CN106299135B - A kind of high efficiency large area perovskite solar cell and preparation method thereof - Google Patents
A kind of high efficiency large area perovskite solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN106299135B CN106299135B CN201610936781.4A CN201610936781A CN106299135B CN 106299135 B CN106299135 B CN 106299135B CN 201610936781 A CN201610936781 A CN 201610936781A CN 106299135 B CN106299135 B CN 106299135B
- Authority
- CN
- China
- Prior art keywords
- light absorbing
- absorbing layer
- sio
- nano
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of high efficiency large area perovskite solar cell, component photoelectric conversion efficiency is 13%-14%.Perovskite solar cell light absorbing layer stephanoporate framework is siller tin oxide nanoparticle and nanometer Al2O3、ZrO2Or SiO2The stephanoporate framework film that high temperature sintering is formed, film porosity are 30%-50%, and film thickness 400-800nm, surface square resistance is 102‑103Ω；Perovskite light absorbing material is smooth and uniform CH3NH2PbI3Crystalline film；Hole transmission layer is smooth and uniform brown lead oxide and silica plural gel film, is formed with light absorbing layer and is well contacted, surface square resistance 102‑103Ω.It saves raw material simultaneously as silver ion reducing agent, conductive component and light absorbing layer framework material component using tin salt in the present invention and simplifies light absorbing layer stephanoporate framework preparation process, large area perovskite solar cell photoelectric conversion efficiency and stability can be improved.
Description
Technical field
The present invention relates to a kind of high efficiency large area perovskite solar cell and preparation method thereof, especially a kind of insulation
Body nanoparticle and low-resistance siller tin oxide Nanocomposites as light absorbing layer framework material large area perovskite too
Positive electricity pond and preparation method thereof, belongs to new energy and new material technology field.
Technical background
Perovskite solar cell be usually by transparent conducting glass, compacted zone, perovskite light absorbing layer, hole transmission layer and
Five part of back electrode composition.Perovskite light absorbing layer is usually by perovskite light absorbing material and as the porous nanometer material of skeleton
Film is constituted, and perovskite light absorbing layer is the core of perovskite solar cell, is inhaled by light absorbing layer skeleton and perovskite light
Material composition is received, thickness is generally 200-600nm, and main function is to absorb sunlight and generate electron-hole pair, and energy is high
Effect transmission electron-hole pair.
Common perovskite light absorbing layer skeleton nano material includes nano-TiO2、SnO2、ZnO、WO3、ReO、BaSnO3、
SrTiO3Equal semiconductor materials and Al2O3、ZrO2、SiO2Equal insulating materials, the most commonly used is nano-TiOs2Semiconductor material.Bone
Composition, appearance structure and the preparation process of frame nano material influence perovskite light absorbing layer performance very big.
Perovskite light absorbing layer skeleton nano-TiO2Membrane preparation method is first by nano-TiO2Slurry or colloid are coated on glass
On matrix, the high-temperature process at 400-500 DEG C is sintered to fix it and is formed on glass matrix.For example, Lausanne, SUI is federal
Institute of Technology patent of invention US20150200377（2015-07-16）；Korea Research Inst. of Chemical Technology patent of invention US
20160005547（2016-01-07）；Japan Ricoh company patent of invention US2015279573（2015-10-01）.
Nano-TiO2The shortcomings that light absorbing layer stephanoporate framework is：（1）Nano-TiO2It can make organic perovskite light absorbing material light
Catalytic decomposition destroys solar cell light conversion properties stabilizability；（2）Nano-TiO2Bone porous porosity is relatively low, light reflects
Strong and light transmittance is low, cannot function as thicker light absorbing layer stephanoporate framework；（3）It is suitable as the bone porous partial size 30- of absorbed layer
The nano-TiO of 60nm2Be not easy preparation and it is unstable；（4）Nano-TiO2Bone porous surface square resistance is excessive, it is also necessary to
Adulterating conductive component improves.
To improve the bone porous performance of light absorbing layer, exploitation is had conducted extensive research both at home and abroad.For example, in Wuhan University
In patent of invention CN104505409 (2015-04-08), TiO is replaced with stannic oxide2It is received as perovskite light absorbing layer skeleton
Rice material, the perovskite light absorbing layer photoelectric conversion efficiency of preparation are up to 12.5%, and main cause is the electric conductivity of stannic oxide
More preferably.In North China Electric Power University patent of invention CN105070836 (2015-11-18), with BaSnO3Instead of TiO2As calcium titanium
The perovskite light absorbing layer photoelectric conversion efficiency of mine light absorbing layer skeleton nano material, preparation is up to 11.5%, it may be possible to
BaSnO3Electron mobility to be apparently higher than TiO2Electron mobility.It is sent out in ISIS INNOVATION LIMITED company of Britain
Bright patent US20150249170 (2015-09-03) and US20150129034（2015-05-14）In, using nanometer Al2O3Generation
For nano-TiO2As perovskite light absorbing material skeleton, it is therefore prevented that nano-TiO2The light of organic perovskite light absorbing material is urged
Change and decompose, so that light absorbing layer photoelectric conversion efficiency be made to maintain higher level.
With CH3NH2PbI3Semiconductor material for the perovskite light absorbing material of representative, itself have certain electronics or
Cavity transmission ability, in small area and ultra-thin perovskite solar cell, even if not using framework material or using insulation
Also photoelectric conversion efficiency with higher when body framework material.But for large area and thicker perovskite solar cell, calcium titanium
The ability in mine light absorbing material self transmission electronics or hole is too late, and framework material is also used as the quick transmission in electronics or hole logical
Road, if the internal resistance of framework material is excessive, to will lead to electrons and holes a large amount of compound inside light absorbing layer.
Analyze existing patented technology discovery, in the presence of light absorbing layer stephanoporate framework, the photoelectricity of perovskite solar cell
Transfer efficiency just will be greatly reduced；Photoelectric conversion efficiency when using semiconducting backbone material is generally greater than using insulator skeleton
Photoelectric conversion efficiency when material.The current not clear semiconducting backbone material with which technical indicator can make perovskite too
Positive electricity pond has optimal photoelectric conversion efficiency.Low electrical resistant material is loaded on insulating material can be convenient ground controlled material
Surface square resistance uses it that can overcome nano-TiO as light absorbing layer framework material2Light absorbing layer stephanoporate framework material lacks
Point.
Hole transmission layer can promote electrons and holes in functional layer interfacial separation, reduce charge recombination and adjust level-density parameter
Property, help to improve photoelectric conversion efficiency of the solar battery.It is main at present in perovskite solar cell to apply 2,2 ', 7,7 '-
Four [N, N- two (4- methoxyphenyl) amino] two fluorenes of -9,9 '-spiral shell（spiro-OMeTAD）As hole mobile material
Photoelectric conversion efficiency is improved, since organic hole transport material is unstable and expensive, is not suitable for area battery application, with
Cuprous iodide is that the inorganic hole transporter of representative is researching and developing.Some patents disclose the calcium of no hole transmission layer
Titanium ore solar cell, but its photoelectric conversion efficiency is usually all relatively low, it is also necessary to seek the inorganic hole transmission material of Cheap highly effective
Material just adapts to the development of stability large area perovskite solar cell.
Summary of the invention
The object of the present invention is to provide a kind of high efficiency large area perovskite solar cells, by anti-reflection coated glass, receive
Rice silica transition zone, tin oxide transparent conductive film, titanium dioxide dense layer, light absorbing layer stephanoporate framework, perovskite light
Absorbing material, hole transmission layer, silver-colored back electrode, sealing film and battery back-sheet overlapping composition, it is characterized in that high efficiency large area
Perovskite solar cell is 200-300mm, width 15-30mm by length, is divided into the strip inside battery series connection collection of 1mm
In groups at, and use Al2O3、ZrO2Or SiO2Insulator nanometer particle load siller tin oxide (Ag-SnO2) low resistance nanoparticle
As light absorbing layer framework material, using tin salt simultaneously as silver ion reducing agent, conductive component and light absorbing layer skeleton material
Expect component, regulate and control the surface square resistance of stephanoporate framework material with can be convenient, thin film solar cell dimensional effect can be overcome,
Improve large area perovskite solar cell photoelectric conversion efficiency and stability.
Anti-reflection coated glass is with a thickness of 1.0-3.2mm, one side coating nano silica antireflective coating in the present invention
Solar cell glass, it is seen that light transmittance 93.8%-94.2%.
Nano silica transition zone is with a thickness of 20-100nm in the present invention, and partial size is the compact silicon dioxide of 5-10nm
Film.
Tin oxide transparent conductive film chemical composition is in the present invention：SnO2FxAgy, x=0.1-0.5, y=0.05-0.2, table
Face square resistance 5-10 Ω is that soluble silver salt and chlorination are filled on the fluorine-doped tin oxide gel mould of sol-gal process preparation
Stannous reducing agent is heat-treated at 450-500 DEG C and is prepared, and the soluble silver salt is silver nitrate, silver ammonia complex, acetic acid
Silver, silver salicylate, glyoxalic acid silver and silver citrate.
Titanium dioxide dense layer is with a thickness of 20-50nm in the present invention, and partial size is the compact titanium dioxide film of 2-5nm.
Light absorbing layer stephanoporate framework is by low-resistance nanometer Ag-SnO in the present invention2Being supported on partial size is 30-60nm's
Insulator Al2O3、ZrO2Or SiO2The stephanoporate framework laminated film that high temperature sintering is formed on nanoparticle, stephanoporate framework material group
It is at molar ratio：Ag：SnO2：（Al2O3、ZrO2Or SiO2）=1：3-5：5-15, film porosity are 30%-50%, pore diameter 5-
20nm, film thickness 400-800nm, surface square resistance are 102-103Ω。
Nanometer Ag-SnO in the present invention2Particle is a kind of good conductive material, is that metallic silver and tin oxide are formed
Solid solution is mainly used as the electrical contact material of switch and relay, the flexibility of existing metallic silver in early days, and has the height of tin oxide hard
Degree and high-melting-point characteristic, but the porosity of siller tin oxide film is low, individually cannot function as light absorbing layer stephanoporate framework material.It will receive
Rice Ag-SnO2Particle and insulator Al2O3、ZrO2Or SiO2Nanocomposites play the larger feature of its partial size, both maintained
Its excellent conductive performance, and improve the porosity of laminated film.
Perovskite light absorbing material is smooth and uniform CH in the present invention3NH2PbI3Crystalline film, by the two of lead iodide methylamine
Methylformamide solution be filled into the hole of stephanoporate framework laminated film crystallize formed, the drying and forming-film at 100-200 DEG C and
At.
Hole-transporting layer of the present invention be smooth and uniform brown lead oxide-silica dioxide gel film, be by partial size be 30-
Nanometer titanium dioxide lead button of 80nm, which condenses on perovskite light absorbing layer, to be formed, PbO2It is formed with light absorbing layer and is well contacted,
Thicknesses of layers is 30-80nm, surface square resistance 102-103Ω。
Brown lead oxide in the present invention has good electric conductivity, is mainly used as electrochemical electrode material in early days, is a kind of
Potential novel hole transport material.The crystalline particle of brown lead oxide of usual method preparation is relatively large in diameter, with receiving in the present invention
Rice silica can make brown lead oxide partial size be limited in 30-80nm as template.
Back electrode is nano-silver thread in the present invention or flake nano silver particles are that conductive component and polymer binder form
Conductive silver glue, sintering forms silver-colored back electrode at 100-200 DEG C, and surface square resistance is 1-5 Ω.
It is polyethylene vinyl acetate or polyvinyl butyral hot melt film that film is sealed in the present invention.
Battery back-sheet is the plate glass or macromolecule plate material of 1-3mm in the present invention.
It is a further object of the present invention to provide a kind of preparation methods of large area perovskite solar cell, by antireflective conduction
Glass preparation, the preparation of titanium dioxide dense layer, the preparation of perovskite light absorbing layer, hole transmission layer preparation, nano silver back electrode system
Standby and six part of cell package composition, preparation process include the following steps：
（1）Coating ethyl orthosilicate acidic hydrolysis is formed on the non-coated surface of antireflective plating film solar cell glass,
Partial size is 5-10nm, the nano silica hydrosol that mass percentage concentration is 5%, film plating layer dry solidification, shape at 150 DEG C
At the nano silica transition zone with a thickness of 50-100 nm；
（2）It is coated with pink salt ammonium hydroxide hydrolysis-oxalic acid peptisation preparation on nano silica transition zone, and adds ammonium fluoride
Fluorine-doped tin oxide nano-sized hydrosol, film plating layer dry solidification at 150 DEG C, formed fluorine-doped tin oxide gel mould, thicknesses of layers
600-800nm；It is coated with soluble silver salt solution 2-3 times on fluorine-doped tin oxide gel mould, is filled into it in gel membrane pores,
The ethanol solution for the stannous chloride that further coating quality percentage concentration is 10%, in-situ reducing forms nano silver particles, in 450-
It is heat-treated 0.5-1h at 500 DEG C, Fluorin doped is made to enter tin oxide lattice and is sintered nano silver particles, the doped stannum oxide of formation
Transparent conductive film chemical composition is：SnO2FxAgy, x=0.1-0.5, y=0.05-0.2,10 Ω of surface square resistance 5-；
（3）It is 15-30mm that doped tin oxide transparent conductive film, which is divided into width, is spaced the strip of 1mm, is divided into a system
Sub- battery to be prepared is arranged, it is water-soluble to be coated with the butyl titanate nano-titanium dioxide that in ethanol water prepared by acidic hydrolysis
Glue, film plating layer curing and drying at 150 DEG C form the titanium dioxide dense layer with a thickness of 20-50nm；
（4）Aluminate, zirconate or silicic acid ester hydrolysis are obtained into Al2O3、ZrO2Or SiO2Nano-sized hydrosol adds it
For the polyaminoester emulsion of quality 0.2%-1.0% as stabilizer, forming partial size is 30-60nm, and mass percentage concentration is receiving for 5%-7%
Rice Al2O3、ZrO2Or SiO2The hydrosol；
（5）To nanometer Al2O3、ZrO2Or SiO2Soluble stannous salting liquid is added in the hydrosol, to molten at 60-80 DEG C
Silver nitrate solution, Ag are added dropwise in liquid+Ion is attracted to a nanometer Al first2O3、ZrO2Or SiO2On particle surface, further with
Sn2+Reaction generates nano Ag particles, and silver nitrate solution is added dropwise to complete subsequent continuous insulation reaction 0.5-2h, and adding hydrogen peroxide makes
The oxidation of stannous particle, generates nanometer Ag-SnO2Particle and nanometer Al2O3、ZrO2Or SiO2The composite Nano hydrosol, in the hydrosol
The cohesion that nano Ag particles have effectively been blocked in the presence of organic acid dispersant and polyaminoester emulsion stabilizer is grown up, partial size 5-
10nm, control raw material molar ratio are： Ag+：Sn2+：（Al2O3、ZrO2Or SiO2） =1： 3-5：5-15, the solubility
Tin salt is stannous chloride, nitric acid stannous or stannous acetate；
（6）It heats and dries at being coated with the composite Nano hydrosol 1-3 times, 150 DEG C on the titanium dioxide dense layer of substrate material
It is dry, it then is heat-treated 0.5-1.0h at 450-500 DEG C, decomposes organic matter completely, composite nanoparticle is made to be sintered to form thickness
Degree is the light absorbing layer stephanoporate framework of 400-800nm, and stephanoporate framework material constitutive molar ratio is：Ag：SnO2：（Al2O3、ZrO2Or
SiO2）=1：3-5：5-15, film porosity are 30%-50%, and pore diameter 5-20nm, surface square resistance is 102-103Ω；
（7）The dimethyl formyl for the lead iodide methylamine that coating quality percentage concentration is 10% on light absorbing layer stephanoporate framework
Amine aqueous solution 2-3 times fills up the bone porous hole of light absorbing layer, and heat drying 2-3h, is filled into light absorption at 150 DEG C
Lead iodide methylamine crystallization in layer stephanoporate framework layer forms perovskite light absorbing layer in conjunction with stephanoporate framework material；
（8）Ethyl orthosilicate is hydrolyzed to obtain the nanometer titanium dioxide that mass percentage concentration is 5% in ethanol water neutral and alkali
Silica solution, colloidal sol pH are 9-10, Nano-meter SiO_22Partial size is 30-50nm, is added with stirring acetic acid lead solution, makes Pb2+It is adsorbed on
Nano-meter SiO_22On particle surface, it is heated to 50-60 DEG C, aqueous hydrogen peroxide solution is added, reaction 1-3h generates brown PbO2 -SiO2
Complex sol, with spare, nanometer PbO after biscuit ware funnel vacuum filter2Partial size is 30-80nm, and control material molar ratio is：
Silica：Lead acetate：Hydrogen peroxide=1：0.1-0.2：1-2；
（9）PbO is coated on perovskite light absorbing layer2-SiO2Nanometer titanium dioxide lead is condensed in perovskite by complex sol
On light absorbing layer, PbO2It is formed with light absorbing layer and is well contacted, the dry sky being made with a thickness of 30-80 nm at 150 DEG C
Cave transport layer, surface square resistance 102-103Ω；
（10）It carries out slotting for second on the hole transport layer, etching depth to fluorine-doped tin oxide transparency conducting layer will be empty
It is 15-30mm that cave transport layer, which is divided into width, is spaced the strip of 1mm, is connected convenient for sub- battery；Coating thickness is 800-
The conductive silver glue of 1200nm is heat-treated 0.5-1h at 100-200 DEG C, and nano silver is sintered to form silver-colored back electrode, surface square electricity
Resistance is 1-5 Ω；
（11）Nano silver back electrode is subjected to third time fluting etching, depth to hole transmission layer completes the string of sub- battery
Connection connection, from first and the collector of last sub- battery draws outer connecting wire；
（12）Polyvinyl acetate or polyvinyl butyral hot melt film are opened on silver-colored back electrode surface upper berth one, then covers one piece
Battery back-sheet, heat laminated encapsulation form battery component, and perovskite solar cell component photoelectric conversion efficiency is 13%-14%.
Experimental raw ethyl orthosilicate used in the present invention, four normal propyl alcohol ester of zirconic acid, tin tetrachloride, stannous chloride, dioxy
Change manganese, ascorbic acid, plumbi nitras, hydrogen peroxide, lead iodide, iodine methylamine, butyl titanate, ammonium hydroxide, ammonium fluoride, silver nitrate, nitre
Acid, ethyl alcohol, dimethylformamide and acetone are commercially available chemically pure reagent；Solar cell glass, conductive silver glue and polyurethane cream
Liquid is commercial goods.
The light transmittance of transparent thin-film material is with 920 type spectrophotometer test sample of Lambda in 400- in the present invention
The transmitance of 760nm visible-range calculates；The square resistance of thin-film material is measured with four probe sheet resistance of ST2258C type and is tried.Too
Positive battery efficiency is using the small-sized solar module tester simulated solar optical tests customized.
The beneficial effects of the present invention are embodied in：
（1）The present invention uses Al2O3、ZrO2Or SiO2The low-resistance siller tin oxide nanoparticle conduct of nanometer particle load
Light absorbing layer framework material reduces stephanoporate framework film resistor；
（2）Using tin salt simultaneously as silver ion reducing agent, conductive component and light absorbing layer framework material in the present invention
Component saves raw material and simplifies stephanoporate framework preparation process；
（3）Al is utilized in the present invention2O3、ZrO2Or SiO2The stable advantage of nanoparticle performance, can be improved large area calcium
Titanium ore photoelectric conversion efficiency of the solar battery and stability；
（4）The present invention, simply with low-cost sol-gal process technique, is easy to carry out solar cell using process equipment
Expand and realize industrial application.
Specific embodiment
Embodiment 1
On the non-coated surface of the antireflective plating film solar cell glass of one piece of 200mm × 300mm just with spreading rod coating
The silester partial size that acidic hydrolysis is formed in ethanol water is 5-10nm, the nanometer titanium dioxide that mass percentage concentration is 5%
The silicon hydrosol, film plating layer dry solidification at 150 DEG C form the nano silica transition zone with a thickness of 100 nm, and glass is saturating
Light rate increases to 95.5%.The further hydrolysis of coating tin tetrachloride ammonium hydroxide and oxalic acid peptization, and add the stannic oxide matter of ammonium fluoride
The fluorine-doped tin oxide nano-sized hydrosol that percentage concentration is 5% is measured, film plating layer dry solidification at 150 DEG C is formed with a thickness of 600nm
Fluorine-doped tin oxide gel mould.The ethyl alcohol for the silver nitrate that coating quality percentage concentration is 10% on fluorine-doped tin oxide gel mould is molten
Liquid 3 times, it is coated the ethanol solution for the stannous chloride that mass percentage concentration is 10%, 0.5h, shape are heat-treated at 450-500 DEG C
At tin oxide transparent conductive film, 5.9 Ω of surface square resistance.
Doped tin oxide transparent conductive film is divided into 200mm × 15mm, is spaced the strip of 1mm, be divided into it is a series of to
The sub- battery of preparation；It is coated with the nano-silica that the butyl titanate partial size that acidic hydrolysis is formed in ethanol water is 2-5nm
Change the titanium hydrosol, film plating layer curing and drying at 150 DEG C forms the titanium dioxide dense layer with a thickness of 20nm.
Weak aqua ammonia is added into four normal propyl alcohol aqueous solution of ester of zirconic acid to pH value of solution 8-9, is stirred to react 24-36h, zirconate is complete
All-hydrolytic forms the nanometer hydrated ZrO that partial size is 60nm2Particle adds the polyaminoester emulsion stabilizer of its quality 0.5%, obtains
The nano zirconium dioxide hydrosol for being 7% to mass percentage concentration.
To nanometer ZrO2Nitric acid stannous reducing agent solution is added in the hydrosol, nitric acid is added dropwise into solution at 60-80 DEG C
Silver-colored weak solution, Ag+Ion is attracted to a nanometer ZrO first2On particle surface, further with the Sn in solution2+Reaction generates Ag
Nanoparticle, AgNO3Solution is added dropwise to complete subsequent continuous insulation reaction 1.0h, and adding hydrogen peroxide aoxidizes stannous particle, raw
At nanometer Ag-SnO2Particle and nanometer ZrO2The compound hydrosol, Ag nano particle diameter are 5nm, and raw material molar ratio is：
Ag+：Sn2+：ZrO2=1：5：10.
Ag-SnO is coated on the titanium dioxide dense layer of substrate material2/ZrO2At the composite Nano hydrosol 2 times, 150 DEG C
Then heating, drying is heat-treated 0.5h, the Ag-SnO that sintering is formed with a thickness of 500nm at 450-500 DEG C2/ ZrO2Light absorption
Layer stephanoporate framework, film porosity are 42%, and pore diameter 15nm, surface square resistance is 620 Ω.
With the dimethyl of the stick coating method lead iodide methylamine that coating quality percentage concentration is 10% on light absorbing layer stephanoporate framework
Formamide solution 2 times, heat drying 2h, is filled into Ag-SnO at 150 DEG C2/ZrO2Lead iodide first in light absorbing layer skeleton
Amine crystallizes to form black perovskite light absorbing layer.
Ethyl orthosilicate is hydrolyzed to obtain the nano silica that mass percentage concentration is 5% in ethanol water neutral and alkali
Colloidal sol, Nano-meter SiO_22Partial size is 30-50nm, is added with stirring acetic acid lead solution, makes Pb2+It is adsorbed on Nano-meter SiO_22Particle surface
On, it is heated to 50-60 DEG C, aqueous hydrogen peroxide solution is added, reaction 1-3h generates brown PbO2-SiO2Raw material is added in complex sol
Molar ratio is：Silica：Lead acetate：Hydrogen peroxide=1：0.1：1, with spare, nanometer after biscuit ware funnel vacuum filter
PbO2Partial size is 50nm.PbO is coated on perovskite light absorbing layer2-SiO2Complex sol, at 150 DEG C it is dry be made with a thickness of
The hole transmission layer of 60 nm, 360 Ω of surface square resistance.
It carries out slotting for second on the hole transport layer, etching depth passes hole to fluorine-doped tin oxide transparency conducting layer
It is 15mm that defeated layer, which is divided into width, is spaced the strip of 1mm, is coated with the conductive silver glue of thickness 1000nm, at 180 DEG C at heat
0.5h is managed, nano silver is sintered to form silver-colored back electrode, and surface square resistance is 2.6 Ω.
Nano silver back electrode is subjected to third time fluting etching, 200mm × 15mm is divided into, is spaced the rectangle of 1mm, depth
To hole transmission layer, the series connection of sub- battery is completed, from first and the collector of last sub- battery draws outer connection
Conducting wire.
Polyvinyl acetate hot melt film is opened on silver-colored back electrode surface upper berth one, then covers one piece of glass back plate, heating layer press seal
Dress composition battery component, measuring battery component photoelectric conversion efficiency with small-sized solar module tester is 13.2%.
Embodiment 2
Antireflective electro-conductive glass and the preparation of titanium dioxide dense layer first are completed by embodiment 1, gets out light absorbing layer substrate
Material.
Weak aqua ammonia is added into ethyl orthosilicate aqueous solution to pH value of solution 9-10, is stirred to react 24-36h, ethyl orthosilicate
Complete hydrolysis forms the nano-silicon dioxide particle that partial size is 50nm, adds the polyaminoester emulsion stabilizer of its quality 1.0%,
Obtain the nano silica hydrosol that mass percentage concentration is 5%.
To Nano-meter SiO_22Stannous acetate reducing agent solution is added in the hydrosol, nitric acid is added dropwise into solution at 60-80 DEG C
Silver-colored weak solution, Ag+Ion is attracted to Nano-meter SiO_2 first2On particle surface, further with the Sn in solution2+Reaction is generated and is received
Rice Ag particle, AgNO3Solution is added dropwise to complete subsequent continuous insulation reaction 0.5h, and adding hydrogen peroxide aoxidizes stannous particle, raw
At nanometer Ag-SnO2Particle and Nano-meter SiO_22The compound hydrosol, Ag nano particle diameter are 8nm, and raw material molar ratio is：
Ag+：Sn2+：SiO2=1：5：15.
Heating, drying at being coated with the composite Nano hydrosol 2 times, 150 DEG C on the titanium dioxide dense layer of substrate material, so
0.5h, the Ag-SnO that sintering is formed with a thickness of 800nm are heat-treated at 450-500 DEG C afterwards2/SiO2Light absorbing layer stephanoporate framework is thin
Membrane porosity is 48%, pore diameter 15nm, and surface square resistance is 760 Ω.
With the dimethyl of the stick coating method lead iodide methylamine that coating quality percentage concentration is 10% on light absorbing layer stephanoporate framework
Formamide solution 2 times, heat drying 2h, is filled into Ag-SnO at 150 DEG C2/SiO2Lead iodide first in light absorbing layer skeleton
Amine crystallizes to form black perovskite light absorbing layer.
Ethyl orthosilicate is hydrolyzed to obtain the nano silica that mass percentage concentration is 5% in ethanol water neutral and alkali
Colloidal sol, Nano-meter SiO_22Partial size is 30-50nm, is added with stirring acetic acid lead solution, makes Pb2+It is adsorbed on Nano-meter SiO_22Particle surface
On, it is heated to 50-60 DEG C, aqueous hydrogen peroxide solution is added, reaction 1-3h generates brown PbO2-SiO2Raw material is added in complex sol
Molar ratio is：Silica：Lead acetate：Hydrogen peroxide=1：0.15：1, with spare, nanometer after biscuit ware funnel vacuum filter
PbO2Partial size is 70nm.PbO is coated on perovskite light absorbing layer2-SiO2Complex sol, at 150 DEG C it is dry be made with a thickness of
The hole transmission layer of 80 nm, 270 Ω of surface square resistance.
It carries out slotting for second on the hole transport layer, etching depth passes hole to fluorine-doped tin oxide transparency conducting layer
It is 15mm that defeated layer, which is divided into width, is spaced the strip of 1mm, is coated with the conductive silver glue of thickness 1000nm, at 180 DEG C at heat
0.5h is managed, nano silver is sintered to form silver-colored back electrode, and surface square resistance is 2.5 Ω.
Nano silver back electrode is subjected to third time fluting etching, 200mm × 15mm is divided into, is spaced the rectangle of 1mm, depth
To hole transmission layer, the series connection of sub- battery is completed, from first and the collector of last sub- battery draws outer connection
Conducting wire.
Polyvinyl acetate hot melt film is opened on silver-colored back electrode surface upper berth one, then covers one piece of glass back plate, heating layer press seal
Dress composition battery component, measuring battery component photoelectric conversion efficiency with small-sized solar module tester is 13.6%.
Claims (7)
1. a kind of high efficiency large area perovskite solar cell, by anti-reflection coated glass, nano silica transition zone, oxidation
Tin transparent conductive film, light absorbing layer stephanoporate framework, perovskite light absorbing material, hole transmission layer, is received titanium dioxide dense layer
The silver-colored back electrode of rice, sealing film and battery back-sheet overlapping composition, it is characterized in that high efficiency large area perovskite solar cell is by growing
Degree is 200-300mm, width 15-30mm, is divided into the integrated composition of strip inside battery series connection of 1mm, and uses Al2O3、
ZrO2Or SiO2Nanometer particle load siller tin oxide nanoparticle as light absorbing layer framework material, using tin salt simultaneously as
Silver ion reducing agent, conductive component and light absorbing layer framework material component, regulate and control the surface of stephanoporate framework material in which can be convenient
Square resistance.
2. high efficiency large area perovskite solar cell as described in claim 1, it is characterized in that light absorbing layer stephanoporate framework be by
Siller tin oxide nanometer particle load is in the nanometer Al that partial size is 30-60nm2O3、ZrO2Or SiO2High temperature sintering is formed on particle, more
Hole on framework material constitutive molar ratio is：Ag：Sn：（Al2O3、ZrO2Or SiO2）=1：3-5：5-15.
3. high efficiency large area perovskite solar cell as described in claim 1, it is characterized in that light absorbing layer stephanoporate framework is table
The smooth and uniform composite material porous membrane in face, film porosity are 30%-50%, pore diameter 5-20nm, and film thickness is
400-800nm, surface square resistance are 102-103Ω。
4. high efficiency large area perovskite solar cell as described in claim 1, it is characterized in that perovskite light absorbing material is flat
Sliding uniform CH3NH2PbI3Crystalline film is filled into light absorbing layer stephanoporate framework by the dimethyl formamide solution of lead iodide methylamine
Hole in crystallize formed, the drying and forming-film at 100-200 DEG C.
5. high efficiency large area perovskite solar cell as described in claim 1, it is characterized in that hole transmission layer is smooth and uniform
Brown lead oxide-silica dioxide gel film, be by partial size be 30-80nm nanometer titanium dioxide lead button condense in perovskite light inhale
It receives and is formed on layer, formed with light absorbing layer and well contacted, thicknesses of layers 30-80nm, surface square resistance 102-103Ω。
6. the preparation method of high efficiency large area perovskite solar cell described in a kind of claim 1, by antireflective electro-conductive glass
Preparation, titanium dioxide dense layer preparation, perovskite light absorbing layer preparation, hole transmission layer preparation, nano silver back electrode preparation and
Six part of cell package composition, it is characterized in that the preparation method of perovskite light absorbing layer is：
（1）Aluminate, zirconate or silicic acid ester hydrolysis are obtained into Al2O3、ZrO2Or SiO2Nano-sized hydrosol adds its quality
For the polyaminoester emulsion of 0.2%-1.0% as stabilizer, forming partial size is 30-60nm, and mass percentage concentration is the nanometer of 5%-7%
Al2O3、ZrO2Or SiO2The hydrosol；
（2）To nanometer Al2O3、ZrO2Or SiO2Soluble stannous salting liquid is added in the hydrosol, is dripped at 60-80 DEG C into solution
Add silver nitrate solution, Ag+Ion is attracted to a nanometer Al first2O3、ZrO2Or SiO2On particle surface, further with Sn2+Reaction
Nano Ag particles are generated, silver nitrate solution is added dropwise to complete subsequent continuous insulation reaction 0.5-2h, and adding hydrogen peroxide makes stannous grain
Son oxidation, generates nanometer Ag-SnO2Particle and nanometer Al2O3、ZrO2Or SiO2The composite Nano hydrosol, organic acid in the hydrosol
The cohesion that nano Ag particles have effectively been blocked in the presence of dispersing agent and polyaminoester emulsion stabilizer is grown up, partial size 5-10nm,
Controlling raw material molar ratio is： Ag+：Sn2+：（Al2O3、ZrO2Or SiO2） =1： 3-5：5-15, the solubility tin salt
It is stannous chloride, nitric acid stannous or stannous acetate；
（3）Heating, drying at being coated with the composite Nano hydrosol 1-3 times, 150 DEG C on the titanium dioxide dense layer of substrate material, so
Be heat-treated 0.5-1.0h at 450-500 DEG C afterwards, decompose organic matter completely, make composite nanoparticle be sintered to be formed with a thickness of
The light absorbing layer stephanoporate framework of 400-800nm, stephanoporate framework material constitutive molar ratio are：Ag：SnO2：（Al2O3、ZrO2Or SiO2）
=1：3-5：5-15, film porosity are 30%-50%, and pore diameter 5-20nm, surface square resistance is 102-103Ω；
（4）The dimethylformamide for the lead iodide methylamine that coating quality percentage concentration is 10% on light absorbing layer stephanoporate framework is molten
Liquid 2-3 times fills up the bone porous hole of light absorbing layer, and heat drying 2-3h, it is more to be filled into light absorbing layer at 150 DEG C
Lead iodide methylamine crystallization in hole on framework layer forms smooth and uniform perovskite light absorbing layer in conjunction with stephanoporate framework material.
7. the preparation method of high efficiency large area perovskite solar cell as claimed in claim 6, it is characterized in that hole transmission layer
Preparation method is：
（1）It is molten that ethyl orthosilicate in ethanol water neutral and alkali is hydrolyzed to obtain the nano silica that mass percentage concentration is 5%
Glue, colloidal sol pH are 9-10, Nano-meter SiO_22Partial size is 30-50nm；
（2）Acetic acid lead solution is added under stirring into nano silicon dioxide sol, makes Pb2+It is adsorbed on Nano-meter SiO_22Particle surface
On, it is heated to 50-60 DEG C, aqueous hydrogen peroxide solution is added, generates brown PbO after reacting 1-3h2-SiO2Complex sol, control are former
Expect that molar ratio is：Silica：Lead acetate：Hydrogen peroxide=1：0.1-0.2：1-2, with biscuit ware funnel vacuum filter standby
With nanometer PbO in complex sol2Partial size is 30-80nm；
（3）PbO is coated on perovskite light absorbing layer2-SiO2Complex sol makes brown lead oxide condense in perovskite light absorbing layer
On, it is formed with light absorbing layer and is well contacted, the dry hole transmission layer being made with a thickness of 30-80 nm, surface at 150 DEG C
Square resistance 102-103Ω。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610936781.4A CN106299135B (en) | 2016-10-25 | 2016-10-25 | A kind of high efficiency large area perovskite solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610936781.4A CN106299135B (en) | 2016-10-25 | 2016-10-25 | A kind of high efficiency large area perovskite solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106299135A CN106299135A (en) | 2017-01-04 |
| CN106299135B true CN106299135B (en) | 2018-11-23 |
Family
ID=57720207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610936781.4A Expired - Fee Related CN106299135B (en) | 2016-10-25 | 2016-10-25 | A kind of high efficiency large area perovskite solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106299135B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113488651B (en) * | 2020-08-31 | 2022-11-25 | 中南大学 | Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof |
| CN113725313A (en) * | 2021-09-01 | 2021-11-30 | 昆山娟伟腾光伏科技有限公司 | Flat heterojunction inorganic thin film solar cell and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014175473A (en) * | 2013-03-08 | 2014-09-22 | Osaka Gas Co Ltd | Perovskite-type photoelectric conversion apparatus using an inorganic hole transport material |
| CN104167293A (en) * | 2014-08-08 | 2014-11-26 | 青岛科技大学 | Dye-sensitized solar cell photoanode and producing method thereof |
| CN104300083A (en) * | 2014-09-29 | 2015-01-21 | 中国科学院广州能源研究所 | Method for preparing organic-inorganic perovskite structure heterocomplex thin film solar cell |
-
2016
- 2016-10-25 CN CN201610936781.4A patent/CN106299135B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014175473A (en) * | 2013-03-08 | 2014-09-22 | Osaka Gas Co Ltd | Perovskite-type photoelectric conversion apparatus using an inorganic hole transport material |
| CN104167293A (en) * | 2014-08-08 | 2014-11-26 | 青岛科技大学 | Dye-sensitized solar cell photoanode and producing method thereof |
| CN104300083A (en) * | 2014-09-29 | 2015-01-21 | 中国科学院广州能源研究所 | Method for preparing organic-inorganic perovskite structure heterocomplex thin film solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106299135A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104409642B (en) | Preparation method of perovskite/P-type quantum dot composite solar cell | |
| CN105762283B (en) | A kind of perovskite solar cell light absorption layer Nano sol coating liquid and preparation method | |
| WO2015007094A1 (en) | Mesoscopic solar cell based on perovskite light absorption material and preparation method thereof | |
| Li et al. | Zinc-doped SnO 2 nanocrystals as photoanode materials for highly efficient dye-sensitized solar cells | |
| CN104091889A (en) | Semi-conductor perovskite solar cell and preparing method thereof | |
| CN105932159B (en) | A kind of perovskite solar cell hole transmission layer Composite Coatings film liquid and preparation method | |
| CN106449984B (en) | A kind of stable large area perovskite solar cell and preparation method thereof | |
| Zhang et al. | Novel bilayer structure ZnO based photoanode for enhancing conversion efficiency in dye-sensitized solar cells | |
| CN106252518A (en) | One is low blocks large area perovskite solar cell and preparation method thereof | |
| CN105789339A (en) | Perovskite solar cell nano silicon dioxide coating liquid and application thereof | |
| CN107579134A (en) | Full-inorganic perovskite solar cell prepared based on continuous spin coating and its preparation method and application | |
| CN106299135B (en) | A kind of high efficiency large area perovskite solar cell and preparation method thereof | |
| CN102539487A (en) | Air-sensitive material compounded by titanium dioxide nanometer lines and stannic oxide nanometer particles and preparation method thereof | |
| CN106128772B (en) | A kind of preparation method of vulcanized lead quantum dot photovoltaic battery | |
| CN102324316B (en) | Compound light anode and preparation method thereof | |
| Wang et al. | Effects of ZnSe modification on the perovskite films and perovskite solar cells based on ZnO nanorod arrays | |
| CN106410036A (en) | Large-area perovskite solar cell and preparation method thereof | |
| CN106159096B (en) | A kind of double-side photic large area perovskite solar cell and preparation method thereof | |
| CN109671846A (en) | Perovskite solar battery and its preparation using three-dimensional structure graphene as back electrode | |
| Zhu et al. | Synthesis of highly‐ordered hierarchical ZnO nanostructures and their application in dye‐sensitized solar cells | |
| KR101347702B1 (en) | Hierarchically structured titanium dioxide powder manufacturing method and quantum-dot-sensitized solar cell manufacturing method using the same | |
| CN108511197B (en) | Based on three layers of TiO2The dye cell of laminated film | |
| JP2005251591A (en) | Manufacturing method of negative electrode in dye-sensitized solar cell | |
| CN104681291A (en) | Preparation method of titanium dioxide nanotube composite film electrode | |
| JP6765658B2 (en) | A pressed molded product containing particles of a metal composite anion compound and its use, and a method for producing the pressed molded product. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181123 Termination date: 20191025 |