CN105609644B - A kind of environmentally friendly perovskite photovoltaic material and preparation method thereof - Google Patents
A kind of environmentally friendly perovskite photovoltaic material and preparation method thereof Download PDFInfo
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- CN105609644B CN105609644B CN201510960960.7A CN201510960960A CN105609644B CN 105609644 B CN105609644 B CN 105609644B CN 201510960960 A CN201510960960 A CN 201510960960A CN 105609644 B CN105609644 B CN 105609644B
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001768 cations Chemical class 0.000 claims abstract description 16
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 230000026030 halogenation Effects 0.000 claims description 12
- 238000005658 halogenation reaction Methods 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical group Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- -1 sulfate radical Chemical class 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 58
- 239000013078 crystal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 229940071870 hydroiodic acid Drugs 0.000 description 6
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- TYRSHWJNDCWRJW-UHFFFAOYSA-N [Pb].P(O)(O)(O)=O Chemical compound [Pb].P(O)(O)(O)=O TYRSHWJNDCWRJW-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XDLSXXMJBCNXPS-UHFFFAOYSA-N [Pb].CN Chemical class [Pb].CN XDLSXXMJBCNXPS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of environmentally friendly perovskite photovoltaic material and preparation method thereof.The present invention is by by the photovoltaic material CH of traditional perovskite structure3NH3PbX3（Wherein X represents one or more halogens）In cation Pb replaced using environment amenable magnesium, barium, zinc, anion prepares the photovoltaic material of environment amenable perovskite structure using the technical scheme of the replacement such as sulfate radical, nitrate anion, phosphate radical.
Description
Technical field
The present invention relates to the field in photovoltaic material field, the more particularly to photovoltaic material of perovskite structure.
Background technology
Any and calcium titanate CaTiO that the material of perovskite structure refers to3Material with same crystal structure, experiment hair
It is existing, after metal halide material formation perovskite structure, in photovoltaic solar cell as acquisition layer be it is very effective,
Can successfully it convert solar energy into electrical energy, based on the discovery, 2009, the material of perovskite structure was formally applied to film
In solar cell, within the next few years, the material of perovskite structure has great development in photovoltaic art, and photoelectricity turns
Change rate constantly to be lifted, particularly metal halide perovskite-like material, its raw material is generally cheap lead, halogen and amine salt, come
Extensively, the more conventional silica-base material of manufacturing cost is lower, in terms of optoelectronic transformation efficiency, and it is developed into from initial 3.8% in source
15.9% has only used the time less than 5 years, and progressively close to the efficiency of silicon-based photovoltaic material, some scholars are further foretold
Its electricity conversion will exceed the photovoltaic material of monocrystalline silicon class quickly, reach 30%, therefore use the photovoltaic material of perovskite structure
The solar cell of material is possible to replace completely the solar cell of traditional use silicon class photovoltaic material.
CH3NH3PbX3 （X represents halogen, mainly including Cl, Br, I）It is a kind of main generation in perovskite photovoltaic material
Table, the dye transfer in the quick magnificent solar cell of dyestuff, its absorption coefficient is high, and manufacturing cost is low, can also be by right
The regulation of composition, band gap when changing color and being used as photovoltaic material.But it is used as CH3NH3PbX3In main part
Pb elements but there is larger toxicity, and easily leakage, cause soil and environmental pollution, harmful to human, therefore find lead
Substitute element is very important.Halide anion stability therein also not good enough simultaneously, under moist or hot environment
Easily chemically react, the solar cell failure for causing its assembling to obtain is had in practical application by whole battery
It is packaged, causing the manufacturing cost of battery increases, therefore it is also necessary to find the substitute element of more preferable halogen simultaneously.
Sn substitutions or hydridization Pb perovskite photovoltaic material tentatively it have been successfully prepared at present, it has wider array of light absorbs
Spectrum and higher circuit photocurrent density, but directly using Sn replace the perovskite solar cell of Pb elements be difficult to show it is good
Good light conversion performance, and need not must not keep in crystal still containing a certain amount of Pb to maintain Sn valence state, extend light
The life-span of raw particle, meanwhile, relative to CH3NH3PbX3Perovskite-like photovoltaic material, the preparation process of Sn based perovskites is complicated, work
Skill condition is harsh, and yield is relatively low, also counteracts that it develops.
CH3NH3PbX3Crystal is typical ABX3Configuration, wherein organic molecule methylamine be located at by Pb and X-shaped into octahedron
Bosom, with the difference of temperature, different phases, at normal temperatures, CH are presented in crystal3NH3PbX3Crystal is Tetragonal, is prohibited
Bandwidth is about 1.55eV；The upper valence band of its energy band is made up of the σ antibondings generated through orbital hybridization of halogen atom and Pb atoms,
Lower valence band is made up of the organic molecule state being occupied, conduction band bottom is made up of the outer-shell electron of Pb atoms, and conduction band top is not by occupying
Organic molecule state is constituted, organic cation CH3NH3 ﹢Main function be charge compensation, and Pb ions and halide ion are then main
Influence the width of conduction band, the band edge of valence band and forbidden band.Therefore, it can be adjusted by the replacement to metal cation Pb and halogen X
The photovoltaic performance of perovskite crystal, can adjust perovskite crystal steady in photoelectric conversion process to the replacement of organic cation
It is qualitative.
The content of the invention
It is an object of the invention to provide a kind of photovoltaic material of the perovskite structure of environmentally friendly stabilization, it can
Instead of the photovoltaic material of the perovskite structure of traditional halogenation methylamine lead class.
The technical scheme is that：
A kind of preparation method of environmentally friendly perovskite photovoltaic material, comprises the following steps：
1）It is prepared by the first base material
Halogenation methylamine is dissolved in the organic solution that halogenation methylamine is obtained in the first organic solvent, lead halide is dissolved in into first has
The organic solution of lead halide is obtained in machine solvent, the organic solution of halogenation methylamine is slowly dropped into thereafter the organic solution of lead halide
In, in heating 20 ~ 30min at 70 ~ 90 DEG C, obtain the first base material；
2）Anion is replaced
Lead salt is dissolved in the organic solution that lead salt is obtained in the second organic solvent, the first base material is added into having for lead salt
In machine solution, stirring obtains mixed liquor, by the mixed liquor in heating 20 ~ 30min at 40 ~ 60 DEG C, to described in heating process
Acetic acid to heating is constantly added dropwise in mixed liquor to terminate, solution is stood at room temperature filtered after 30 ~ 60min thereafter, what is obtained consolidates
Body is the second base material；
The lead salt is the one or more in plumbi nitras, lead sulfate, lead phosphate；
3）Cation is replaced
The 3rd organic solvent is added into the second base material, then chloride is dissolved in the salting liquid after water and is added thereto, is stirred
Mixture is obtained, by the mixture in being heated at reflux at 100 ~ 120 DEG C in 60 ~ 90min, heating process into the mixture
Liquor kalii iodide to heating is constantly added dropwise to terminate, the mixture is down to room temperature thereafter and centrifuged in temperature-fall period,
Add HI in the solid obtained after to centrifugation and centrifuge again after being sufficiently stirred for, the solid of gained is scrubbed, dry after be institute
State environmentally friendly perovskite photovoltaic material；
The chloride is the one or more in barium chloride, zinc chloride, stannic chloride, magnesium chloride.
Wherein step 1）Primarily to obtaining the structure of basic methylamine lead halide perovskite-like, the present invention is main to be used
The method that cation or anion are replaced, rather than by raw material directly prepare environmentally friendly perovskite photovoltaic material be because
The crystal directly prepared largely has occurred that transformation on crystal formation, no longer with identical structure, therefore loses
Photovoltaic property；Step 1）Described in the heating that refers to of the first base material terminate after entire mixture, and be more than wherein single
One solid or liquid；
Step 2）Preferably 0.5 ~ 1 drop/sec of the rate of addition of middle acetic acid, its main purpose is the displacement effect for strengthening anion
Really, in this step the replacement of anion be it is incomplete, i.e., and not all step 1）In halogen in obtained methylamine lead halide
Element is all substituted by nitric acid, sulfuric acid or phosphate radical, and on the one hand the replacement of this step is simple to be replaced or mix to halogen
It is miscellaneous, on the other hand primarily to step 3）The replacement of cationic can more completely, more effectively, if sun can be improved further
After ion replacement method, directly cation can be also replaced without this step, certainly, if being not intended to replace cation,
And only halogen is replaced, the concentration and ratio of each reagent can also be adjusted, step 2 is only completed）, without further being walked
Rapid 3）Operation；
Step 3）The concentration of middle chloride preferably 0.5 ~ 1.5mol/L, HI concentration are preferably 0.2 ~ 0.5mol/L, and it adds
The amount entered is untill when solid masses is no longer significantly reduced；In this step liquor kalii iodide be added to strengthen cation
Replace effect, preferably 0.5 ~ 1 drop/sec of its rate of addition；The process that the mixture is down into room temperature can be natural cooling,
Pressure cooling can be carried out by the cooldown rate less than 10 DEG C/min, in the method, if not by step 2）And directly enter
Row step 3）Can make it that the replacement of cation is less efficient, but if the step can be improved, and be not intended to the moon from
, can not be by step 2 if son is replaced）And directly carry out the replacement of cation.
One preferred embodiment of above-mentioned preparation method is：The halogenation methylamine is selected from CH3NH3I、CH3NH3Br、
CH3NH3One or more in Cl；The lead halide is selected from PbCl2、PbBr2、PbI2In one or more.
Another preferred embodiment of the preparation method is：First organic solvent is gamma-butyrolacton or N, N- bis-
NMF（DMF）.
Another preferred embodiment of the preparation method is：Second organic solvent is the mixture of DMF and ethanol,
The volume ratio of wherein DMF and ethanol is 1:3~1:5.
Second solvent is also an option that the mixture of other organic solvents, and it needs the condition met to be on the one hand to ensure lead
The dissolving of salt, on the other hand needs to whole reaction without other interference effects, and the volume ratio of DMF and ethanol can be according to lead salt
Actual dissolving situation carry out selective adjustment.
Another preferred embodiment of the preparation method is：3rd organic solvent is DMF.
Another preferred embodiment of the preparation method is：The concentration of halogenation methylamine in the halogenation methylamine organic solution
For 0.5~1.0mol/L.
Another preferred embodiment of the preparation method is：The concentration of lead halide is in the lead halide organic solution
0.5~1.5mol/L.
If halogenation lead solution is in step 1 in the present invention）Reaction after through determine have obvious excess, then behind lead
Higher concentration may be selected in salting liquid, acetic acid, chloride solution, liquor kalii iodide.
Another preferred embodiment of the preparation method is：The concentration of the acetic acid is 1.5 ~ 2.0mol/L.
Another preferred embodiment of the preparation method is：：In the liquor kalii iodide concentration of KI be 1.5 ~
2.0mol/L。
Present invention further proposes a kind of environmentally friendly perovskite photovoltaic material, its by aforementioned preparation process or its
Any preferred embodiment is prepared, in use, being used after being processed as the light-absorption layer of solar cell, is passed through
Solar cell further is obtained with hole mobile material, separation layer, FTO glass, the assembling to electrode, also can be in the photovoltaic material
Other photovoltaic materials are coated on material, and further solar cell is made in assembling.
Beneficial effects of the present invention are predominantly by traditional CH3NH3PbX3Toxic element Pb in photovoltaic material used magnesium,
Barium, zinc, tin etc. are replaced, while used anionic part sulfate radical, nitrate anion, phosphate radical etc. to replace, obtained new material
Environmentally friendly, stability is high.
Embodiment
Embodiment 1
1）It is prepared by the first base material
By CH3NH3I is dissolved in the CH for obtaining that concentration is 0.5mol/L in gamma-butyrolacton3NH3I organic solutions, by PbCl2It is dissolved in
The PbCl that concentration is 0.5mol/L is obtained in gamma-butyrolacton2Organic solution, by CH3NH3I organic solution is slowly dropped into PbCl2
Organic solution in stirring obtain mixed solution, in heating 30min at 70 DEG C, obtain the first base material；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 10% lead sulfate of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:3, sulfuric acid lead solution is obtained, the first base material is added in sulfuric acid lead solution, stirring obtains mixed liquor, will be mixed
Liquid is closed in heating continuous dropwise addition acetic acid in 30min, heating process at 40 DEG C, acetate concentration is 1.5mol/L, and rate of addition is 1
Drop/sec, it is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 60min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）The isometric DMF of middle gamma-butyrolacton, then barium chloride is dissolved in after water obtained
Concentration be added thereto for 0.5mol/L solution, stirring obtains mixture, and the mixture is heated at reflux at 100 DEG C
Concentration is constantly added dropwise into the mixture in 90min, heating process for 1.5mol/L liquor kalii iodide to heating to terminate, drips
Acceleration is 1 drop/sec, the mixture is down into room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after obtain
Concentration is added in solid for 0.2mol/L hydroiodic acid and is centrifuged again after being sufficiently stirred for, the solid of gained is scrubbed, dry after
As described environmentally friendly perovskite photovoltaic material.
Embodiment 2
1）It is prepared by the first base material
By CH3NH3Cl is dissolved in the CH for obtaining that concentration is 0.5mol/L in gamma-butyrolacton3NH3I organic solutions, by PbCl2It is molten
The PbCl that concentration is 0.75mol/L is obtained in gamma-butyrolacton2Organic solution, by CH3NH3Cl organic solution is slowly dropped into
PbCl2Organic solution in stirring obtain mixed solution, in heating 25min at 70 DEG C, obtain the first base material；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 15% lead sulfate of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:3, sulfuric acid lead solution is obtained, the first base material is added in sulfuric acid lead solution, stirring obtains mixed liquor, will be mixed
It is 1.5mol/L that liquid, which is closed, in heating continuous dropwise addition acetic acid in 25min, heating process, acetate concentration at 50 DEG C, and rate of addition is every 2
Second 1 drips, and is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 60min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）The isometric DMF of middle gamma-butyrolacton, then barium chloride is dissolved in after water obtained
Concentration be added thereto for 0.75mol/L solution, stirring obtains mixture, and the mixture is heated at reflux at 100 DEG C
Concentration is constantly added dropwise into the mixture in 80min, heating process for 1.5mol/L liquor kalii iodide to heating to terminate, drips
Acceleration is 1 drop/sec, the mixture is down into room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after obtain
Concentration is added in solid for 0.3mol/L hydroiodic acid and is centrifuged again after being sufficiently stirred for, the solid of gained is scrubbed, dry after
As described environmentally friendly perovskite photovoltaic material.
Embodiment 3
1）It is prepared by the first base material
By CH3NH3I is dissolved in the CH for obtaining that concentration is 0.7mol/L in gamma-butyrolacton3NH3I organic solutions, by PbI2It is dissolved in
The PbCl that concentration is 1.0mol/L is obtained in gamma-butyrolacton2Organic solution, by CH3NH3I organic solution is slowly dropped into PbI2's
Stirring obtains mixed solution in organic solution, in heating 20min at 80 DEG C, obtains the first base material；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 13% lead phosphate of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:4, phosphoric acid lead solution is obtained, the first base material is added in phosphoric acid lead solution, stirring obtains mixed liquor, will be mixed
Liquid is closed in heating continuous dropwise addition acetic acid in 20min, heating process at 50 DEG C, acetate concentration is 1.5mol/L, and rate of addition is every
Second 1 drips, and is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 40min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）The isometric DMF of middle gamma-butyrolacton, then zinc chloride is dissolved in after water obtained
Concentration be added thereto for 1.0mol/L solution, stirring obtains mixture, and the mixture is heated at reflux at 110 DEG C
Concentration is constantly added dropwise into the mixture in 70min, heating process for 1.5mol/L liquor kalii iodide to heating to terminate, drips
Acceleration is 1 drop/sec, the mixture is down into room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after obtain
Concentration is added in solid for 0.5mol/L hydroiodic acid and is centrifuged again after being sufficiently stirred for, the solid of gained is scrubbed, dry after
As described environmentally friendly perovskite photovoltaic material.
Embodiment 4
1）It is prepared by the first base material
By CH3NH3I is dissolved in the CH for obtaining that concentration is 0.7mol/L in DMF3NH3I organic solutions, by PbBr2It is dissolved in DMF
Obtain the PbBr that concentration is 1.5mol/L2Organic solution, by CH3NH3I organic solution is slowly dropped into PbBr2Organic solution in
Stirring obtains mixed solution, in heating 25min at 80 DEG C, obtains the first base material；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 15% lead phosphate of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:4, phosphoric acid lead solution is obtained, the first base material is added in phosphoric acid lead solution, stirring obtains mixed liquor, will be mixed
Liquid is closed in heating continuous dropwise addition acetic acid in 20min, heating process at 60 DEG C, acetate concentration is 1.7mol/L, and rate of addition is every
Second 1 drips, and is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 50min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）DMF isometric middle DMF, then zinc chloride is dissolved in the concentration obtained after water
It is added thereto for 1.5mol/L solution, stirring obtains mixture, by the mixture in being heated at reflux 60min at 120 DEG C, plus
Concentration is constantly added dropwise into the mixture in thermal process for 1.5mol/L liquor kalii iodide to heating to terminate, rate of addition is
1 drop/sec, the mixture is down to room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after in obtained solid plus
Enter hydroiodic acid that concentration is 0.2mol/L and centrifuge again after being sufficiently stirred for, the solid of gained is scrubbed, dry after be described
Environmentally friendly perovskite photovoltaic material.
Embodiment 5
1）It is prepared by the first base material
By CH3NH3Cl is dissolved in the CH for obtaining that concentration is 1.0mol/L in DMF3NH3Cl organic solutions, by PbBr2It is dissolved in DMF
In obtain concentration be 1.5mol/L PbBr2Organic solution, by CH3NH3Cl organic solution is slowly dropped into PbBr2It is organic molten
Stirring obtains mixed solution in liquid, in heating 30min at 90 DEG C, obtains the first base material；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 10% plumbi nitras of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:5, lead nitrate solution is obtained, the first base material is added in lead nitrate solution, stirring obtains mixed liquor, will be mixed
Liquid is closed in heating continuous dropwise addition acetic acid in 20min, heating process at 40 DEG C, acetate concentration is 1.5mol/L, and rate of addition is every
Second 1 drips, and is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 60min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）DMF isometric middle DMF, then magnesium chloride is dissolved in the concentration obtained after water
It is added thereto for 1.0mol/L solution, stirring obtains mixture, by the mixture in being heated at reflux 60min at 110 DEG C, plus
Concentration is constantly added dropwise into the mixture in thermal process for 1.5mol/L liquor kalii iodide to heating to terminate, rate of addition is
1 drop/sec, the mixture is down to room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after in obtained solid plus
Enter hydroiodic acid that concentration is 0.3mol/L and centrifuge again after being sufficiently stirred for, the solid of gained is scrubbed, dry after be described
Environmentally friendly perovskite photovoltaic material.
Embodiment 6
1）It is prepared by the first base material
By CH3NH3I is dissolved in the CH for obtaining that concentration is 0.8mol/L in DMF3NH3I organic solutions, by PbI2It is dissolved in DMF and obtains
To the PbI that concentration is 1.0mol/L2Organic solution, by CH3NH3I organic solution is slowly dropped into PbI2Organic solution in stir
Mixed solution is obtained, in heating 30min at 90 DEG C, the first base material is obtained；
2）Anion is replaced
Quality is dissolved in the mixture of DMF and ethanol for 13% lead sulfate of the first base material quality, wherein DMF and second
The volume ratio of alcohol is 1:5, sulfuric acid lead solution is obtained, the first base material is added in sulfuric acid lead solution, stirring obtains mixed liquor, will be mixed
It is 1.5mol/L that liquid, which is closed, in heating continuous dropwise addition acetic acid in 20min, heating process, acetate concentration at 50 DEG C, and rate of addition is every 2
Second 1 drips, and is added dropwise to after heating terminates at room temperature to stand solution and is filtered after 40min, obtained solid is the second base material；
3）Cation is replaced
Added and step 1 into the second base material）DMF isometric middle DMF, then stannic chloride is dissolved in the concentration obtained after water
It is added thereto for 1.5mol/L solution, stirring obtains mixture, by the mixture in being heated at reflux 80min at 100 DEG C, plus
Concentration is constantly added dropwise into the mixture in thermal process for 2.0mol/L liquor kalii iodide to heating to terminate, rate of addition is
Drip within every 2 seconds 1, the mixture be down to room temperature thereafter and centrifuged in temperature-fall period, to centrifugation after in obtained solid
Concentration is added for 0.5mol/L hydroiodic acid and is centrifuged again after being sufficiently stirred for, the solid of gained is scrubbed, dry after be institute
State environmentally friendly perovskite photovoltaic material.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferably embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and embodiment, and these modifications and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (10)
1. a kind of preparation method of environmentally friendly perovskite photovoltaic material, it is characterised in that：Comprise the following steps：
It is prepared by the first base material
Halogenation methylamine is dissolved in the organic solution that halogenation methylamine is obtained in the first organic solvent, it is organic molten that lead halide is dissolved in into first
The organic solution of lead halide is obtained in agent, the organic solution of halogenation methylamine is slowly dropped into the organic solution of lead halide thereafter,
In heating 20~30min at 70~90 DEG C, the first base material is obtained；
Anion is replaced
Lead salt is dissolved in the organic solution that lead salt is obtained in the second organic solvent, the first base material is added into the organic molten of lead salt
In liquid, stirring obtains mixed liquor, and the mixed liquor is mixed in 20~30min of heating, heating process at 40~60 DEG C to described
Close constantly dropwise addition acetic acid to heating in liquid to terminate, solution is stood at room temperature filtered after 30~60min thereafter, obtained solid
For the second base material；
The lead salt is the one or more in plumbi nitras, lead sulfate, lead phosphate；
Cation is replaced
The 3rd organic solvent is added into the second base material, then chloride is dissolved in the salting liquid after water and is added thereto, stirring is obtained
Mixture, by the mixture in being heated at reflux at 100~120 DEG C in 60~90min, heating process into the mixture not
Disconnected dropwise addition liquor kalii iodide to heating terminates, and the mixture is down into room temperature thereafter and centrifuged in temperature-fall period, to
Add HI in the solid obtained after centrifugation and centrifuge again after being sufficiently stirred for, the solid of gained is scrubbed, dry after be described
Environmentally friendly perovskite photovoltaic material；
The chloride is the one or more in barium chloride, zinc chloride, stannic chloride, magnesium chloride.
2. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：The halogen
It is selected from CH to change methylamine3NH3I、CH3NH3Br、CH3NH3One or more in Cl；The lead halide is selected from PbCl2、PbBr2、
PbI2In one or more.
3. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：Described
One organic solvent is gamma-butyrolacton or N,N-dimethylformamide（DMF）.
4. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：Described
Two organic solvents are the mixture of DMF and ethanol, and the volume ratio of wherein DMF and ethanol is 1:3~1:5.
5. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：Described
Three organic solvents are DMF.
6. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：The halogen
The concentration for changing halogenation methylamine in methylamine organic solution is 0.5~1.0mol/L.
7. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：The halogen
The concentration for changing lead halide in lead organic solution is 0.5~1.5mol/L.
8. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：The vinegar
The concentration of acid is 1.5~2.0mol/L.
9. the preparation method of environmentally friendly perovskite photovoltaic material according to claim 1, it is characterised in that：The iodine
The concentration for changing KI in potassium solution is 1.5~2.0mol/L.
10. a kind of environmentally friendly perovskite photovoltaic material, it is characterised in that：As the system any one of claim 1~9
Preparation Method is prepared.
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| CN107170887B (en) * | 2017-03-22 | 2019-06-28 | 宁波大学 | One kind having BaCl2The perovskite solar battery and its manufacturing method of decorative layer |
| CN107141221A (en) * | 2017-05-11 | 2017-09-08 | 北京大学深圳研究生院 | A kind of perovskite structural material and preparation method thereof, application |
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| CN110085745B (en) * | 2019-04-11 | 2023-08-01 | 宁波大学 | High-substitution-rate high-efficiency perovskite solar cell and preparation method thereof |
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| CN104393109A (en) * | 2014-10-28 | 2015-03-04 | 合肥工业大学 | Chemical vapor deposition preparation method for perovskite solar cell |
| CN104934539A (en) * | 2015-07-01 | 2015-09-23 | 中国华能集团清洁能源技术研究院有限公司 | Solar cell adopting metal transparent electrode and preparation of solar cell |
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| CN101814582A (en) * | 2010-04-01 | 2010-08-25 | 复旦大学 | Inorganic-organic semiconductor combined element having transverse photovoltaic effect and preparation method thereof |
| CN104393109A (en) * | 2014-10-28 | 2015-03-04 | 合肥工业大学 | Chemical vapor deposition preparation method for perovskite solar cell |
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