery of traditional structure, metal electrode under high temperature both can effectively be stopped to expand to the nocuousness of calcium titanium ore bed
Dissipate can effectively prevent the water oxygen in air and enter calcium titanium ore bed again prevents the decomposition of calcium titanium ore bed, to substantially increase perovskite
The water oxygen stability and thermal stability of battery have important practical value and directive significance to perovskite battery industryization.
Wherein, the perovskite battery preparation method with graphene barrier layer the following steps are included:
Step (1): being sequentially prepared electron transfer layer, perovskite absorbed layer and hole transmission layer on substrate after cleaning,
Obtain perovskite cell matrix；
Step (2): gold electrode is evaporated on the composite film layer of the containing graphene of CVD method preparation, PDMS is bonded in gold
On electrode, barrier layer matrix is obtained, barrier layer matrix is then immersed in removal composite film layer growth substrate in etching liquid, is obtained
To the composite film layer for being covered with PDMS and gold electrode；
The first p-type graphene film side in composite film layer is fitted in the sky of perovskite cell matrix by step (3)
In the transport layer of cave, then removes the PDMS in composite film layer on the second p-type graphene film and stop to get to graphene
The perovskite battery of layer.
Wherein, step 1: substrate pre-treatment；
(1) FTO glass zinc powder and dilute hydrochloric acid are etched into the strip structure of 4mm*25mm；Dilute hydrochloric acid is by 1 volume mass
The concentrated hydrochloric acid of score 38% and the water of 4 volumes mix.
(2) the FTO glass etched is successively cleaned by ultrasonic in acetone, isopropanol, ethyl alcohol each 5 minutes, is dried with nitrogen.
Step 2: perovskite thin film cell matrix is prepared；
(1) one layer of TiO2 is deposited as electron transport material on the surface FTO etched using hydro-thermal heat preservation sedimentation；
(2) using solution spin-coating method, spin coating calcium titanium ore bed, solution used are CH3NH3I and PbI2 on the electron transport layer
Mixed solution, solution concentration 1.2mol/L；
(3) solution spin-coating method spin coating hole transmission layer Spiro-MeOTAD on calcium titanium ore bed is used, for having for hole
Effect transports and the bonding with composite film layer, and Spiro-MeOTAD solution concentration is 90mg/mL.
Step 3: laminated film is prepared；
(1) golden film that graphene layer is evaporated on copper-based single layer laminated film, by the PDMS of 0.3mm and Au/ graphene/copper
Bonding, obtains the stratiform PDMS/Ag/ graphene/copper barrier layer matrix for stacking gradually assembling；
(2) barrier layer matrix is placed in the ammonium persulfate solution of 30mg/mL, is got rid of using the method repeatedly washed by water
The graphene of the growth of copper-based bottom back side；
(3) 3-5h is stood in the solution, etches away the THIN COMPOSITE that copper-based bottom obtains stacking gradually the stratiform PDMS/Au of assembling
Laminated film is finally placed in clean culture dish by film with cleaning in deionized water three times, is dried stand-by.
Step 4: perovskite battery of the preparation based on graphene barrier layer；
(1) thermal station temperature is set as 85 DEG C, laminated film is placed in thermal station after temperature is warming up to 85 DEG C and is heated
10min；
(2) perovskite battery is placed in a mold, with tweezers by the laminated film of heating and perovskite cell matrix
The smooth seamless fitting of hole transmission layer；
(3) the perovskite battery posted is placed in mold, the chlorobenzene solution of 50mL is then drawn with liquid-transfering gun, is suspended from
Above battery at 5mm, solvent is carried out to fitting part and is fumigated, realizes the multiple layer film of sweat graphene and the nothing of hole transmission layer
Seam fitting, then 85-95 DEG C of removal PDMS is heated to device.
The method of the invention is improved using the graphene of two-dimensional material, perovskite in conjunction with the special construction for forming PNP
Perovskite thin film battery thermal stability and water oxygen stability, then graphene transfer is realized by wet process, it is real using low temperature thermal-adhering
The combination of existing graphene and hole transmission layer, solvent is stifling and/or solvent anneal processing can be such that graphene and hole transmission layer pastes
That closes is more preferable, and this method is easy to operate, and the battery containing graphene of favorable repeatability and preparation can solve perovskite electricity simultaneously
The problem of pond thermal stability and water oxygen stability difference.
In this example, with the perovskite battery on graphene barrier layer, as shown in Figure 1 comprising stack gradually assembling
Transparent conducting glass 1, electron transfer layer 21, perovskite absorbed layer 22, hole transmission layer 33 and gold electrode 4；Positive-negative-positive structure is in
Between hole transmission layer 23 and gold electrode 4, battery efficiency 18.60%, after 80 DEG C of heating in continuous 6 hours, the battery effect
Rate is reduced to 13.80%, and thermal stability is up to 86%；After placing 48h in air, the battery efficiency is reduced to 14.88%, water oxygen
Stability is up to 90%.
However, traditional perovskite battery efficiency of containing graphene is not 15.80%, and at 80 DEG C after continuous 6 hours, the electricity
Pond efficiency is reduced to 8.20%, thermal stability 52%；After placing 48h in air, the battery efficiency is reduced to 9.58%, water oxygen
Stability is 56%.
Specifically, in step (1), substrate is successively cleaned by ultrasonic to each 5 minutes in acetone, isopropanol and ethyl alcohol, then
It is passed through inert gas and dries up the substrate after being cleaned；The substrate is indium tin oxide-coated glass or fluorine-doped tin oxide conduction glass
Glass；In step (1), the material of electron transfer layer 21 uses TiO2、ZnO、SnO2、Nb2O5、In2O3、Zn2SnO4、PC60BM、
PC70BM and C60One or more of；The preparation of electron transfer layer 21 uses precipitating, spin coating, blade coating, silk-screen printing, atomic layer
Deposition or physical vaporous deposition；In step (1), the material of perovskite absorbed layer 22 is ABX3Perovskite crystal, wherein A be
CH3NH3 +、H2N-CH=NH2 +、C3H11SN3 2+, Cs or (CH3)4N+, B Pb, Ge or Sn；X is Cl, Br or I.In addition, hole passes
The material of defeated layer 23 uses Spiro-OMeTAD, PEDOT:PSS, NiO, P3HT, PTAA or CuSCN.
More specifically, in step (2), gold electrode 4 with a thickness of 75-95nm, PDMS with a thickness of 0.25-0.45mm；Contain
The composite film layer 3 of graphene is the single-layer or multi-layer graphene that copper or nickel substrate are grown in by CVD method；Etching liquid is
FeCl3Or (NH4)2S2O8；In step 3, composite film layer 3 and/or perovskite cell matrix 2 are heated to 70-85 DEG C, carried out
First p-type graphene film 31 is bonded with hole transmission layer 23；It is stifling and/or molten that solvent is carried out to fitting part after fitting
Agent annealing, solvent for use are chlorobenzene or toluene；In addition, the separation of PDMS layer and gold electrode 4 be at a temperature of 85-95 DEG C into
Row.
The foregoing is a detailed description of the present invention in conjunction with specific embodiments, and it cannot be said that the present invention is specifically real
It applies and is only limitted to these explanations.For those skilled in the art to which the present invention belongs, before not departing from present inventive concept
It puts, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the scope of protection of the invention.
Claims (9)
1. a kind of perovskite battery with graphene barrier layer, it is characterised in that: include: transparent guide glass (1) and setting
Perovskite cell matrix (2) on transparent guide glass (1), the perovskite cell matrix (2) are equipped with composite film layer
(3), the composite film layer (3) is equipped with the gold electrode (4) being used cooperatively, and the perovskite cell matrix (2) passes through compound
Film layer (3) and the gold electrode (4), which are realized, conducts；
The perovskite cell matrix (2) includes: electron transfer layer (21), perovskite absorbed layer (22) and hole transmission layer
(23), wherein the composite film layer (3) successively includes: that the first p-type graphene film (31), N-type perovskite are thin from the bottom up
Film (32) and the second p-type graphene film (33).
2. according to claim 1 with the perovskite battery on graphene barrier layer, it is characterised in that: the gold electrode (4)
It is that setting is covered on the second p-type graphene film (33), and on the gold electrode (4) by PDMS.
3. according to claim 1 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that:
Step (1): it is sequentially prepared electron transfer layer, perovskite absorbed layer and hole transmission layer on substrate after cleaning, obtains
Perovskite cell matrix；
Step (2): gold electrode is evaporated on the composite film layer of the containing graphene of CVD method preparation, PDMS is bonded in gold electrode
On, barrier layer matrix is obtained, barrier layer matrix is then immersed in removal composite film layer growth substrate in etching liquid, is covered
It is stamped the composite film layer of PDMS and gold electrode；
Step (3) passes the hole that the first p-type graphene film side in composite film layer is fitted in perovskite cell matrix
On defeated layer, the PDMS in composite film layer on the second p-type graphene film is removed then to get arriving with graphene barrier layer
Perovskite battery.
4. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: step
(1) in, substrate is successively cleaned by ultrasonic in acetone, isopropanol and ethyl alcohol each 5 minutes, then passes to inert gas and dries up to obtain
Substrate after cleaning；The substrate is indium tin oxide-coated glass or fluorine-doped tin oxide electro-conductive glass.
5. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: step
(1) in, the material of electron transfer layer (21) uses TiO2、ZnO、SnO2、Nb2O5、In2O3、Zn2SnO4、PC60BM、PC70BM and C60
One or more of；The preparation of electron transfer layer (21) using precipitating, spin coating, blade coating, silk-screen printing, atomic layer deposition or
Physical vaporous deposition.
6. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: step
(1) in, the material of the perovskite absorbed layer (22) is ABX3Perovskite crystal, wherein A is CH3NH3 +、H2N-CH=NH2 +、
C3H11SN3 2+, Cs or (CH3)4N+, B Pb, Ge or Sn；X is Cl, Br or I.
7. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: the sky
The material of cave transport layer (23) uses Spiro-OMeTAD, PEDOT:PSS, NiO, P3HT, PTAA or CuSCN.
8. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: step
(2) in, gold electrode (4) with a thickness of 75-95nm, PDMS with a thickness of 0.25-0.45mm；The composite film layer of containing graphene
It (3) is the single-layer or multi-layer graphene that copper or nickel substrate are grown in by CVD method；Etching liquid is FeCl3Or (NH4)2S2O8。
9. according to claim 3 with the perovskite battery preparation method on graphene barrier layer, it is characterised in that: step 3
In, composite film layer (3) and/or perovskite cell matrix (2) are heated to 70-85 DEG C, carry out the first p-type graphene film
(31) it is bonded with hole transmission layer (23)；And/or solvent anneal processing stifling to fitting part progress solvent, institute after fitting
It is chlorobenzene or toluene with solvent；In addition, the separation of PDMS layer and gold electrode (4) is carried out at a temperature of 85-95 DEG C.
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| CN115867093A (en) * | 2023-02-20 | 2023-03-28 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method and application of perovskite solar cell graphene electron transport layer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384917A (en) * | 2015-11-10 | 2016-03-09 | 华南理工大学 | Conjugated polymer with side chain containing sulfonic acid or sulfonate and plane-inverted organic/inorganic hybrid perovskite solar cell prepared from conjugated polymer |
| CN106449985A (en) * | 2016-11-02 | 2017-02-22 | 陕西师范大学 | Perovskite battery having graphene barrier layer and preparation method |
| CN107768522A (en) * | 2017-11-29 | 2018-03-06 | 湖南师范大学 | A kind of perovskite thin film solar cell using graphene as conductive material and preparation method thereof |
| CN107887511A (en) * | 2017-11-22 | 2018-04-06 | 苏州大学 | A kind of method that perovskite solar cell is prepared based on two-dimensional material graphene phase carbon nitride |
| US20180174762A1 (en) * | 2016-12-16 | 2018-06-21 | Uchicago Argonne, Llc | Hybrid organic-inorganic electron selective overlayers for halide perovoskites |
| US20180366277A1 (en) * | 2017-06-16 | 2018-12-20 | Korea Research Institute Of Chemical Technology | Perovskite solar cell with wide band-gap and fabrication method thereof |
-
2019
- 2019-03-28 CN CN201910243695.9A patent/CN109950406A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384917A (en) * | 2015-11-10 | 2016-03-09 | 华南理工大学 | Conjugated polymer with side chain containing sulfonic acid or sulfonate and plane-inverted organic/inorganic hybrid perovskite solar cell prepared from conjugated polymer |
| CN106449985A (en) * | 2016-11-02 | 2017-02-22 | 陕西师范大学 | Perovskite battery having graphene barrier layer and preparation method |
| US20180174762A1 (en) * | 2016-12-16 | 2018-06-21 | Uchicago Argonne, Llc | Hybrid organic-inorganic electron selective overlayers for halide perovoskites |
| US20180366277A1 (en) * | 2017-06-16 | 2018-12-20 | Korea Research Institute Of Chemical Technology | Perovskite solar cell with wide band-gap and fabrication method thereof |
| CN107887511A (en) * | 2017-11-22 | 2018-04-06 | 苏州大学 | A kind of method that perovskite solar cell is prepared based on two-dimensional material graphene phase carbon nitride |
| CN107768522A (en) * | 2017-11-29 | 2018-03-06 | 湖南师范大学 | A kind of perovskite thin film solar cell using graphene as conductive material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115867093A (en) * | 2023-02-20 | 2023-03-28 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method and application of perovskite solar cell graphene electron transport layer |
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