CN110128670A - Band halo SP-MOF crystal, preparation method and perovskite solar battery - Google Patents
Band halo SP-MOF crystal, preparation method and perovskite solar battery Download PDFInfo
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Abstract
The present invention discloses a kind of oblique hexagonal column shape Pb-MOF crystal of rule, and containing Pb, C, O element, atom number percentage is respectively 5-10%, 55-60% and 35-40%；The side length of bottom surface regular hexagon is 5-10nm, height of column 1-3nm, and the slanted angle between prism and bottom surface is 40-60 °；A kind of oblique SP-MOF crystal of the hexagonal column shape with halo of rule, contain Pb, C, N, O element, its atom number percentage is respectively 1-5%, 75-80%, 3-5% and 15-20%, the side length of bottom surface regular hexagon is 1.2-1.5 μm, height of column is 0.7-1 μm, slanted angle between prism and bottom surface is 40-60 °, and has the halo of 50-60nm width in crystal periphery.SP-MOF is applied to the hole transmission layer of perovskite solar battery, the moisture-proof and photoelectric conversion efficiency of battery can be improved.
Description
Technical field
The present invention relates to a kind of band halo SP-MOF crystal, preparation method and perovskite solar batteries, belong to material conjunction
At field.
Background technique
Metal-organic framework material is that central metallic ions or central metal cluster and organic ligand are passed through self assembly
The crystalline state porous material that journey is formed.Compared with traditional inorganic porous material, metal organic frame (MOFs) material has bigger
Porosity and specific surface area, especially adjustable aperture and variable functional group.It combines inorganic and organic material
The characteristics of material, has potential value with the fields such as separating in storage, catalysis, sensor, gas absorption.The research of MOFs is related to
The fields such as organic chemistry, inorganic chemistry, Coordinative Chemistry, materials chemistry, life science and computer science, in recent years by more
Carry out more concerns.
In recent years, researcher had made more effort in terms of the synthesis of MOFs, such as reasonable selection metal center with
And organic ligand makes MOF have diversified structure and function.MOFs generally passes through the method for hydro-thermal or solvent heat at present, will
Mutually independent metal ion and organic ligand synthesize nano material.While in order to accelerate the crystallization process of material, to obtain
Smaller partial size, people also have investigated new method, such as Microwave-assisted synthesis method, electrochemical synthesis, ultrasonic.Mesh
Before obtained MOF material be largely the frame material for having used new ligand or synthesis, with novel topological structure.Metal
The synthesis of organic framework materials, mainly by shadows such as metal ion, ligand, anion, temperature, the composition of pH value and reaction ratios
It rings, the variation of each factor may cause the change of crystal structure.
In Chinese patent " a kind of using metal organic frame as the preparation method of the lithium cell cathode material of template " (publication number
CN105932285A in), when preparing Pb-MOF (lead base MOF), the organic ligand 4- p-methylphenyl-that need to be 1:2 by molar ratio
Pyridine-N-oxide and Pb (NO3)2(plumbi nitras) is dissolved in the mixing of DMF (N,N-dimethylformamide) and water that volume ratio is 1:1
In solvent, reacted for 24 hours at 80 DEG C of reaction kettle.However, the Pb-MOF that this kind of method is prepared is non crystalline structure, and remain more
Kind impurity.
In existing literature, Congyang Zhang et al. [Nature Communications (2017,8:1138)] is mentioned
Molar ratio is the 1,3,5-H of 1:1 by a kind of preparation method of Pb-MOF3BTC (trimesic acid) and Pb (NO3)2It is dissolved in
In aqueous solution, ultrasonic 30min.The sediment being obtained by filtration later, it is dry with ethanol washing.1,3,5-H in report3BTC is used
High-power ultrasonic mode is dispersed, and after dehydrated alcohol is added, Pb-MOF is obtained by the way of suction filtration, however, the Pb- of its preparation
MOF is also non crystalline structure in irregular shape.
In solar cells, hole transmission layer is applied not only to promote its photoelectric conversion performance, but also can pass through prevention
Moisture or oxygen penetrate into calcium titanium ore bed hereinafter, to improve the long-time stability of device in the environment.Spiro-OMeTAD(2,
2', 7,7'- tetra--dimethoxy diphenylamines-spiro fluorene, is abbreviated as SP) it is used as a kind of novel hole transport material, in solar battery
In be widely used, but since its carrier transfer ability is lower, moisture resistance is poor, needs to improve it.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of band halo SP-MOF crystal, preparation method and
Perovskite solar battery solves the amorphism of metal organic frame and the perovskite battery based on pure SP hole transmission layer
In the low problem of moist environment stability inferior.
To achieve the goals above, a kind of Pb-MOF crystal that the present invention uses, the Pb-MOF crystal are rule oblique six
Side column shape, contains Pb, C, O element in the Pb-MOF crystal, atom number percentage be respectively 5-10%, 55-60% and
35-40%.
Preferably, the side length of the bottom surface regular hexagon of the Pb-MOF crystal be 5-10nm, height of column 1-3nm,
Slanted angle between prism and bottom surface is 40-60 °.
In addition, the present invention also provides a kind of preparation methods of Pb-MOF crystal, comprising the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3BTC aqueous solution stirs 30-40min at 50-75 DEG C, then mixes two kinds of aqueous solutions, so that 1,3,5-H3BTC and Pb
(NO3)2Molar ratio be 1:(0.9-1.25), mixed solution is stirred into 30-40min at room temperature, it is molten to obtain Pb-MOF forerunner
Liquid；
2) it prepares Pb-MOF crystal: Pb-MOF precursor solution ultrasound 30-40min being formed and is precipitated, nothing is added into precipitating
Water-ethanol, is centrifuged 10-20min at revolving speed 9000-10000rpm, then ultrasound 5-10min washing, repeats 6-10 times, finally in
60-70 DEG C of drying 12-14h obtains Pb-MOF crystal.
The present invention also provides a kind of preparation methods with halo SP-MOF crystal, comprising steps of
1) SP-MOF mixed solution is prepared: regular tiltedly hexagonal column shape Pb-MOF crystal powder, SP powder, Li-TFSI is (double
Trifyl acid imide) acetonitrile solution, tBP solution (4- tert .-butylpyridine, purity 96%), FK209 (tris (2-
(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III)tris(bis
(trifluoromethylsulfonyl) imide), cobalt complex) acetonitrile solution mixed with chlorobenzene, content is relative to chlorine
Benzene is respectively 40-50g/L, 85-86g/L, 0.015-0.02L/L, 0.03-0.04L/L, 0.007-0.009L/L, shakes 45-
SP-MOF mixed solution is prepared after 60min；
2) SP-MOF crystal is prepared: the filtering head for being 0.2-0.45 μm with aperture by SP-MOF mixed solution obtained, mistake
Large-size crystals are filtered, obtain small size SP-MOF precursor solution, then with the revolving speed of 3000-5000rpm, be uniformly spin-coated on FTO
On, FTO is rinsed with ethyl alcohol after spin coating 20-40s, obtains the ethanol solution containing SP-MOF crystal, after ethanol solution volatilization, is obtained
To SP-MOF crystal.
Preferably, Li-TFSI is relative to the content of acetonitrile in the acetonitrile solution of Li-TFSI in the step 1)
510-525g/L；FK209 is 395-410g/L relative to the content of acetonitrile in the acetonitrile solution of FK209.
In addition, the present invention also provides it is a kind of using the preparation method be made rule tiltedly hexagonal column shape with halo
SP-MOF crystal.
Preferably, containing Pb, C, N, O element in the SP-MOF crystal, atom number percentage is respectively 1-
5%, 75-80%, 3-5% and 15-20%.
Preferably, the side length of the bottom surface regular hexagon of the SP-MOF crystal is 1.2-1.5 μm, height of column 0.7-
1 μm, the slanted angle between prism and bottom surface is 40-60 °, and has the halo of 50-60nm width in crystal periphery.
In addition, the present invention also provides a kind of perovskite solar energy using the SP-MOF crystal doping hole transmission layer
Battery.
Finally, the present invention provides a kind of processing methods of perovskite solar battery, comprising the following steps:
1) it prepares electron transfer layer: preparing substrate, electron transfer layer is prepared in substrate；
2) it prepares perovskite active layer: preparing perovskite active layer on the electron transport layer；
3) it prepares hole transmission layer: by SP-MOF precursor solution with the revolving speed of 3500-4500rpm, being uniformly spin-coated on calcium titanium
On ore bed, hole transmission layer is prepared after spin coating 15-25s；
4) it prepares metal electrode: preparing metallic silver (Ag) electrode on the hole transport layer.
The present invention is by by finely dispersed organic ligand 1,3,5-H3BTC is uniformly mixed with lead ion, to form rule
After being shaken, being washed, pure Pb-MOF crystal is made in the then Pb-MOF crystal of oblique hexagonal column shape, Pb-MOF crystal contain Pb,
C, O element, atom number percentage is respectively 5-10%, 55-60% and 35-40%.
After Pb-MOF crystal is mixed SP, Pb-MOF crystal can be mutually oriented stacking first along the direction of its crystal bottom surface,
Increase height of column；Then, direction of the Pb-MOF crystal along the oblique each face of hexagonal column shape, the oriented growth in SP, so that Pb-
The outside of MOF forms halo, and SP-MOF crystal contains Pb, C, N, O element, and atom number percentage is respectively 1-5%, 75-
80%, 3-5% and 15-20%, N element therein come from SP, and it is effectively compound that this illustrates that Pb-MOF and SP has occurred, to obtain
Novel substance, i.e. SP-MOF crystal.
After SP-MOF crystal is mixed hole transmission layer, so that the hole transmission layer is more smooth, has preferably crystallization
Degree；This hole transmission layer can by the reflection of generation incident light return calcium titanium ore bed, promote photon energy absorption, and with pure SP hole transport
Layer is compared, the hole transmission layer band gap having the same and higher valence band and conduction band value of doping SP-MOF provided by the invention,
This is more advantageous to hole transmission layer and extracts hole from calcium titanium ore bed, while also promoting transfer of the hole to Ag electrode, hinders electricity
Son is to the compound of calcium titanium ore bed.To make device that there is higher short circuit current and incident photon-to-electron conversion efficiency.In addition, hole transmission layer
With higher hydrophobicity, inhibits moisture to spread to device inside, shield to calcium titanium ore bed, to improve device
Moisture-resistant stability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that Pb-MOF crystal is made in the embodiment of the present invention 1；(a), (b), (c) are it respectively in figure
Oblique view, top view and side view.
Fig. 2 is the growing principle schematic diagram that SP-MOF crystal is made in the embodiment of the present invention 2；(a) is small size Pb- in figure
MOF crystal；(b) it is orientated heap poststack for the direction along crystal bottom surface, forms large scale Pb-MOF crystal, there is bigger column
Body height；(c) it is large-sized Pb-MOF crystal in SP, is grown along crystallographic surface orientation, the halo type SP-MOF of formation
Crystal.
Fig. 3 is the structural schematic diagram that perovskite solar battery is made in the embodiment of the present invention 3.
Fig. 4 is that the TEM figure of sample in embodiment 1,2 is schemed with SEM；(a) scheme for the TEM of Pb-MOF crystal, (b) Pb-MOF is brilliant
The SEM of body schemes, and (c) schemes for the TEM of SP-MOF crystal, and illustration indicates model and orientation corresponding to the SP-MOF crystal.
Fig. 5 is that the hydrophobic angle of the hole transmission layer of pure SP (a) prepared by embodiment 3 and incorporation SP-MOF (b) compares.
Fig. 6 is the ultraviolet-visible spectrogram of pure SP prepared by embodiment 3 and SP-MOF sample.
Fig. 7 is the current density voltage curve figure of device one, device two, device three and device four in embodiment 3.
Fig. 8 is TEM figure and the SEM figure of embodiment 4,5 samples；It (a) is HRTEM (the high power transmitted electron of Pb-MOF crystal
Microscope) figure, (b) scheme for the SEM of Pb-MOF crystal, (c) scheme for the TEM of SP-MOF crystal, illustration indicates SP-MOF crystal institute
Corresponding model and orientation are (d) enlarged drawing of halo.
Fig. 9 is TEM figure and the SEM figure of embodiment 6,7 samples；(a) scheme for the HRTEM of Pb-MOF crystal, (b) be Pb-MOF
The SEM of crystal schemes.
Specific embodiment
Following embodiments are further explanations for the content of present invention using as the explaination to the technology of the present invention content, but
Substantive content of the invention is not limited in described in following embodiments, those skilled in the art can with and should know appoint
What simple change or replacement based on true spirit should belong to protection scope of the presently claimed invention.
Embodiment 1
A kind of preparation method of the Pb-MOF crystal of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3After BTC is dissolved in water, 30min is stirred at 65 DEG C, adds Pb (NO later3)2Solution mixing, so that 1,3,5-H3BTC
With Pb (NO3)2Molar ratio be 1:1, then mixed solution is stirred into 30min at room temperature, prepares Pb-MOF precursor solution；
2) it preparing Pb-MOF crystal: precursor solution ultrasound 30min is formed into white precipitate, dehydrated alcohol is added in precipitating, with
10000rpm is centrifuged 10min, then ultrasound 5min is washed, and is repeated 6 times, and gained precipitating is put into 60 DEG C of baking ovens dry 12h, obtains
To Pb-MOF crystal.
The present invention is first by 1,3,5-H3BTC is dispersed with stirring uniformly at a constant temperature, and Pb (NO is added3)2Afterwards, continuing to stir
Under, organic ligand 1,3,5-H3BTC is uniformly mixed with lead ion, thus the Pb-MOF crystal of the oblique hexagonal column shape of composition rule, warp
Cross concussion after, Pb-MOF crystal settling has obtained pure Pb-MOF crystal by ethanol washing, structure as shown in Figure 1,
(a), (b), (c) are respectively the oblique view, top view and side view of Pb-MOF crystal.
Embodiment 2
A kind of preparation method of the SP-MOF crystal with halo of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) prepare SP-MOF mixed solution: it is molten that Pb-MOF powder, SP powder, the acetonitrile of Li-TFSI is made in Example 1
Liquid, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content relative to chlorobenzene be respectively 48g/L, 85.78g/L,
0.0193L/L, 0.03536L/L, 0.008L/L, wherein content of the Li-TFSI relative to acetonitrile in the acetonitrile solution of Li-TFSI
For 520g/L, FK209 is 400g/L relative to the content of acetonitrile in the acetonitrile solution of FK209, shakes 60min, prepares SP-MOF
Mixed solution；
2) SP-MOF crystal is prepared: the Teflon filtration for being 0.45 μm by SP-MOF mixed solution obtained aperture
Head filtering, obtains the SP-MOF precursor solution containing small size SP-MOF crystal, then with the revolving speed of 3000rpm, be uniformly spin-coated on
On FTO, FTO is rinsed with ethyl alcohol after spin coating 40s, the ethanol solution containing SP-MOF crystal is obtained, volatilizees naturally to ethanol solution
Afterwards, SP-MOF crystal is formed.
As shown in connection with fig. 2, after Pb-MOF mixes SP, Pb-MOF crystal can be along the direction of its crystal bottom surface, phase first
Mutually orientation stacks, and increases height of column；Then Pb-MOF crystal is orientated life along the direction in the oblique each face of hexagonal column shape in SP
It is long, so that the outside of Pb-MOF forms halo.
As shown in figure 4, SP-MOF crystal made from Pb-MOF crystal made from embodiment 1 and embodiment 2 is rule
Oblique hexagonal column shape.Wherein, the TEM that (a) is Pb-MOF schemes, crystal diameter about 15nm, the side length of bottom surface regular hexagon about 9nm,
Height of column about 2nm, about 50 ° of the tilt angle between prism and bottom surface；(b) heap poststack is orientated for Pb-MOF in (a) to be formed
Large scale Pb-MOF crystal SEM figure, about 8 μm of the side length of bottom surface regular hexagon, about 5 μm of height of column, prism and bottom
About 50 ° of tilt angle between face.By EDS (X-ray energy spectrometer) quantitative elementary analysis, Pb, C, O element in Pb-MOF crystal
Atom number percentage be respectively 5.6%, 58.8% and 35.6%；It (c) is the TEM figure of the SP-MOF crystal formed, bottom surface
About 1.5 μm of the side length of regular hexagon, about 0.7 μm of height of column, about 50 ° of the tilt angle between prism and bottom surface, Ke Yiqing
See to Chu the halo at edge, width about 50nm, (c) in illustration indicate orientation corresponding to SP-MOF crystal.Pass through EDS element
Quantitative analysis, find the atom number percentage containing Pb, C, N, O element is respectively 1.4% in the SP-MOF with halo,
77.63%, 3.89% and 17.08%.
Embodiment 3
A kind of processing method of perovskite solar battery, comprising the following steps:
1) prepare substrate and to prepare electron transfer layer: first taking FTO glass, be cut into the sample of 1cm × 1cm, with detergent,
Deionization (DI) water, acetone, isopropanol and ethyl alcohol are successively washed and are dried, and then UV- ozone clean is handled, to remove Surface Oxygen
Compound layer and greasy dirt；
Then TiO is prepared2Diisopropoxy bis-acetylacetonate titanium is added in n-butanol solution, and concussion is uniformly mixed, shape
At TiO2Precursor solution is spin-coated on clean FTO glass, after the 5min that then anneals in 125 DEG C of air, then at 500 DEG C
Re-annealing 30min in Muffle furnace forms TiO2Layer；
2) calcium titanium ore bed is prepared: by MAI (methylpyridinium iodide amine) and PbI2(diiodinating lead) is dissolved in DMF, is vibrated, preparation
Calcium titanium ore bed precursor solution, then by perovskite precursor solution in substrate spin coating 30s；In 24s by EA (acetic acid second
Ester) drop coating is in substrate, the finally gloves close annealing by substrate in nitrogen, formation calcium titanium ore bed；
3) prepare hole transmission layer: the SP-MOF precursor solution in Example 2 drips the calcium titanium ore bed prepared in step 2)
On, spin coating is then carried out, spin coating machine speed 4000rpm is transferred to kept dry in drying box after rotating 20s；
4) it prepares electrode: one layer of Ag electrode, system being deposited by vacuum coating equipment on the hole transmission layer made from step 3)
Standby device one.
Perovskite solar battery is made using the above method, structure is as shown in figure 3, following supreme successively including FTO
Conductive glass layer 5, TiO2Electron transfer layer 4, calcium titanium ore bed 3, hole transmission layer 2 and metal silver electrode 1.
In addition, the Pb-MOF powder in SP-MOF crystal preparation process is removed, other reagents and technique are constant, will obtain
SP-MOF precursor solution prepare device two；
In addition, by the organic ligand 1,3,5-H in Pb-MOF crystal preparation process3BTC aqueous solution removal, other reagents with
Technique is constant, prepares device three；
Finally, by the Pb (NO in Pb-MOF crystal preparation process3)2Solution removal, other reagents and technique are constant, preparation
Device four.
Performance evaluation is carried out to solar battery:
Wherein, Fig. 5 is the hydrophobic angle comparison of the pure SP (a) of preparation and the hole transmission layer of incorporation SP-MOF (b): being distinguished
It takes pure SP, SP-MOF precursor solution of same volume to drip respectively to be tested to obtain on FTO glass, about 30 ° of pure SP hydrophobic angle,
About 70 ° of SP-MOF hydrophobic angle.Illustrate that SP-MOF is more hydrophobic.
Fig. 6 is that pure SP and SP-MOF are spin-coated on the ultraviolet-visible spectrogram on FTO glass.Sample is SP, SP-MOF forerunner
Solution is respectively 4000rpm, rotational time 20s with revolving speed, is spin-coated on FTO glass and obtains.It can in conjunction with the spectrogram of Fig. 6
Know, SP-MOF sample in 420~500nm wave band to the reflection enhancement of light, to will increase the absorption of light.Illustrate in SP-MOF
In, it can be by the way that the reflection of generation incident light be returned calcium titanium ore bed to promote photon energy absorption, and can be to the influx and translocation of light
Device provides higher short circuit current and incident photon-to-electron conversion efficiency.
Fig. 7 is the current density voltage curve figure of device one, device two, device three and device four.It can be seen that device three
There is no difference substantially compared to device two with device four.And use the photoelectricity for being doped with the device one of hole transmission layer of SP-MOF
Transfer efficiency is 13.17%, than device two high 25%, and under 30% relative humidity conditions, the photoelectric conversion efficiency of device one
It is still able to maintain 54% starting efficiency after nine days, and after 7 days, two efficiency of device has descended to the 28% of initial performance.
Embodiment 4
A kind of preparation method of the Pb-MOF crystal of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3After BTC is dissolved in water, 40min is stirred at 75 DEG C, adds Pb (NO later3)2Solution mixing, so that 1,3,5-H3BTC
With Pb (NO3)2Molar ratio be 1:0.9, then mixed solution is stirred into 30min at room temperature, prepares Pb-MOF precursor solution；
2) it prepares Pb-MOF crystal: Pb-MOF precursor solution ultrasound 30min being formed into white precipitate, is added in precipitating anhydrous
Ethyl alcohol is centrifuged 20min with 9000rpm, then ultrasound 7min is washed, and is repeated 10 times, and obtains precipitating being put into 65 DEG C of baking ovens and do
Dry 12h obtains Pb-MOF crystal.
Embodiment 5
A kind of preparation method of oblique SP-MOF crystal of the hexagonal column shape with halo of rule, specifically includes the following steps:
1) it prepares SP-MOF mixed solution: it is molten that Pb-MOF powder, SP powder, the acetonitrile of Li-TFSI is made in embodiment 4
Liquid, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content relative to chlorobenzene be respectively 45g/L, 85.6g/L,
0.0195L/L, 0.0355L/L, 0.0085L/L, wherein content of the Li-TFSI relative to acetonitrile in the acetonitrile solution of Li-TFSI
For 510g/L, FK209 is 410g/L relative to the content of acetonitrile in the acetonitrile solution of FK209, and concussion 50min preparation SP-MOF is mixed
Close solution；
2) SP-MOF crystal is prepared: the polytetrafluoroethyl-ne for being 0.45 μm by SP-MOF mixed solution aperture made from step 1)
The filtering of alkene filtering head obtains the SP-MOF precursor solution containing small size SP-MOF crystal, and with revolving speed 3500rpm, uniformly revolves
It is coated on FTO, rinses FTO with ethyl alcohol after rotation 35s, obtain the ethanol solution containing SP-MOF crystal, to ethanol solution nature
After volatilization, SP-MOF crystal is formed.
Pb-MOF crystal is made to embodiment 4 and embodiment 5 is made SP-MOF crystal and carries out dimension analysis:
As shown in figure 8, Pb-MOF crystal is made for embodiment 4 and embodiment 5 is made SP-MOF crystal is rule oblique six
Side column shape.Wherein, the TEM that (a) is Pb-MOF schemes, the side length of bottom surface regular hexagon about 10nm, height of column about 3nm, oblique side
About 60 ° of tilt angle between face and bottom surface, spacing of lattice 0.268nm.(b) heap poststack is orientated for Pb-MOF in (a) to be formed
Large-sized Pb-MOF crystal SEM figure, about 7 μm of the side length of bottom surface regular hexagon, about 8 μm of height of column.Pass through EDS element
Quantitative analysis, find Pb-MOF crystal in Pb, C, O element atom number percentage be respectively 6.8%, 57.5% with
35.7%.It (c) is the TEM figure of the SP-MOF crystal formed, about 1.3 μm of the side length of bottom surface regular hexagon, about 0.8 μ of height of column
M, about 60 ° of the tilt angle between prism and bottom surface, (c) in illustration indicate SP-MOF crystal corresponding to orientation.(d) it is
The halo enlarged drawing of SP-MOF crystal, halo width about 60nm.By EDS quantitative elementary analysis, the SP-MOF with halo is found
The atom number percentage of middle Pb, C, N, O element is respectively 2.8%, 76.2%, 3.9% and 17.1%.
Embodiment 6
A kind of preparation method of the Pb-MOF crystal of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3After BTC is dissolved in water, 35min is stirred at 50 DEG C, adds Pb (NO later3)2Solution mixing, so that 1,3,5-H3BTC
With Pb (NO3)2Molar ratio be 1:1.25, then mixed solution is stirred into 40min at room temperature, prepares Pb-MOF precursor solution；
2) it prepares Pb-MOF crystal: white precipitate will be formed after Pb-MOF precursor solution ultrasound 40min, be added into precipitating
Dehydrated alcohol is centrifuged 10min with 10000rpm, then ultrasound 10min is washed, and is repeated 6 times, and gained precipitating is put into 60 DEG C of baking ovens
Middle dry 14h, obtains Pb-MOF crystal.
Embodiment 7
A kind of preparation method of oblique SP-MOF crystal of the hexagonal column shape with halo of rule, specifically includes the following steps:
1) it prepares SP-MOF mixed solution: it is molten that Pb-MOF powder, SP powder, the acetonitrile of Li-TFSI is made in embodiment 6
Liquid, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content relative to chlorobenzene be respectively 50g/L, 85.65g/L,
0.0190L/L, 0.0350L/L, 0.0075L/L, wherein content of the Li-TFSI relative to acetonitrile in the acetonitrile solution of Li-TFSI
For 525g/L, FK209 is 395g/L relative to the content of acetonitrile in the acetonitrile solution of FK209, and concussion 45min preparation SP-MOF is mixed
Close solution；
2) SP-MOF crystal is prepared: the Teflon filtration head mistake for being 0.22 μm by SP-MOF mixed solution aperture
Filter is obtained the SP-MOF precursor solution containing small size SP-MOF crystal and is uniformly spin-coated on FTO with 5000rpm revolving speed, revolved
FTO is rinsed with ethyl alcohol after painting 20s, obtains the ethanol solution containing SP-MOF crystal, after ethanol solution volatilizees naturally, is formed
SP-MOF crystal.
Pb-MOF crystal is made to embodiment 6 and SP-MOF crystal is made in embodiment 7, carries out dimension analysis:
As shown in figure 9, it is the oblique of rule that SP-MOF crystal, which is made, with embodiment 7 in the Pb-MOF crystal that embodiment 6 obtains
Hexagonal column shape.The TEM that (a) is Pb-MOF in figure schemes, the side length of bottom surface regular hexagon about 8nm, height of column about 1nm, tiltedly
About 40 ° of tilt angle between side and bottom surface, spacing of lattice is respectively 0.228nm and 0.273nm.It (b) is Pb-MOF in (a)
The SEM for being orientated large-sized Pb-MOF crystal that heap poststack is formed schemes, and about 8 μm of the side length of bottom surface regular hexagon.Pass through EDS element
Quantitative analysis, find Pb-MOF crystal in Pb, C, O element atom number percentage be respectively 8.2%, 55.4% with
36.4%.About 1.4 μm of side length of the SP-MOF crystal bottom surface regular hexagon of formation, about 0.7 μm of height of column, prism and bottom surface
Between about 40 ° of tilt angle, the halo width about 50nm of formation.By EDS quantitative elementary analysis, the SP- with halo is found
The atom number percentage of Pb, C, N, O element is respectively 4.1%, 75.6%, 4.2% and 16.1% in MOF.
Embodiment 8
A kind of preparation method of the Pb-MOF crystal of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3After BTC is dissolved in water, 30min is stirred at 60 DEG C, adds Pb (NO later3)2Solution mixing, so that 1,3,5-H3BTC
With Pb (NO3)2Molar ratio be 1:1.1, then mixed solution is stirred into 35min at room temperature, prepares Pb-MOF precursor solution；
2) it prepares Pb-MOF crystal: Pb-MOF precursor solution ultrasound 35min then being formed into white precipitate, add into precipitating
Enter dehydrated alcohol, 15min is centrifuged with 9500rpm, ultrasonic 8min is washed, is repeated 8 times, and gained precipitating is put into 65 DEG C of baking ovens
Dry 13h, obtains Pb-MOF crystal.
Embodiment 9
A kind of preparation method of the SP-MOF crystal with halo of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) it prepares SP-MOF mixed solution: it is molten that Pb-MOF powder, SP powder, the acetonitrile of Li-TFSI is made in embodiment 8
Liquid, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content relative to chlorobenzene be respectively 40g/L, 85.7g/L,
0.0194L/L, 0.0353L/L, 0.0078L/L, wherein content of the Li-TFSI relative to acetonitrile in the acetonitrile solution of Li-TFSI
For 515g/L, FK209 is 405g/L relative to the content of acetonitrile in the acetonitrile solution of FK209, and concussion 45min preparation SP-MOF is mixed
Close solution；
2) SP-MOF crystal is prepared: the Teflon filtration head mistake for being 0.22 μm by SP-MOF mixed solution aperture
Filter obtains the SP-MOF precursor solution containing small size SP-MOF crystal, and with 4000rpm revolving speed, is uniformly spin-coated on FTO,
FTO is rinsed with ethyl alcohol after spin coating 30s, obtains the ethanol solution containing SP-MOF crystal, after ethanol solution volatilizees naturally, is formed
SP-MOF crystal.
Pb-MOF crystal is made to embodiment 8 and SP-MOF crystal is made in embodiment 9, carry out dimension analysis: embodiment 8 is made
It obtains Pb-MOF crystal and the oblique hexagonal column shape that SP-MOF crystal is rule is made in embodiment 9.The Pb-MOF crystal of formation,
The side length of bottom surface regular hexagon about 8nm, height of column about 2nm, about 50 ° of the tilt angle between prism and bottom surface.Pass through EDS
Quantitative elementary analysis, find Pb-MOF crystal in Pb, C, O element atom number percentage be respectively 7.5%, 56.7% with
35.8%.The SP-MOF crystal of formation have halo, about 1.2 μm of the side length of bottom surface regular hexagon, about 0.8 μm of height of column,
About 50 ° of tilt angle between prism and bottom surface, the halo width about 55nm of formation.Pass through EDS quantitative elementary analysis, discovery
The atom number percentage of Pb, C, N, O element is respectively 3.5%, 77.4%, 3.8% and 15.3% in SP-MOF with halo.
Embodiment 10
A kind of preparation method of the Pb-MOF crystal of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-
H3After BTC is dissolved in water, 35min is stirred at 70 DEG C, adds Pb (NO later3)2Solution mixing, so that 1,3,5-H3BTC
With Pb (NO3)2Molar ratio be 1:1.2, then mixed solution is stirred into 30min at room temperature, prepares Pb-MOF precursor solution；
2) it prepares Pb-MOF crystal: Pb-MOF precursor solution ultrasound 40min then being formed into white precipitate, add into precipitating
Enter dehydrated alcohol, 15min is centrifuged with 9000rpm, ultrasonic 5min is washed, is repeated 7 times, and gained precipitating is put into 70 DEG C of baking ovens
Dry 12h, obtains Pb-MOF crystal.
Embodiment 11
A kind of preparation method of the SP-MOF crystal with halo of the oblique hexagonal column shape of rule, specifically includes the following steps:
1) it prepares SP-MOF mixed solution: it is molten that Pb-MOF powder, SP powder, the acetonitrile of Li-TFSI is made in embodiment 10
Liquid, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content relative to chlorobenzene be respectively 42g/L, 85.8g/L,
0.0192L/L, 0.0355L/L, 0.0081L/L, wherein content of the Li-TFSI relative to acetonitrile in the acetonitrile solution of Li-TFSI
For 521g/L, FK209 is 402g/L relative to the content of acetonitrile in the acetonitrile solution of FK209, and concussion 55min preparation SP-MOF is mixed
Close solution；
2) SP-MOF crystal is prepared: the Teflon filtration head mistake for being 0.45 μm by SP-MOF mixed solution aperture
Filter obtains the SP-MOF precursor solution containing small size SP-MOF crystal, and with 4500rpm revolving speed, is uniformly spin-coated on FTO,
FTO is rinsed with ethyl alcohol after spin coating 35s, obtains the ethanol solution containing SP-MOF crystal, after ethanol solution volatilizees naturally, is formed
SP-MOF crystal.
Pb-MOF crystal is made to embodiment 10 and SP-MOF crystal is made in embodiment 11, carries out dimension analysis: embodiment
The oblique hexagonal column shape that SP-MOF crystal is rule is made in 10 obtained Pb-MOF crystal and embodiment 11.The Pb-MOF of formation is brilliant
Body, the side length of bottom surface regular hexagon about 10nm, height of column about 3nm, about 40 ° of the tilt angle between prism and bottom surface.
By EDS quantitative elementary analysis, find the atom number percentage of Pb, C, O element in Pb-MOF crystal be respectively 8.6%,
55.1% and 36.3%.The SP-MOF crystal of formation have halo, about 1.5 μm of the side length of bottom surface regular hexagon, height of column
About 1 μm, about 45 ° of the tilt angle between prism and bottom surface, the halo width about 60nm of formation.Quantitatively divided by EDS element
Analysis finds that the atom number percentage of Pb, C, N, O element in the SP-MOF with halo is respectively 2.1%, 79.3%, 3.2% and
15.4%.
Using method of the invention, regular tiltedly hexagonal column shape Pb-MOF crystal can be prepared and the oblique hexagonal column shape band of rule is dizzy
SP-MOF, is applied to the hole transmission layer of perovskite solar battery by the SP-MOF crystal of ring, and the moisture-proof of battery can be improved
Property and photoelectric conversion efficiency.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of Pb-MOF crystal, which is characterized in that the Pb-MOF crystal is rule tiltedly hexagonal column shape, the Pb-MOF crystal
In contain Pb, C, O element, atom number percentage is respectively 5-10%, 55-60% and 35-40%.
2. a kind of Pb-MOF crystal according to claim 1, which is characterized in that positive six side in the bottom surface of the Pb-MOF crystal
The side length of shape is 5-10nm, height of column 1-3nm, and the slanted angle between prism and bottom surface is 40-60 °.
3. a kind of preparation method of any one of claim 1-2 Pb-MOF crystal, which comprises the following steps:
1) Pb-MOF precursor solution is prepared: by 1,3,5-H3BTC and Pb (NO3)2It is dissolved in water respectively, wherein 1,3,5-H3BTC
Aqueous solution stirs 30-40min at 50-75 DEG C, then mixes two kinds of aqueous solutions, so that 1,3,5-H3BTC and Pb (NO3)2's
Molar ratio is 1:(0.9-1.25), mixed solution is stirred into 30-40min at room temperature, obtains Pb-MOF precursor solution；
2) it prepares Pb-MOF crystal: Pb-MOF precursor solution ultrasound 30-40min being formed and is precipitated, anhydrous second is added into precipitating
Alcohol is centrifuged 10-20min, then ultrasound 5-10min washing at revolving speed 9000-10000rpm, repeats 6-10 times, finally in 60-70
DEG C drying 12-14h obtain Pb-MOF crystal.
4. a kind of preparation method with halo SP-MOF crystal, which is characterized in that comprising steps of
1) prepare SP-MOF mixed solution: by any one of the claim 1-3 rule tiltedly hexagonal column shape Pb-MOF crystal powder,
Spiro-OMeTAD powder, the acetonitrile solution of Li-TFSI, tBP solution, FK209 acetonitrile solution mixed with chlorobenzene, content phase
It is respectively 40-50g/L, 85-86g/L, 0.015-0.02L/L, 0.03-0.04L/L, 0.007-0.009L/L, shake for chlorobenzene
SP-MOF mixed solution is prepared after swinging 45-60min；
2) prepare SP-MOF crystal: the filtering head for being 0.2-0.5 μm with aperture by SP-MOF mixed solution obtained filters out big
Sized crystals obtain small size SP-MOF precursor solution, then with the revolving speed of 3000-5000rpm, are uniformly spin-coated on FTO, spin coating
FTO is rinsed with ethyl alcohol after 20-40s, obtains the ethanol solution containing SP-MOF crystal, after ethanol solution volatilization, obtains SP-
MOF crystal.
5. a kind of preparation method with halo SP-MOF crystal according to claim 4, which is characterized in that the step 1)
In, Li-TFSI is 510-525g/L relative to the content of acetonitrile in the acetonitrile solution of Li-TFSI；In the acetonitrile solution of FK209
FK209 is 395-410g/L relative to the content of acetonitrile.
6. a kind of SP-MOF with halo that the oblique hexagonal column shape of rule is made using any one of the claim 4-5 preparation method
Crystal.
7. the SP-MOF crystal with halo of the oblique hexagonal column shape of rule according to claim 6, which is characterized in that the SP-
Contain Pb, C, N, O element in MOF crystal, atom number percentage is respectively 1-5%, 75-80%, 3-5% and 15-20%.
8. the SP-MOF crystal with halo of the oblique hexagonal column shape of rule according to claim 7, which is characterized in that the SP-
The side length of the bottom surface regular hexagon of MOF crystal is 1.2-1.5 μm, and height of column is 0.7-1 μm, the inclination between prism and bottom surface
Angle is 40-60 °, and has the halo of 50-60nm width in crystal periphery.
9. a kind of perovskite solar-electricity using any one of the claim 4-8 SP-MOF crystal doping hole transmission layer
Pond.
10. the processing method of perovskite solar battery described in a kind of claim 9, which comprises the following steps:
1) it prepares electron transfer layer: preparing substrate, electron transfer layer is prepared in substrate；
2) it prepares perovskite active layer: preparing perovskite active layer on the electron transport layer；
3) it prepares hole transmission layer: by SP-MOF precursor solution with the revolving speed of 3500-4500rpm, being uniformly spin-coated on calcium titanium ore bed
On, hole transmission layer is prepared after spin coating 15-25s；
4) it prepares metal electrode: preparing metal silver electrode on the hole transport layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932285A (en) * | 2016-06-02 | 2016-09-07 | 华南师范大学 | Preparation method for lithium battery anode material by taking metal organic frame as template |
| US20180366539A1 (en) * | 2016-03-09 | 2018-12-20 | The Regents Of The University Of California | Graded bandgap perovskite solar cell |
| CN109233816A (en) * | 2018-10-25 | 2019-01-18 | 陕西科技大学 | A kind of lead coordination polymer ion fluorescence probe material and its preparation method and application |
| CN109400899A (en) * | 2018-10-25 | 2019-03-01 | 陕西科技大学 | A kind of lead coordination polymer and its preparation method and application |
-
2019
- 2019-05-15 CN CN201910405439.5A patent/CN110128670B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180366539A1 (en) * | 2016-03-09 | 2018-12-20 | The Regents Of The University Of California | Graded bandgap perovskite solar cell |
| CN105932285A (en) * | 2016-06-02 | 2016-09-07 | 华南师范大学 | Preparation method for lithium battery anode material by taking metal organic frame as template |
| CN109233816A (en) * | 2018-10-25 | 2019-01-18 | 陕西科技大学 | A kind of lead coordination polymer ion fluorescence probe material and its preparation method and application |
| CN109400899A (en) * | 2018-10-25 | 2019-03-01 | 陕西科技大学 | A kind of lead coordination polymer and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HOMA SADEGHZADEH ET AL.: "Sonochemical synthesis and structural characterization of a nano-structure Pb(II) benzentricarboxylate coordination polymer: new precursor to pure phase nanoparticles of Pb(II) oxide", 《JOURNAL OF COORDINATION CHEMISTRY》 * |
| XU-SHENG GAO ET AL.: "Stereochemically Active and Inactive Lone Pairs in Two Room-Temperature Phosphorescence Coordination Polymers of Pb2+ with Different Tricarboxylic Acids", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944161A (en) * | 2020-08-05 | 2020-11-17 | 北京理工大学 | Eu-MOFs interface modification layer in perovskite solar cell |
| CN111944161B (en) * | 2020-08-05 | 2021-11-09 | 北京理工大学 | Eu-MOFs interface modification layer in perovskite solar cell |
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