CN109285951A - A kind of low temperature flexibility perovskite solar battery and preparation method thereof - Google Patents

A kind of low temperature flexibility perovskite solar battery and preparation method thereof Download PDF

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Publication number
CN109285951A
CN109285951A CN201811088865.2A CN201811088865A CN109285951A CN 109285951 A CN109285951 A CN 109285951A CN 201811088865 A CN201811088865 A CN 201811088865A CN 109285951 A CN109285951 A CN 109285951A
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layer
solar battery
solution
low temperature
colloidal solution
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吕银花
蔡冰
王鹏
张志群
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SICHUAN RESEARCH CENTER OF NEW MATERIALS
ANSHAN HIFICHEM Co Ltd
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SICHUAN RESEARCH CENTER OF NEW MATERIALS
ANSHAN HIFICHEM Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4213Comprising organic semiconductor-inorganic semiconductor hetero-junctions
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0002Deposition of organic semiconductor materials on a substrate
    • H01L51/0003Deposition of organic semiconductor materials on a substrate using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/30Materials
    • H01L2251/301Inorganic materials
    • H01L2251/303Oxides, e.g. metal oxides
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention discloses a kind of low temperature flexibility perovskite solar battery, from bottom to up successively include substrate, electron transfer layer, perovskite absorbed layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is the compacted zone of low-temperature annealing.By selecting suitable material to prepare electron transfer layer, can also have preferable electric conductivity without high-temperature annealing process, ensure that the photoelectric conversion performance of solar battery.Invention additionally discloses a kind of preparation methods of above-mentioned low temperature flexibility perovskite solar battery.

Description

A kind of low temperature flexibility perovskite solar battery and preparation method thereof
Technical field
The present invention relates to perovskite area of solar cell, and in particular to a kind of low temperature flexibility perovskite solar battery and Preparation method.
Background technique
Solar energy has been to be concerned by more and more people as a kind of cleaning, environmental protection, cheap, rich reserves the energy.In light In the Solar uses mode such as hot-cast socket, photoelectric conversion and Photochemical convertion, photoelectric conversion is due to its permanent, spatter property, spirit The features such as active the research and development direction as present hot topic.The basic device of solar energy photoelectric conversion is solar battery.
Traditional solar battery is limited by weight, thickness, and the physical properties such as portability and bend resistance degree use field Scape is typically only capable to be layed in vacant lot and room item by biggish limitation.The architectural characteristic for changing solar battery makes it become soft It is soft to have more application scenarios, it might even be possible to become object that can be carry-on, with it is various it is wearable, can roll over Folded electronic product and intelligent movable device such as Google glass, smartwatch, health monitoring wrist strap etc. the micromation of electronic product, Portable growth requirement and the external energy of mating appearance.
Problem is that electron transfer layer the most commonly used in perovskite solar battery is TiO at present2.However it uses TiO2When preparation electricity ground transport layer, the annealing process by 450 DEG C of temperatures above is needed, otherwise photoelectric conversion efficiency is undesirable. At this temperature, the flexible substrates being made of organic material can be denaturalized failure and even be carbonized, can not normal use, thus it is serious Limit application of the perovskite solar battery in the devices such as flexibility.
Summary of the invention
In view of this, the application provides a kind of flexible perovskite solar-electricity of electron transfer layer for including low-temperature annealing Pond and preparation method thereof, by selecting suitable material to prepare electron transfer layer, without high-temperature annealing process Also there can be preferable electric conductivity, ensure that the photoelectric conversion performance of solar battery.
In order to solve the above technical problems, technical solution provided by the invention is a kind of low temperature flexibility perovskite solar-electricity Pond, from bottom to up successively include substrate, electron transfer layer, perovskite absorbed layer, hole transmission layer, to electrode layer, the substrate Fexible film including being coated with conductive layer;The electron transfer layer is the compacted zone of low-temperature annealing.
Preferably, the material of the compacted zone is selected from SnO2、Sb:SnO2、In:SnO2、Nb:SnO2In any one.
Preferably, the SnO2Or Sb:SnO2/In:SnO2/Nb:SnO2In tin oxide nano crystal size be 2-5nm.
Preferably, any one of the material of the fexible film in PEN, PET, PDMS and PI.
Preferably, the material of the conductive layer is ITO or FTO.
The application also provides a kind of preparation method of low temperature flexibility perovskite solar battery, includes the following steps:
C is dispersed by stannum oxide nano-crystal2H5OH or (CH3)2In CHOH, the oxidation that concentration is 0.05-1.5mol/L is formed Tin colloid solution;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed, electron transfer layer is obtained;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Preferably, C is being dispersed by stannum oxide nano-crystal2H5OH or (CH3)2In CHOH, forming concentration is 0.05- Further include following steps before the tin oxide colloidal solution step of 1.5mol/L:
It will include SnCl4·5H2O、SnCl2·2H2O、C4H6O4Sn and C8H12O8The reaction of at least one of Sn substance is former (CH is added in material2OH)2In solution is made, in the solution molar concentration of Sn ion be 0.1-3mol/L;
The CH for adjusting the pH value of solution to 7-10, in the glacial acetic acid with glacial acetic acid and ammonium hydroxide3In COOH and ammonium hydroxide NH3·H2The molar ratio of O is 1:1.5 to 1:5;
It reacts solution 10-120 minutes in 60-190 DEG C of temperature, generates colloidal solution;
The precipitating obtained after colloidal solution described in eccentric cleaning, as stannum oxide nano-crystal.
Preferably, colloidal solution step described in the eccentric cleaning includes:
A. C is added in the solution of the colloid obtained after the reaction2H5OH or (CH3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 5-30min minutes with the revolving speed of 2000-10000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band precipitating is retained;
Sequence of the colloidal solution made from step c since step a according to a, b, step c is recycled and is executed, cycle-index More than or equal to three times.
It preferably, further include doped chemical in the reaction raw materials, the doped chemical includes any in Sb, In, Nb The molar ratio of one kind, the doped chemical and Sn are 0:4 to 1:4.
Preferably, described that the tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed, annealing temperature is 80-180℃。
The application compared with prior art, it has the advantage that:
Compared to existing TiO2Material, SnO2The electron transfer layer of material preparation has broader band gap, higher electronics Mobility can be realized the more preferable matching with perovskite material energy level, to be conducive to the injection efficiency of carrier.
Electron transfer layer is prepared in 2-5nm stannum oxide nano-crystal using partial size, since tin oxide nano crystal size is smaller and Uniformly, and there is better crystal property, electron transfer layer only needs just to have outstanding conduction by low temperature annealing process Performance so that the flexible substrates of organic material will not because of high annealing deformed damaged.In the case where guaranteeing material situation flexible Higher incident photon-to-electron conversion efficiency is realized, the application prospect of low temperature flexibility perovskite solar battery is improved.
From PEN (polyethylene naphthalate), PET (polyethylene terephthalate), PDMS (polydimethylsiloxanes Alkane) and the materials such as PI (polyimides) in select a kind of material the solar battery prepared have enough soft as substrate Property, it can arbitrarily be bent kinking to a certain extent.
Partial size can be obtained in the stannum oxide nano-crystal of the highly crystalline of 2-5nm, then by the solwution method of simple process It is coated onto flexible substrates by spin-coating method and is annealed at low temperature, just can complete the electricity of perovskite solar battery The preparation of sub- transport layer.It in conjunction with prior art prepared by the other function layer structure of perovskite solar battery and is completed, it can be complete At the production of flexible solar battery.Required raw material is conveniently easy to get in stannum oxide nano-crystal synthesis process, operating technology side Just, the reaction condition of preparation engineering requires low, has preferable repeatability, so as to be produced on a large scale.
Further, the elements such as a certain amount of Sb, In, Nb are adulterated when preparing stannum oxide nano-crystal, can further be mentioned High SnO2Crystal property and by SnO2The photoelectric properties for the electron transfer layer prepared, and then improve the photoelectricity of solar battery Transfer efficiency.
Divalent tin ion is oxidized easily in air as tetravalent tin, therefore tin source in this application can use pink salt Or stannous salt, the product after end reaction is all SnO2, the preparation of stannum oxide nano-crystal is had not significant impact.Wherein C4H6O4Sn and C8H12O8It is respectively tin acetate (II) and tin acetate (IV) that Sn, which corresponds to Chinese,.
In order to reduce the introducing of excess ions, the inorganic salts for the Sb/In/Nb being added in reaction raw materials or organic cooperation Villaumite or acetate can be selected in object, such as: C10H25NbO5、NbCl5、InCl3、SbCl3At least one of, it is convenient for subsequent preparation Cleaning separation is carried out in the process.It should be noted that adulterating the Sb:SnO generated after Sb/In/Nb in reaction raw materials2/In: SnO2/Nb:SnO2Nanocrystalline, main component is still SnO2, SnO is also predominantly detected when carrying out materialization characterization2Performance, So the stannum oxide nano-crystal mentioned in the application includes SnO2The Sb:SnO of nanocrystalline and Sb/In/Nb doping2/In:SnO2/ Nb:SnO2It is nanocrystalline.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of low temperature flexibility perovskite solar battery of the present invention;
Fig. 2 is the battery performance test curve of low temperature flexibility perovskite solar battery embodiment 1 of the present invention;
Fig. 3 is the battery performance test curve of low temperature flexibility perovskite solar battery embodiment 4 of the present invention;
Fig. 4 is that the transmission electron microscope of stannum oxide nano-crystal in low temperature flexibility perovskite solar battery embodiment 1 of the present invention shines Piece.
Appended drawing reference: to electrode layer 1, hole transmission layer 2, perovskite absorbed layer 3, electron transfer layer 4, substrate 5.
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, embodiments herein provides a kind of low temperature flexibility perovskite solar battery, from bottom to up successively Including substrate 5, electron transfer layer 4, perovskite absorbed layer 3, hole transmission layer 2, to electrode layer 1, substrate 5 includes being coated with conductive layer Fexible film;Electron transfer layer 4 is the compacted zone of low-temperature annealing, and the material of the compacted zone includes SnO2、Sb:SnO2、In: SnO2、Nb:SnO2In any one, the SnO2Or Sb:SnO2/In:SnO2/Nb:SnO2In tin oxide nano crystal size For 3-5nm.Any one of the material of the fexible film in PEN, PET, PDMS and PI;The material of the conductive layer is ITO or FTO.
The embodiment of the present application also provides a kind of preparation method of low temperature flexibility perovskite solar battery, including walks as follows It is rapid:
It takes including SnCl4·5H2O、SnCl2·2H2O、C4H6O4Sn and C8H12O8The reaction raw materials of at least one of Sn add Enter (CH2OH)2In solution is made, in the solution molar concentration of Sn ion be 0.1-3mol/L;It further include mixing in reaction raw materials Miscellaneous element, the doped chemical include any one in Sb, In, Nb, and the molar ratio of the doped chemical and Sn are 0:4 to 1: 4;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 7-10, the CH in glacial acetic acid3In COOH and ammonium hydroxide NH3·H2The molar ratio of O is 1:1.5 to 1:5;
It reacts solution 10-120 minutes in 60-190 DEG C of temperature, generates colloidal solution;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. C is added in colloidal solution after the reaction2H5OH or (CH3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 5-30min minutes with the revolving speed of 2000-10000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band precipitating is retained;
Sequence of the obtained precipitating of step c since step a according to step a, b, c is recycled and is executed, cycle-index is big In or equal to three times;
Colloidal solution described in eccentric cleaning, obtained precipitating are stannum oxide nano-crystal;
C is dispersed by stannum oxide nano-crystal2H5OH or (CH3)2In CHOH, the oxidation that concentration is 0.05-1.5mol/L is formed Tin colloid solution;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 80-180 DEG C, Obtain electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 1
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates Nb:SnO made from Nb2, the Nb:SnO2 The partial size of middle stannum oxide nano-crystal is 2-5nm.The fexible film is PEN material, and the conductive layer is ITO material.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take SnCl4·5H2(CH is added in O2OH)2In solution is made, in the solution molar concentration of Sn ion be 3mol/ L;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 10, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:5;
It reacts solution 10 minutes in 190 DEG C of temperature, generates the colloidal solution of white;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. C is added in colloidal solution2H5OH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 5 minutes with the revolving speed of 10000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band white precipitate is retained;
The colloidal solution that step c is obtained executes three times since step a according to the sequence circulation of step a, b, c;
The precipitating obtained after wash cycles is stannum oxide nano-crystal.
C is dispersed by stannum oxide nano-crystal2H5In OH, the tin oxide colloidal solution that concentration is 1.5mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 180 DEG C, is obtained To electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 2
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates Nb:SnO made from Nb2, the Nb:SnO2 The partial size of middle stannum oxide nano-crystal is 2-5nm.The fexible film is PEN material, and the conductive layer is ITO material.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take SnCl2·2H2(CH is added in O2OH)2In solution is made, in the solution molar concentration of Sn be 0.5mol/L;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 8, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:2;
It reacts solution 60 minutes in 100 DEG C of temperature, generates the colloidal solution of white;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. (CH is added in colloidal solution3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 16 minutes with the revolving speed of 6000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band white precipitate is retained;
The colloidal solution that step c is obtained executes three times since step a according to the sequence circulation of step a, b, c;
The precipitating obtained after wash cycles is stannum oxide nano-crystal.
(CH is dispersed by stannum oxide nano-crystal3)2In CHOH, the tin oxide colloidal solution that concentration is 1.5mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 150 DEG C, is obtained To electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 3
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates Nb:SnO made from Nb2, the Nb:SnO2 The partial size of middle stannum oxide nano-crystal is 2-5nm.The fexible film is PEN material, and the conductive layer is ITO material.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take C4H6O4(CH is added in Sn2OH)2In solution is made, in the solution molar concentration of Sn ion be 0.1mol/L;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 7, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:1.5;
It reacts solution 90 minutes in 60 DEG C of temperature, generates the colloidal solution of white;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. C is added in colloidal solution2H5OH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 20 minutes with the revolving speed of 2000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band white precipitate is retained;
The colloidal solution that step c is obtained executes four times since step a according to the sequence circulation of step a, b, c;
The precipitating obtained after wash cycles is stannum oxide nano-crystal.
C is dispersed by stannum oxide nano-crystal2H5In OH, the tin oxide colloidal solution that concentration is 0.05mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 140 DEG C, is obtained To electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 4
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates Nb:SnO made from Nb2, the Nb:SnO2 The partial size of middle stannum oxide nano-crystal is 2-5nm.The material of the fexible film is PET material, it is preferred that the conductive layer is FTO material.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take SnCl4·5H2(CH is added in O2OH)2In solution is made, the molar concentration of Sn ion is in the solution 2.5mol/L;It further include C in the reaction raw materials10H25NbO5, the molar ratio of Nb and Sn are 0.1:4;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 9.5, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:4;
It reacts solution 20 minutes in 160 DEG C of temperature, generates the colloidal solution of white;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. (CH is added in colloidal solution3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 15 minutes with the revolving speed of 5000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution that lower layer has white precipitate is retained;
The colloidal solution that step c is obtained executes five times since step a according to the sequence circulation of step a, b, c;
The precipitating obtained after wash cycles is the stannum oxide nano-crystal of Nb doping.
(CH is dispersed by stannum oxide nano-crystal3)2In CHOH, the tin oxide colloidal solution that concentration is 1.2mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 120 DEG C, is obtained To electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 5
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates In:SnO made from In2, the In:SnO2 The partial size of middle stannum oxide nano-crystal is 2-5nm.The fexible film is PDMS material, and the material of the conductive layer is ITO.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take SnCl2·2H2(CH is added in O2OH)2In solution is made, in the solution molar concentration of Sn ion be 2mol/ L;It further include InCl in the reaction raw materials3, the molar ratio of In and Sn are 0.4:4;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 9, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:3;
It reacts solution 30 minutes in 140 DEG C of temperature, generates the colloidal solution of white;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. (CH is added in colloidal solution3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 12 minutes with the revolving speed of 6000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band white precipitate is retained;
The colloidal solution that step c is obtained executes three times since step a according to the sequence circulation of step a, b, c;
The precipitating obtained after wash cycles is the stannum oxide nano-crystal of In doping.
C is dispersed by stannum oxide nano-crystal2H5In OH, the tin oxide colloidal solution that concentration is 1mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 100 DEG C, is obtained To electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 6
A kind of low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite suction from bottom to up Receive layer, hole transmission layer, to electrode layer, the substrate includes the fexible film for being coated with conductive layer;The electron transfer layer is low The compacted zone of temperature annealing, the material of the compacted zone, which is included in reaction raw materials, adulterates Sb:SnO made from Sb2, the Sb:SnO2 The partial size of middle stannum oxide nano-crystal is that fexible film described in 2-5nm is PI material, and the conductive layer is FTO material.
The preparation method of above-mentioned low temperature flexibility perovskite solar battery, includes the following steps:
Take SnCl4·5H2(CH is added in O2OH)2In solution is made, the molar concentration of Sn ion is in the solution 1.5mol/L;It further include SbCl in the reaction raw materials3, the molar ratio of Sb and Sn are 1:4;
Glacial acetic acid and ammonium hydroxide is added, the pH value of solution is adjusted to 9, the CH in glacial acetic acid3NH in COOH and ammonium hydroxide3· H2The molar ratio of O is 1:3;
It reacts solution 80 minutes in 100 DEG C of temperature, generates beige colloidal solution;
The colloidal solution obtained after reaction is cleaned in accordance with the following steps:
A. (CH is added in colloidal solution3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 20 minutes with the revolving speed of 7000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of the light brown precipitating of underlying band is retained;
The obtained colloidal solution of step c is executed four times since step a according to the sequence circulation of step a, b, c;
The light brown precipitating obtained after wash cycles is the stannum oxide nano-crystal of Sb doping.
(CH is dispersed by stannum oxide nano-crystal3)2In CHOH, the tin oxide colloidal solution that concentration is 0.8mol/L is formed;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed within the temperature range of 80 DEG C, is obtained Electron transfer layer;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
Embodiment 7
Referring to FIG. 2, carrying out performance detection to the low temperature flexibility perovskite solar battery that embodiment 1 provides, pass through J-V Data in curve graph are it is found that JSCFor 21.32mA/cm2、VOCFor 1.01V, FF 0.4403, substitutes into above-mentioned formula and is calculated, PCE when solar battery is just prepared is 9.49%.
Referring to FIG. 3, carrying out performance detection to the low temperature flexibility perovskite solar battery that embodiment 4 provides, pass through J-V Data in curve graph are it is found that JSCFor 19.99mA/cm2、VOCFor 1.04V, FF 0.4857, substitutes into above-mentioned formula and is calculated, PCE when solar battery is just prepared is 10.11%.
Wherein, PCE is photoelectric conversion efficiency (Power Conversion Efficiency), it and JSC(short circuit current is close Degree), VOCThere is following relationship between (open-circuit voltage) and FF (fill factor):
PCE=JSC×VOC×FF
Wherein, FF is fill factor (Fill Factor), is the material property of one with perovskite solar battery itself Relevant value.Electric property detection is all carried out to solar battery made from embodiment 1-6, obtains the positive and negative of solar battery J-V data are swept, and data preparation is as follows:
Referring to FIG. 4, obtained during low temperature flexibility preparation method of solar battery provided by the present application aoxidize sijna After meter Jing Jing over-sampling is dry, by transmission electron microscope observing, it can be seen that, the uniform particle sizes of stannum oxide nano-crystal are distributed in 2-5nm's In section.Using the lesser stannum oxide nano-crystal of partial size, low-temperature annealing is only needed i.e. in the spin coating preparation process of solar battery The good tin oxide compacted zone of crystallinity can be obtained, there is better electric conductivity, so that solar battery obtained be made to have Higher photoelectric conversion efficiency.Low-temperature annealing be denaturalized substrate will not because of temperature is excessively high in annealing process, avoid Influence of the high annealing process to flexible substrates, has prepared structurally flexible, easy to use, while having the conversion of high light electricity The solar battery of efficiency improves the application range and the efficiency of solar energy utilization of solar battery.
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 low temperature flexibility perovskite solar battery successively includes substrate, electron transfer layer, perovskite absorption from bottom to up Layer, hole transmission layer, to electrode layer, which is characterized in that the substrate includes the fexible film for being coated with conductive layer;The electronics passes Defeated layer is the compacted zone of low-temperature annealing.
2. low temperature flexibility perovskite solar battery as described in claim 1, which is characterized in that the material of the compacted zone selects From SnO2、Sb:SnO2、In:SnO2、Nb:SnO2In any one.
3. such as right with require 2 as described in low temperature flexibility perovskite solar battery, which is characterized in that the SnO2Or Sb: SnO2/In:SnO2/Nb:SnO2In tin oxide nano crystal size be 2-5nm.
4. low temperature flexibility perovskite solar battery as described in claim 1, which is characterized in that the material of the fexible film Any one in PEN, PET, PDMS and PI.
5. low temperature flexibility perovskite solar battery as described in claim 1, which is characterized in that the material of the conductive layer is ITO or FTO.
6. a kind of preparation method of low temperature flexibility perovskite solar battery, which comprises the steps of:
C is dispersed by stannum oxide nano-crystal2H5OH or (CH3)2In CHOH, the tin oxide glue that concentration is 0.05-1.5mol/L is formed Liquid solution;
The tin oxide colloidal solution is spin-coated on the fexible film for being coated with conductive layer;
The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and is annealed, electron transfer layer is obtained;
Spin coating perovskite absorbed layer on the electron transport layer;
The spin coating hole transmission layer on the perovskite absorbed layer;
It is deposited on the hole transport layer to electrode layer.
7. the preparation method of low temperature flexibility perovskite solar battery as claimed in claim 6, which is characterized in that will aoxidize Tin is nanocrystalline to be scattered in C2H5OH or (CH3)2In CHOH, the tin oxide colloidal solution step that concentration is 0.05-1.5mol/L is formed Before further include following steps:
It will include SnCl4·5H2O、SnCl2·2H2O、C4H6O4Sn and C8H12O8The reaction raw materials of at least one of Sn substance add Enter (CH2OH)2In solution is made, in the solution molar concentration of Sn ion be 0.1-3mol/L;
The CH for adjusting the pH value of solution to 7-10, in the glacial acetic acid with glacial acetic acid and ammonium hydroxide3In COOH and ammonium hydroxide NH3·H2The molar ratio of O is 1:1.5 to 1:5;
It reacts solution 10-120 minutes in 60-190 DEG C of temperature, generates colloidal solution;
Colloidal solution described in eccentric cleaning, obtained precipitating are stannum oxide nano-crystal.
8. the preparation method of low temperature flexibility perovskite solar battery as claimed in claim 7, which is characterized in that the centrifugation Cleaning the colloidal solution step includes:
A. C is added in colloidal solution2H5OH or (CH3)2CHOH is simultaneously sufficiently mixed;
B. mixed solution is centrifuged 5-30 minutes with the revolving speed of 2000-10000r/min;
C. the upper solution after centrifugation is removed, the colloidal solution of underlying band precipitating is retained;
Sequence of the colloidal solution made from step c since step a according to a, b, step c is recycled and is executed, cycle-index is greater than Or it is equal to three times.
9. the preparation method of low temperature flexibility perovskite solar battery as claimed in claim 7, which is characterized in that the reaction It further include doped chemical in raw material, the doped chemical includes any one in Sb, In, Nb, the doped chemical and Sn's Molar ratio is 0:4 to 1:4.
10. the preparation method of low temperature flexibility perovskite solar battery as claimed in claim 6, which is characterized in that described to incite somebody to action The tin oxide colloidal solution is spin-coated on electro-conductive glass layer surface and anneals, and annealing temperature is 80-180 DEG C.
CN201811088865.2A 2018-09-18 2018-09-18 A kind of low temperature flexibility perovskite solar battery and preparation method thereof Pending CN109285951A (en)

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