CN108806829A - The controllable metal-oxide film and its preparation method and application in metal oxide paste, aperture - Google Patents
The controllable metal-oxide film and its preparation method and application in metal oxide paste, aperture Download PDFInfo
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Abstract
The present invention relates to the controllable metal-oxide film and its preparation method and application in metal oxide paste, aperture, the metal oxide paste includes：Metal oxide nanoparticles, binder, nonionic surfactant and non-alcohols high boiling solvent.
Description
Technical field
The present invention relates to the preparation field of mesoporous material, more particularly to a kind of metal oxide paste, a kind of aperture are controllable
Metal-oxide film and preparation method thereof.
Background technology
Mesoporous material is widely used in the numerous areas such as absorption, separation, catalysis, biology, detection, energy conversion and storage,
People's concern is received all the time.The controllable metal-oxide film in aperture is designed and prepared to urge it in photovoltaic device, light
Application in the fields such as agent and lithium ion battery is of great significance.Such as in dye-sensitized solar cells and Jie's sight type calcium
In titanium ore solar cell, the aperture for regulating and controlling photo-anode film peomotes effective infiltration of light absorbent, and finally improves
Battery performance.
Chinese patent (publication number CN101777430A) discloses a kind of preparation method of mesoporous titanium dioxide film, to slurry
Ethyl cellulose and terpinol are added in material, mesoporous hole is left in the film after calcining removal.However the technical solution obtains
The aperture obtained is limited by titanium dioxide grain size.Abdi-Jalebi M et al. are adjusted by changing the grain size of nano-titanium dioxide
The aperture (Journal of Physical Chemistry letters, 2016,7,3264) of control gained film, the technical side
Case still cannot achieve the film that grain size is identical and aperture size is different.Addition macromolecule is another effective increase hole
The method of diameter.However, apply macromolecule as template in sol-gel method, Hydrolyze method or hydro-thermal method, the TiO obtained2
Mesoporous layer aperture is confined to 10nm or so mostly, in addition the TiO obtained by template agent method2Crystallinity is low, is unfavorable for interface and powers on
The fast transfer of son.Jong Hak Kim etc., which are reported, uses PVC-g-POEM graft copolymers as template, uses sol-gel
Method is prepared for aperture adjustable TiO within the scope of 28~73nm2Mesoporous layer (Chemical Communications, 2010,46,
1935).However, the usual thermal stability of mesopore film obtained by template agent method is not high, 450 DEG C or more of temperature calcination is easy to make
At caving in for film duct, therefore TiO2Nanocrystalline crystallinity is not usually high, and surface impurity removes unclean, mesopore film
Defect it is more.
Invention content
Present invention seek to address that easily being regulated and controled using the metal-oxide film aperture control method of open report at present
It the problem of influence film performances such as narrow range, film thickness are uncontrollable, film heat stability is poor, organic impurities removal is not clean, proposes
A kind of new slurry containing nonionic surfactant and non-alcohols high boiling solvent and it is based on non-ionic surface active
The aperture control method of agent and non-alcohols high boiling solvent synergistic effect.
In the first aspect of the present invention, a kind of metal oxide paste is provided comprising：Metal oxide nanoparticles,
Binder, nonionic surfactant and non-alcohols high boiling solvent.
According to the present invention, contain nonionic surfactant and non-alcohols high boiling solvent in metal oxide paste,
When the metal oxide paste is used to prepare film, nonionic surfactant is mutually concluded in non-alcohols high boiling solvent
Micella is formed, pore creating material and aperture adjustment agent are used as.Calcining removal after due to its steric effect leave in the film it is mesoporous
Hole.Therefore by regulating and controlling the component and composition of nonionic surfactant and non-alcohols high boiling solvent, film can be realized
The regulation and control in aperture.The non-alcohols high boiling solvent used in the present invention refers to without containing hydroxyl, and boiling point is organic at 100 DEG C or more
Solvent.Its high boiling characteristic of used solvent can ensure metal oxide paste stability at room temperature and good
Film forming.
Preferably, the metal oxide is selected from TiO2、ZnO、SnO2、ZrO2、Al2O3、NiO、SiO2、BaSnO2、
SrTiO3、Zn2SnO4、CaTiO3、BaTiO3、MgAl2O4、SiZrO3、FeTiO3At least one of.
Preferably, the nonionic surfactant is in block copolymer, polyoxyethylene ether, fluorinated surfactant
It is at least one.
Preferably, the non-alcohols high boiling solvent is selected from butyl, butyl acetate, diethylene glycol (DEG)
At least one of ethyl ether acetate ester, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, isophorone.
Preferably, the binder is selected from ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, gathers
At least one of ethylene oxide.
Preferably, metal oxide nanoparticles, nonionic surfactant, binder and non-alcohols high boiling solvent
Mass ratio is (0.1~0.3):(0.01~0.6):(0.01~1):(0.5~100).By adjusting the ratio, can regulate and control by
The aperture of film made from the metal oxide paste.
Preferably, in the metal oxide paste, the mass percentages of metal oxide nanoparticles is 5~
20%, the mass percentage of binder is 2~10%, and the mass percentage of nonionic surfactant is 1~45%, non-
The mass percentage of alcohols high boiling solvent is 30~90%.By adjusting the content of each component, especially non-ionic surface
The content of activating agent and/or non-alcohols high boiling solvent can regulate and control the hole of the film made from the metal oxide paste
Diameter.
In the second aspect of the present invention, a kind of preparation method for the metal-oxide film that aperture is controllable is provided comprising
Following steps：(1) film is made in any of the above-described metal oxide paste；(2) gained film is calcined, it is controllable obtains aperture
Metal-oxide film.
According to the present invention it is possible to regulate and control hole based on nonionic surfactant and non-alcohols high boiling solvent synergistic effect
Diameter, non-alcohols high boiling solvent can mix with nonionic surfactant, and the group of non-alcohols high boiling solvent will not position
In the hydrophilic between hydrophobic grouping of nonionic surfactant.Moreover, the present invention can directly using nano particle slurry come
Film, without template.The present invention can be made that aperture is controllable and modification scope is wide, film thickness is controllable, film heat stability
Good, impurity removes clean metal-oxide film, and preparation process is simple, of low cost, has wide range of applications.
Preferably, the aperture of the metal-oxide film is continuously adjusted within the scope of 10~100nm.
Preferably, the porosity of the metal-oxide film is continuously adjusted in 2~80% ranges.
Preferably, by adjusting nonionic surfactant and/or non-alcohols height boiling in the metal oxide paste
Type and/or the content of solvent are put to regulate and control aperture.
In the third aspect of the present invention, a kind of perovskite solar cell is provided, is contained by any of the above-described preparation method
The controllable metal-oxide film in the aperture of preparation.
The metal-oxide film can be as the electron transfer layer of perovskite solar cell so that the perovskite sun
Energy battery has higher fill factor and photoelectric conversion efficiency.
Description of the drawings
Fig. 1 is TiO in embodiment 12The electromicroscopic photograph of film.
Fig. 2 is TiO in comparative example 12The electromicroscopic photograph of film.
Fig. 3 is TiO2The pore size distribution curve of film, from left to right respectively comparative example 1, embodiment 1, embodiment 2,
Embodiment 3, embodiment 4.
Fig. 4 is TiO2Nitrogen adsorption-desorption curve of film, from left to right respectively comparative example 1, embodiment 1, embodiment
2, embodiment 3, embodiment 4.
Fig. 5 is that the positive and negative of perovskite solar cell sweeps current density voltage curve in embodiment 1.
Fig. 6 is that the positive and negative of perovskite solar cell sweeps current density voltage curve in embodiment 2.
Fig. 7 is that the positive and negative of perovskite solar cell sweeps current density voltage curve in embodiment 3.
Fig. 8 is that the positive and negative of perovskite solar cell sweeps current density voltage curve in embodiment 4.
Specific implementation mode
It is further illustrated the present invention below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
It is disclosed that a kind of metal oxide paste (referred to as " slurry ") comprising：Metal oxide nanoparticles glue
Tie agent, nonionic surfactant and non-alcohols high boiling solvent.
In the present invention, metal oxide is not particularly limited, from the point of view of application, metal oxide preferably half
Conductor metal oxide.In addition, metal oxide can be single oxide or metal composite oxide.One embodiment
In, metal oxide nanoparticles are selected from TiO2、ZnO、SnO2、ZrO2、Al2O3、NiO2、SiO2、BaSnO2、SrTiO3、
Zn2SnO4、CaTiO3、BaTiO3、MgAl2O4、SiZrO3、FeTiO3At least one of.
The size of metal oxide nanoparticles can cause porosity in 10~100nm ranges, the grain diameter of bigger
(porositys of i.e. following metal-oxide films) drastically reduce and have an adverse effect.The shape of metal oxide nanoparticles
Looks can be spherical, prismatic, rice-shaped, rodlike, fibrous etc..
Mass percentage of the metal oxide nanoparticles in metal oxide paste can be 0.1~25%, more excellent
It is selected as 5~20%.Too high or too low metal oxide mass percentage can influence the rheological property of slurry, to influence
Its filming performance.
Contain binder in the slurry of the disclosure, the metal oxide paste can be made to be more suitable for silk-screen printing, to obtain
High-quality thin film that can be graphical and controllable film thickness.It is fine that binder can be selected from ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl
Tie up at least one of element, polyethylene glycol, polyoxyethylene, preferably ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose
At least one of.Mass percentage of the binder in metal oxide paste can be 0.01~20%, more preferably 2~
10%.Binder content is too low or excessively high, cannot achieve effective silk-screen printing and obtains high-quality thin film.
Nonionic surfactant refers to non-ionizing surfactant in aqueous solution.Nonionic surfactant is in water
Neutralizing in organic solvent has preferable dissolubility, and stability is high in the solution so that the choosing of solvent in metal oxide paste
It is more extensive to select range, it is unrestricted.In one preferred embodiment, nonionic surfactant is selected from block copolymer, polyoxy
At least one of vinethene, fluorinated surfactant.Block copolymer can be diblock copolymer, triblock copolymer, how embedding
Section copolymer etc., such as can be selected from polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) triblock copolymer
Object, P123 ((EO)20(PO)70(EO)20)、F127((EO)106(PO)70(EO)106) etc..Fluorinated surfactant refers to fluorocarbon chain
For the surfactant of non-polar group, such as it can be selected from FSN-100 (CF3(CF2)5(EO)14)、FSO-100(CF3(CF2)4
(EO)10) etc..
Mass percentage of the nonionic surfactant in metal oxide paste can be 0.01~60%, nonionic
The content of surfactant can not be excessively high, otherwise can form excessive pore volume, and excessively loose structure can cause film mechanical
The reduction of intensity causes the cracking that caves in of film in subsequent thin film calcination process.It is highly preferred that nonionic surfactant exists
Mass percentage in metal oxide paste is 1~45%, effectively aperture adjustment may be implemented in the range, simultaneously
The mechanical strength for not interfering with film avoids the cracking that caves in of film.
Non-alcohols high boiling solvent refers to without containing hydroxyl, and the solvent of boiling point higher (100 DEG C or more).One is preferably implemented
In mode, non-alcohols high boiling solvent can be selected from glycol ether, glycol ether acetate etc., specifically can be selected from diethylene glycol fourth
Ether, butyl acetate, diethylene glycol ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether
At least one of propionic ester, isophorone.
Mass percentage of the non-alcohols high boiling solvent in metal oxide paste can be 25~98%, more preferably
30~90%.
In the disclosure, non-alcohols high boiling solvent can mix with nonionic surfactant, and non-alcohols higher boiling is molten
The group of agent will not be located at the hydrophilic between hydrophobic grouping of nonionic surfactant.If using alcohols solvent, group
The hydrophilic between hydrophobic grouping of nonionic surfactant can be located at, cause the expansion of nonionic surfactant micella, lead
It causes to crack in film calcination process and cave in, to cannot achieve the gain effect of aperture adjustment.If using low boiling point solvent, gold
Belonging to oxide slurry, solvent therein may slowly volatilize at room temperature, change the component of slurry, on the one hand influence its printing
The relative changes of its filming performance, another aspect solvent and nonionic surfactant ratio can also influence gained membrane pore size
Variation.
In the slurry of the disclosure, nonionic surfactant can mutually be concluded in non-alcohols high boiling solvent forms glue
Beam, as pore creating material and aperture adjustment agent.Since its steric effect leaves hole in the film after calcining removal.
By composition and ratio (the i.e. non-ionic surface active for regulating and controlling ionic surface active agent and non-alcohols high boiling solvent
The ratio etc. of ratio, the two and metal oxide particle between the type of agent and/or non-alcohols high boiling solvent, the two
At least one of in), the aperture of the film formed by the slurry can be regulated and controled.
In an embodiment of the present invention, metal oxide nanoparticles, nonionic surfactant mass ratio (0.1
~0.3):(0.01~0.6) is adjustable, it is preferable that 1:(0.1~3) is adjustable, it is highly preferred that 1:(0.2~2) is adjustable.
In an embodiment of the present invention, metal oxide nanoparticles, non-alcohols high boiling solvent mass ratio (0.1
~0.3):(0.5~100) is adjustable, it is preferable that 1:(5~50) are adjustable, it is highly preferred that 1:(6~20) are adjustable.
In an embodiment of the present invention, nonionic surfactant, non-alcohols high boiling solvent mass ratio (0.01~
0.6):(0.5~100) is adjustable, it is preferable that 1:(0.8~50) is adjustable, it is highly preferred that 1:(2~30) are adjustable.
In an embodiment of the present invention, metal oxide nanoparticles, nonionic surfactant and non-alcohols higher boiling
The mass ratio of solvent is (0.1~0.3):(0.01~0.6):(0.5~100) is adjustable.
In an embodiment of the present invention, metal oxide nanoparticles, binder mass ratio in (0.1~0.3):
(0.01~1) is adjustable, it is preferable that 1:(0.1~0.8) is adjustable.
In an embodiment of the present invention, metal oxide nanoparticles, nonionic surfactant, binder and non-alcohols
The mass ratio of high boiling solvent is (0.1~0.3):(0.01~0.6):(0.01~1):(0.5~100).
By adjusting any one of the above or a variety of ratios, the aperture of gained film can be regulated and controled, such as make the hole of film
Diameter is continuously adjusted within the scope of 10~100nm.
Then, as an example, illustrating the preparation method of above-mentioned metal oxide paste.
Metal oxide nanoparticles are scattered in alcohols solvent, metal oxide dispersion is obtained.
Above-mentioned alcohols solvent can be lower alcohol, such as the alcohol that carbon atom number is 1~4, can specifically enumerate methanol, ethyl alcohol,
N-butanol, isopropanol etc..The mass ratio of metal oxide nanoparticles and alcohols solvent can be the ratio suitable for preparing dispersion liquid,
For example, 1：(5~100).
Dispersing method can be selected from one or more combinations in magnetic agitation, ultrasound, shaking table mixing, high shear dispersion.
Nonionic surfactant, binder and non-alcohols high boiling solvent are added into metal oxide dispersion, point
Dissipate uniform, acquisition mixed solution.Dispersing method can be as described above.
The alcohols solvent in mixed solution is removed, metal oxide paste is obtained.The method of removal alcohols solvent for example may be used
For vacuum distillation etc..
The metal oxide paste of the disclosure can be used for preparing metal-oxide film, and metal-oxide film obtained
Aperture is controllable.
In one embodiment, by metal oxide paste film forming, calcining, the controllable metal-oxide film in aperture is obtained.
The optional range of film build method is wide, such as silk-screen printing, scraper method, spin-coating method can be used etc..Pass through these film forming sides
Method can readily control film thickness.For example, the thickness of the metal-oxide film of gained can regulate and control in 0.1~30 μ m.
Calcination temperature can be 400~600 DEG C.In the disclosure, calcining at such a temperature will not cause collapsing for film duct
It collapses.
After calcining, binder, nonionic surfactant and non-alcohols high boiling solvent are removed, and it is thin to be formed with hole
Film.As described above, by regulating and controlling nonionic surfactant and/or non-alcohols high boiling solvents in metal oxide paste
Type and/or content, can regulate and control the aperture of gained metal-oxide film, such as aperture is made to connect within the scope of 10~100nm
It is continuous adjustable.
A kind of method in the aperture of regulation and control metal-oxide film is also disclosed herein, i.e., by regulating and controlling above-mentioned metal oxide
The composition of slurry, to regulate and control the aperture of the metal-oxide film formed by the metal oxide paste.
The controllable metal-oxide film in aperture disclosed herein can be used for photovoltaic device, photochemical catalyst and lithium ion battery
Equal fields.
A kind of perovskite solar cell is also disclosed herein, contains the controllable metal-oxide film in above-mentioned aperture.
The controllable metal-oxide film in the aperture for example can be used as the electron transfer layer of perovskite solar cell.The hole
The controllable metal-oxide film of diameter can promote effective infiltration of the perovskite light absorbent in its hole, while increase calcium
The interfacial contact area of titanium ore and metal oxide semiconductor is more advantageous to the fast transfer of carrier, therefore can improve calcium titanium
The performance of mine solar cell.
The other structures of perovskite solar cell are not particularly limited, and structure well known in the art can be used.One is shown
In example, perovskite solar cell includes transparent conductive substrate, hole blocking layer, electron transfer layer (the controllable gold in aperture successively
Belong to sull), perovskite light absorbing layer, hole transmission layer, metal is to electrode.
A kind of new hole to act synergistically based on nonionic surfactant and non-alcohols high boiling solvent is herein proposed
Diameter regulates and controls method.The technical solution can continuously regulate and control aperture within the scope of 10~100nm, and film can by printing, spin coating,
Prepared by the different process such as scraper method, film thickness is controllable, and simple process has wide range of applications.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
(1) sol-gel method is used to prepare TiO2Weight ratio is 5 by nano particle：1 butyl titanate and acetic acid
Mixed solution is added drop-wise in deionized water, and acid adding adjusts solution pH value, and to be that 1,80 DEG C of reactions obtain blue and white in 6 hours translucent molten
Liquid is subsequently placed in water heating kettle at 250 DEG C and keeps the temperature 12 hours, collects white precipitate, grain size 20 is obtained after being washed with water and ethyl alcohol
The TiO of~30nm2Nano particle.
(2) by TiO2Nano particle is dissolved in ethanol solution, is uniformly dispersed.
(3) P123 (being purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd) and ethyl cellulose (30-60mpas,
It is purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd) it is scattered in ethyl alcohol in advance, and and TiO2Ethanol solution mixes,
TiO2Mass ratio with P123 is 1:0.3, TiO2Mass ratio with ethyl cellulose is 1:0.4.
(4) 2-Butoxyethyl acetate is added into above-mentioned mixed liquor, is uniformly mixed, P123 and 2-Butoxyethyl acetate
Mass ratio be 0.3:3.3.
(5) it is evaporated under reduced pressure removal alcohol solvent in 20mbar, obtains TiO2Slurry.
(6) FTO electro-conductive glass cleans 10min with lye, deionized water, acetone and EtOH Sonicate respectively, uses compressed air
Drying.
(7) the spin coating TiO on electro-conductive glass2Compacted zone, precursor solution are tetraisopropyl titanate (0.3mol/L), acetyl
The ethanol solution of acetone (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L).Presoma is paved with electro-conductive glass, rotation
Apply rotating speed 3000rpm, time 20s.It is handled at 70 DEG C with titanium tetrachloride aqueous solution (40mM) after calcining 1h at 500 DEG C
40min obtains hole blocking layer, and thickness is about 10-60nm.
(8) TiO is applied2Slurry spin coating TiO on the hole blocking layer2Film, spin coating rotating speed 4000rpm, time 30s,
500 DEG C of calcining 30min, film thickness is about 300nm.Fig. 1 is the electromicroscopic photograph of gained film, it can be seen that is dispersed in film
For several aperture sizes in tens of to up to a hundred nanometers of macropore, pore volume is big, is conducive to the effective of light absorbent in solar cell
Infiltration.
(9) spin coating perovskite light absorbent CH3NH3PbI3.By the PbI of 1.383g2, 0.477g CH3NH3I and 212.7 μ L
DMSO be dissolved in 1.9047mLDMF acquisition perovskite precursor solution.Perovskite precursor solution is spread in into above-mentioned system
On the substrate got ready, spin coating rotating speed 5000rpm, time 20s are added dropwise anti-solvent ether in 6s, then anneal at 100 DEG C
10min obtains perovskite active layer.
(10) on the perovskite active layer spin coating spiro-OMeTAD chlorobenzene solution (72.3mg/mL), spin coating turn
Fast 4000rpm, time 30s obtain hole transmission layer.
(11) vacuum thermal evaporation silver electrode, silver electrode thickness are 100nm on the hole transport layer.
Embodiment 2
According to the method for embodiment 1, in addition to following step has change, other steps are identical.
TiO in step (2)2Ratio with P123 is 1:0.5.
The mass ratio of P123 and 2-Butoxyethyl acetate is 0.5 in step (4):3.1.
Embodiment 3
According to the method for embodiment 1, in addition to following step has change, other steps are identical.
TiO in step (2)2Ratio with P123 is 1:1.
The mass ratio of P123 and 2-Butoxyethyl acetate is 1 in step (4):2.6.
Embodiment 4
According to the method for embodiment 1, in addition to following step has change, other steps are identical.
TiO in step (2)2Ratio with P123 is 1:2.
The mass ratio of P123 and 2-Butoxyethyl acetate is 2 in step (4):1.6.
Embodiment 5
According to the method for embodiment 1, in addition to following step has change, other steps are identical.
Keep the temperature 12 hours at 120 DEG C in reaction kettle in step (1), obtain grain size 10~15nm TiO2Nano particle.
TiO in step (2)2Ratio with P123 is 1:1.
The mass ratio of P123 and 2-Butoxyethyl acetate is 1 in step (4):3.
Embodiment 6
According to the method for embodiment 1, in addition to following step has change, other steps are identical.
In step (1) plus ammonium hydroxide to adjust pH value be 10, keep the temperature 5 hours at 50 DEG C in reaction kettle, obtain grain size 60~
The TiO of 80nm2Nano particle.
TiO in step (2)2Ratio with P123 is 1:1.
The mass ratio of P123 and 2-Butoxyethyl acetate is 1 in step (4):3.
Embodiment 7
Use F127 for nonionic surfactant in step (2), TiO2Ratio with F127 is 1:1.
The mass ratio of P123 and 2-Butoxyethyl acetate is 1 in step (4):3.
Embodiment 8
10mmol BaCl2·2H2O、10mmol SnCl4·5H2O and 5mmol C6H8O7It is dissolved in 170mL hydrogen peroxide
In aqueous solution, add ammonium hydroxide by pH value adjustment to 10 or so, 60min is aged at 90 DEG C, is cleaned obtained with water and ethyl alcohol respectively
Colloidal sol, final BaSnO3Nano particle is scattered in ethyl alcohol.
P123 and ethyl cellulose are scattered in ethyl alcohol in advance, and and BaSnO3Ethanol solution mixes, BaSnO3With P123's
Mass ratio is 1:3, BaSnO3Mass ratio with ethyl cellulose is 1:0.5.
2-Butoxyethyl acetate is added into above-mentioned mixed liquor, is uniformly mixed, P123 and 2-Butoxyethyl acetate
Mass ratio is 3:5.5.
It is evaporated under reduced pressure removal alcohol solvent in 20mbar, obtains BaSnO3Slurry.
Using BaSnO3Slurry for rotary coating BaSnO3Film, spin coating rotating speed 4000rpm, time 30s calcine 30min at 500 DEG C,
Film thickness is about 300nm.
Comparative example 1
By TiO2Nano particle (the preparation method is the same as that of Example 1) is dissolved in ethanol solution, is uniformly dispersed.
Ethyl cellulose is scattered in ethyl alcohol in advance, and and TiO2Ethanol solution mixes.
Terpinol is added into above-mentioned mixed liquor, is uniformly mixed.
It is evaporated under reduced pressure removal alcohol solvent in 20mbar, obtains TiO2Slurry.
Electro-conductive glass FTO cleans 10min with lye, deionized water, acetone and EtOH Sonicate respectively, is blown with compressed air
It is dry.
The spin coating TiO on electro-conductive glass2Compacted zone, precursor solution are tetraisopropyl titanate (0.3mol/L), levulinic
The ethanol solution of ketone (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L).Presoma is paved with electro-conductive glass, spin coating
Rotating speed 3000rpm, time 20s.Processing 40min is carried out at 70 DEG C with titanium tetrachloride aqueous solution (40mM) after calcining 1h at 500 DEG C,
Hole blocking layer is obtained, thickness is about 10-60nm.
Using TiO2Slurry spin coating TiO on the hole blocking layer2Film, spin coating rotating speed 4000rpm, time 30s, at 500 DEG C
30min is calcined, film thickness is about 300nm.
Spin coating perovskite light absorbent CH3NH3PbI3.By the PbI of 1.383g2, 0.477g CH3NH3I's and 212.7 μ L
DMSO is dissolved in acquisition perovskite precursor solution in 1.9047mLDMF.Perovskite precursor solution is spread in into above-mentioned preparation
On good substrate, anti-solvent ether is added dropwise in 6s in spin coating rotating speed 5000rpm, time 20s, and then anneal at 100 DEG C 10min,
Obtain perovskite active layer.
The chlorobenzene solution (72.3mg/mL) of spin coating spiro-OMeTAD, spin coating rotating speed on the perovskite active layer
4000rpm, time 30s obtain hole transmission layer.
Vacuum thermal evaporation silver electrode on the hole transport layer, silver electrode thickness are 100nm.
Comparative example 2
TiO is prepared using sol-gel method2Weight ratio is 5 by nano particle：The mixing of 1 butyl titanate and acetic acid
Solution is added drop-wise in deionized water, and it is that 1,80 DEG C of reactions obtain the translucent solution of blue and white in 6 hours that acid adding, which adjusts solution pH value, so
It is placed in water heating kettle at 250 DEG C and keeps the temperature 12 hours, collect white precipitate, 20~30nm of grain size is obtained after being washed with water and ethyl alcohol
TiO2Nano particle.
By TiO2Nano particle is dissolved in ethanol solution, is uniformly dispersed.
Ethyl cellulose (30-60mpas is purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd) is scattered in advance
In ethyl alcohol, and and TiO2Ethanol solution mixes, TiO2Mass ratio with ethyl cellulose is 1:0.4.
2-Butoxyethyl acetate is added into above-mentioned mixed liquor, is uniformly mixed, TiO2With 2-Butoxyethyl acetate
Mass ratio is 1:3.6.
It is evaporated under reduced pressure removal alcohol solvent in 20mbar, obtains TiO2Slurry.
TiO2Film preparation and perovskite solar cell are prepared with comparative example 1.
Comparative example 3
TiO2Nanometer grain preparation method is the same as comparative example 2.
By TiO2Nano particle is dissolved in ethanol solution, is uniformly dispersed.
(30-60mpas is purchased from for P123 (being purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd) and ethyl cellulose
Sigma-Aldrich (Shanghai) trade Co., Ltd) it is scattered in ethyl alcohol in advance, and and TiO2Ethanol solution mixes, TiO2With
The mass ratio of P123 is 1:1, TiO2Mass ratio with ethyl cellulose is 1:0.4.
Terpinol is added into above-mentioned mixed liquor, is uniformly mixed, the mass ratio of P123 and terpinol is 1:2.6.
It is evaporated under reduced pressure removal alcohol solvent in 20mbar, obtains TiO2Slurry.
TiO2Film preparation and perovskite solar cell are prepared with comparative example 1.
Fig. 1 is TiO in embodiment 12The electromicroscopic photograph of film, Fig. 2 are TiO in comparative example 12The electromicroscopic photograph of film, can be with
Find out compared with Example 1, the TiO that comparative example 1 is obtained2The hole of film is less, and aperture size is small, metal provided by the invention
The membrane pore size and pore volume bigger that oxide slurry is obtained are applied to catalysis or area of solar cell, can obtain more preferable
Performance.
The specific surface area of gained film is measured using BET specific surface area test method.Mould is calculated based on BJH pore-size distributions
Type, the pore-size distribution and porosity of film as obtained by nitrogen adsorption-desorption test method measurement.
Fig. 3 is TiO2The pore size distribution curve of film, from left to right respectively comparative example 1, embodiment 1, embodiment 2,
Embodiment 3, embodiment 4.Fig. 4 is TiO2Nitrogen adsorption-desorption curve of film, from left to right respectively comparative example 1, real
Apply example 1, embodiment 2, embodiment 3, embodiment 4.Table 1 show 1~3 gained film of Examples 1 to 8 and comparative example surface area,
Grain size, aperture, porosity.From Fig. 3,4 and table 1 as can be seen that Examples 1 to 8 can obtain mesopore film, and by adjusting gold
The ratio for belonging to oxide and nonionic surfactant can regulate and control the aperture of gained film.With the preparation of existing mesopore film
Method (comparative example 1) is compared, and the aperture of the film obtained by embodiment is greater than comparative example 1, and aperture is adjustable.With contain only non-alcohol
Class high boiling solvent, the metal oxide paste (comparative example 2) without containing nonionic surfactant are compared, and nonionic table is passed through
The synergistic effect of face activating agent and non-alcohols high boiling solvent can obtain the higher mesopore film of aperture bigger, porosity.It is right
Ratio 3 is the metal oxide paste containing nonionic surfactant and alcohols high boiling solvent, identical with component ratio
Embodiment 3 is compared, and aperture and porosity significantly reduce, and further demonstrates the present invention by nonionic surfactant and non-alcohol
Class high boiling solvent acts synergistically to realize the regulation and control in aperture.
Table 1
(the 100mW/cm under a standard sunlight2), the current-voltage of test gained perovskite solar cell is bent
Line, and corresponding short-circuit current density, open-circuit voltage, fill factor and photoelectric conversion efficiency is calculated.Fig. 5~8 show reality
It applies the positive and negative of the perovskite solar cell of the gained of example 1~4 and sweeps current density voltage curve, table 2 shows Examples 1 to 4 and right
Current density, voltage, fill factor, the photoelectric conversion efficiency of 1~3 gained perovskite solar cell of ratio.
Table 2
From Fig. 5~8 and table 2 as can be seen that the photoelectric current of perovskite solar cell, filling obtained by Examples 1 to 4 because
Son and photoelectric conversion efficiency are superior to comparative example 1~3, it is shown that adjustable metal sull application in aperture proposed by the present invention
In the huge advantage of perovskite solar cell.
Claims (10)
1. a kind of metal oxide paste, which is characterized in that including：Metal oxide nanoparticles, binder, non-ionic surface
Activating agent and non-alcohols high boiling solvent.
2. metal oxide paste according to claim 1, which is characterized in that the metal oxide is selected from TiO2、ZnO、
SnO2、ZrO2、Al2O3、NiO、SiO2、BaSnO2、SrTiO3、Zn2SnO4、CaTiO3、BaTiO3、MgAl2O4、SiZrO3、FeTiO3
At least one of.
3. metal oxide paste according to claim 1 or 2, which is characterized in that the nonionic surfactant choosing
From at least one of block copolymer, polyoxyethylene ether, fluorinated surfactant.
4. metal oxide paste according to any one of claim 1 to 3, which is characterized in that the non-alcohols height boiling
Point solvent is selected from butyl, butyl acetate, diethylene glycol ether acetate, propylene glycol monomethyl ether, propylene glycol
At least one of methyl ether acetate, propylene glycol monomethyl ether acetate, isophorone.
5. metal oxide paste according to any one of claim 1 to 4, which is characterized in that the binder is selected from
At least one of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, polyoxyethylene.
6. metal oxide paste according to any one of claim 1 to 5, which is characterized in that metal oxide nano
Particle, nonionic surfactant, binder and non-alcohols high boiling solvent mass ratio be（0.1~0.3）:（0.01~
0.6）:（0.01~1）:（0.5~100）.
7. a kind of preparation method for the metal-oxide film that aperture is controllable, which is characterized in that include the following steps：
（1）Film is made in metal oxide paste according to any one of claims 1 to 6；
（2）Gained film is calcined, the controllable metal-oxide film in aperture is obtained.
8. preparation method according to claim 7, which is characterized in that the aperture of the metal-oxide film 10~
It is continuously adjusted within the scope of 100nm.
9. preparation method according to claim 7 or 8, which is characterized in that by adjusting in the metal oxide paste
Nonionic surfactant and/or the type and/or content of non-alcohols high boiling solvents regulate and control aperture.
10. a kind of perovskite solar cell, which is characterized in that containing by the preparation side described in any one of claim 7 to 9
The controllable metal-oxide film in aperture prepared by method.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153051A (en) * | 2007-09-06 | 2008-04-02 | 复旦大学 | Ordered mesoporous material with ultra-large bore diameter and method of producing the same |
| KR20110075329A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 휘닉스소재 | Method of preparing titania nano-powder for dye-sensitized solar cell, method of preparing titania nano-dispersion, and photocatalyst |
| CN102173390A (en) * | 2011-01-20 | 2011-09-07 | 复旦大学 | Ordered mesoporous metal oxide material with ultra-large aperture and preparation method thereof |
| CN104538193A (en) * | 2014-12-18 | 2015-04-22 | 中国科学院上海硅酸盐研究所 | Titanium dioxide slurry and preparation method and application thereof |
-
2018
- 2018-06-08 CN CN201810589013.5A patent/CN108806829B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153051A (en) * | 2007-09-06 | 2008-04-02 | 复旦大学 | Ordered mesoporous material with ultra-large bore diameter and method of producing the same |
| KR20110075329A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 휘닉스소재 | Method of preparing titania nano-powder for dye-sensitized solar cell, method of preparing titania nano-dispersion, and photocatalyst |
| CN102173390A (en) * | 2011-01-20 | 2011-09-07 | 复旦大学 | Ordered mesoporous metal oxide material with ultra-large aperture and preparation method thereof |
| CN104538193A (en) * | 2014-12-18 | 2015-04-22 | 中国科学院上海硅酸盐研究所 | Titanium dioxide slurry and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李梅: "金属氧化物多孔纳米固体的制备及其复合发光材料的性质研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112542547A (en) * | 2020-12-08 | 2021-03-23 | 西北工业大学 | Preparation method of perovskite solar cell thin film absorption layer |
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