CN117897029A - Organic-inorganic hybrid hole transport material and application thereof - Google Patents
Organic-inorganic hybrid hole transport material and application thereof Download PDFInfo
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- 230000005525 hole transport Effects 0.000 title claims abstract description 115
- 239000000463 material Substances 0.000 title claims abstract description 59
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical class [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims abstract description 60
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 229910013232 LiMoO2 Inorganic materials 0.000 claims abstract description 18
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 93
- 239000000843 powder Substances 0.000 claims description 65
- 238000004528 spin coating Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 23
- 230000032258 transport Effects 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 238000007740 vapor deposition Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 230000007774 longterm Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- -1 halide anion Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000037230 mobility Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 229910010177 Li2MoO3 Inorganic materials 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
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Abstract
The invention discloses an organic-inorganic hybrid hole transport material and application thereof, and belongs to the technical field of perovskite solar cells, wherein a series of lithium molybdate is added into P3HT when a hole transport layer is prepared: li 2MoO3、LiMoO2、LiMoSxO1‑x (x is more than or equal to 0 and less than or equal to 1) or Li xMo2O4 (x is more than or equal to 1 and less than or equal to 2) are prepared to obtain various lithium molybdate hybrid P3HT, the lithium molybdate hybrid P3HT is applied to perovskite batteries in solar batteries, a positive structure is adopted in the perovskite batteries, a hole transport layer is made of the novel lithium molybdate hybrid P3HT, the preparation method of the perovskite materials is controllable in operation and high in reproducibility, and meanwhile, the energy conversion efficiency and the device stability of the perovskite solar batteries can be obviously improved by the application of the perovskite materials in the solar batteries.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to an organic-inorganic hybrid hole transport material and application thereof.
Background
A great number of natural environmental problems make people around the world more and more aware of the difficulties we are facing at present, such as the damage to the atmosphere caused by the excessive reliance on traditional fossil fuels, and therefore a viable method is needed to create high density clean energy. After the first perovskite solar cell was prepared from 2009, a solar cell based on perovskite structure materials has attracted worldwide attention. The absorption coefficient of the perovskite material is as high as 10 5. As an emerging solar cell technology, perovskite solar cells have many advantages, such as low cost, simple manufacturing process, and the possibility of manufacturing flexible, transparent and stacked cells, etc., and their unique defect characteristics make perovskite crystalline materials exhibit properties of both n-type and p-type semiconductors, and their applications are more diverse. With the continuous progress of scientific research and the continuous innovation of technology, perovskite solar cells are expected to contribute to solving energy crisis and environmental problems.
Perovskite is defined as any compound that crystallizes in the ABX 3 structure, consisting of BX 6 octahedra sharing angles, component a being able to neutralize the total charge. In the case of an organometallic trihalide perovskite, the chemical formula of the perovskite compound can be described as ABX 3, where a is a monovalent cation (methylammonium (CH 3NH3 +(MA+)), formamidine (CH (NH 2)2+(FA+)),Cs+, etc.), B is a divalent metal cation (Pb 2+Sn2+, etc.), and X is a halide anion (Cl -Br-I-). Unfortunately, the introduction of the organic component causes thermal instability of the perovskite material.
Organic-inorganic hybrid Perovskite Solar Cells (PSCs) achieved authentication efficiencies as high as 26.1%, but CsPbX 3 exhibited instability under humid, light and high temperature conditions. However, for perovskite solar cells of n-p-i structure, the top hole transport layer HTL will directly affect the efficiency and stability of the perovskite solar cell, wherein the high cost spira-ome tad is widely used as a hole transport material, but a water absorbing lithium salt needs to be doped to improve its hole extraction capability, which affects the stability of the device. There have been many studies on the selection of poly-3-hexylthiophene (P3 HT) as a hole transport material at low cost, undoped, high thermal stability, and a wide temperature range. Perovskite solar cell performance rapidly decays under conditions of water oxygen, photo-thermal and the like, and poor long-term stability hinders the commercialization progress of the devices. Therefore, research on a feasibility strategy to greatly improve the stability problem of the perovskite solar cell has important significance.
Disclosure of Invention
The present invention aims to further improve the long-term stability problem of CsPbI 3 by doping a novel lithium molybdate salt in the hole transport layer P3 HT. The invention provides an organic-inorganic hybrid hole transport material and application thereof, wherein the novel lithium molybdate Li 2MoO3LiMoO2LiMoSxO1-x (wherein x is more than or equal to 0 and less than or equal to 1) and Li xMo2O4 (wherein x is more than or equal to 1 and less than or equal to 2) are doped in the hole transport material P3HT and are applied to a hole transport layer of a perovskite solar cell, so that the energy conversion efficiency and the device stability of the perovskite solar cell can be effectively improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
One of the technical schemes of the invention is as follows:
providing an organic-inorganic hybrid hole transport material doped with lithium molybdate in P3 HT;
The lithium molybdate salt includes: li 2MoO3LiMoO2LiMoSxO1-x (x is equal to or more than 0 and equal to or less than 1) or Li xMo2O4 (x is equal to or more than 1 and equal to or less than 2).
Further, the organic-inorganic hybrid hole transport material is P3HT+lithium molybdate, and the volume ratio of the P3HT to the lithium molybdate is 50:1.
Further, the organic-inorganic hybrid hole transport material is P3HT+Li 2MoO3P3HT+LiMoO2P3HT+LiMoSxO1-x (x is more than or equal to 0 and less than or equal to 1) or P3HT+Li xMo2O4 (x is more than or equal to 1 and less than or equal to 2). Wherein "+" represents the meaning of composite, i.e. a composite of P3HT and Li 2MoO3, or a composite of P3HT and LiMoO 2, or a composite of P3HT and LiMoS xO1-x.
In the invention, a series of lithium molybdate salts are added into P3 HT: li 2MoO3LiMoO2LiMoSxO1-x (x is more than or equal to 0 and less than or equal to 1) or Li xMo2O4 (x is more than or equal to 1 and less than or equal to 2) to prepare various lithium molybdate hybrid P3HT. The perovskite material is applied to a solar cell, adopts a positive structure, and comprises an FTO layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and an electrode from bottom to top, wherein the material of the hole transport layer is formed by the novel lithium molybdate hybridization P3HT, the preparation method of the perovskite material is controllable in operation and has high reproducibility, and meanwhile, the application of the perovskite material in the solar cell can obviously improve the energy conversion efficiency and the device stability of the perovskite solar cell.
Further, the preparation method of the lithium molybdate comprises the following steps:
Mixing Li 2CO3 powder with MoO 3 powder, gradually adding deionized water into the mixed powder, and continuously stirring until the mixed solution is transparent to obtain a lithium molybdate salt solution;
heating the lithium molybdate solution until no bubbles are generated, evaporating to obtain a saturated lithium molybdate solution, wherein the heating temperature is preferably (32+/-0.5) DEG C so as to ensure that the solution is continuously and constantly evaporated;
And filtering and drying the saturated lithium molybdate solution to obtain white polycrystalline powder, namely lithium molybdate.
Further, when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder was 1:1:0 and reacted for 3 hours, li 2MoO3 was produced; when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is 1:2:0 and the reaction is carried out for 4 hours, liMoO 2 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 0.5:1:x (x=0-1) and the reaction is carried out for 3 hours, liMoS xO1-x (the value range of x is more than or equal to 0 and less than or equal to 1) is prepared; when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is x:4:0 (x=1-2) and the reaction is carried out for 2 hours, li xMo2O4 is prepared (the value range of x is more than or equal to 1 and less than or equal to 2).
Further, the specific method for drying comprises the following steps: randomly selecting unoriented irregular small lithium molybdate crystal blocks grown by a crucible descent method as seed crystals, completely immersing the seed crystals into the filtered saturated lithium molybdate salt solution, stirring at a rotating speed of 24r/min, extracting the seed crystals from the saturated lithium molybdate salt solution after the seed crystals grow for 21 days, and drying.
Further, the particle size of the white polycrystalline powder is 100nm or less.
Further, the preparation method of the lithium molybdate comprises the following steps:
Mixing Li 2CO3 powder (purity 99.99%) MoO 3 powder (purity 99.99%) and S powder (purity 99.9%) in a beaker at a molar ratio of 1:1:0, 1:2:0, 0.5:1:x (x=0-1) or x:4:0 (x=1-2), respectively, adding deionized water to the mixed powder gradually, and stirring continuously until the mixed solution is transparent to obtain a lithium molybdate salt solution;
heating the lithium molybdate solution until no bubbles are generated, evaporating to obtain a saturated lithium molybdate solution, wherein the heating temperature is preferably (32+/-0.5) DEG C so as to ensure that the solution is continuously and constantly evaporated;
And filtering and drying the saturated lithium molybdate solution to obtain white polycrystalline powder, namely lithium molybdate.
In the preparation method of the lithium molybdate, when the molar ratio of the Li 2CO3 powder to the MoO 3 powder to the S powder is 1:1:0 and the reaction is carried out for 3 hours, li 2MoO3 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 1:2:0 and the reaction is carried out for 4 hours, liMoO 2 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 0.5:1:x (x=0-1), and after 3 hours of reaction, liMoS xO1-x is prepared (x is more than or equal to 0 and less than or equal to 1); when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is x:4:0 (x=1-2) and the reaction is carried out for 2 hours, li xMo2O4 is prepared (the value range of x is more than or equal to 1 and less than or equal to 2).
The second technical scheme of the invention is as follows:
The application of the organic-inorganic hybrid hole transport material in preparing a hole transport layer.
The third technical scheme of the invention:
A preparation method of a hole transport layer is prepared from the organic-inorganic hybrid hole transport material and comprises the following steps:
Dissolving P3HT into Chlorobenzene (CB) solution, and stirring thoroughly to obtain uniform P3HT solution;
doping lithium molybdate into the P3HT solution to obtain a hole transport layer solution;
Filtering the hole transport layer solution, and spin-coating the solution onto a perovskite absorption layer to obtain a hole transport layer film;
and heating the hole transport layer film to obtain the hole transport layer.
Further, the preparation method of the hole transport layer comprises the following steps:
dissolving P3HT into 1mL of CB solution, and fully stirring to dissolve to obtain uniform 1mol/mL of P3HT solution;
Different concentrations and different types of lithium molybdate (Li 2MoO3LiMoO2LiMoSxO1-x (x is equal to or more than 0 and less than 1) or Li xMo2O4 (x is equal to or more than 1 and less than or equal to 2)) are doped into the P3HT solution respectively to obtain P3HT+Li 2MoO3P3HT+LiMoO2P3HT+LiMoSxO1-x (x is equal to or more than 0 and less than or equal to 1) or P3HT+Li xMo2O4 (x is equal to or less than or equal to 1 and less than or equal to 2) hole transport layer solutions with different concentrations;
Filtering the hole transport layer solution, wherein the diameter of a filter hole required by filtering is 220nm, spin-coating the solution onto a perovskite absorption layer, and the spin-coating rotating speed is 3000rpm and the time is 30s, so as to obtain a hole transport layer film;
and heating the hole transport layer film to obtain the hole transport layer.
The technical scheme of the invention is as follows:
the organic-inorganic hybrid hole transport material or the hole transport layer prepared by the method is applied to a solar cell.
Further, in the above application, the solar cell is an FTO layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and an electrode from bottom to top, wherein the thickness of the FTO layer is 450nm, the thickness of the electron transport layer is 10nm to 50nm, the thickness of the perovskite absorption layer is 300nm to 400nm, the thickness of the hole transport layer is 50nm to 100nm, and the thickness of the electrode is 120nm.
Further, the material of the electron transport layer is TiO 2.
Further, the perovskite absorption layer is made of CsPbI 3.
Further, the material of the electrode is at least one of gold (Au) and silver (Ag).
In the solar cell, the preparation methods of the electron transport layer, the hole transport layer and the electrode are all conventional methods, and can be prepared according to the conventional preparation methods.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) According to the invention, a series of lithium molybdate polycrystalline materials are introduced into a perovskite type solar cell structure as doping materials of a hole transport layer P3HT, li 2MoO3LiMoO2LiMoSxO1-x (wherein x is more than or equal to 0 and less than or equal to 1) and Li xMo2O4 (wherein x is more than or equal to 1 and less than or equal to 2) are respectively doped into the P3HT solution, the four materials are used as seed crystals, a hole transport layer solution containing lithium molybdate and P3HT is obtained, and then the prepared hole transport layer solution is subjected to spin coating, so that a device is prepared. Wherein LiMoS xO1-x (wherein 0.ltoreq.x.ltoreq.1) is doped in the P3HT solution, exhibiting champion efficiency when x=0.5, wherein Li xMo2O4 (wherein 1.ltoreq.x.ltoreq.2) is doped in the P3HT solution, exhibiting champion efficiency when x=1.6. The perovskite efficiency is respectively improved to 18.68(P3HT+Li2MoO3)18.11(P3HT+LiMoO2)19.10(P3HT+LiMoS0.5O0.5) and 19.30 percent (P3HT+Li 1.6Mo2O4) from 15.84 percent of the initial efficiency, and the perovskite long-term stability is effectively improved to 1470h (P3HT+Li 2MoO3)1170h(P3HT+LiMoO2)1860h(P3HT+LiMoS0.5O0.5) and 2500h (P3HT+Li 1.6Mo2O4) from the initial 960h (control group), so that the stability and the photoelectric performance of the perovskite solar cell device can be effectively improved by doping the lithium molybdate salt in the P3 HT.
(2) According to the invention, li 2MoO3LiMoO2LiMoSxO1-x (wherein the value range of x is more than or equal to 0 and less than or equal to 1) and Li xMo2O4 (wherein the value range of x is more than or equal to 1 and less than or equal to 2) are introduced into P3HT, so that the electron transmission and collection of the inorganic perovskite solar cell can be effectively enhanced, and the device performance is improved. Li 2MoO3LiMoO2LiMoSxO1-x (where x is in the range of 0.ltoreq.x.ltoreq.1) and Li xMo2O4 (where x is in the range of 1.ltoreq.x.ltoreq.2) are rarely mentioned and used in inorganic perovskite solar cells. The arrangement mode of lithium molybdate salts such as Li 2MoO3LiMoO2LiMoSxO1-x (wherein the value range of x is 0.ltoreq.x.ltoreq.1), li xMo2O4 (wherein the value range of x is 1.ltoreq.x.ltoreq.2) and the like is formed by metal ions, and each unit is surrounded by distorted molybdic acid ions. In one aspect, the unique structure of Li 2MoO3LiMoO2LiMoSxO1-x (where x is in the range 0.ltoreq.x.ltoreq.1) and Li xMo2O4 (where x is in the range 1.ltoreq.x.ltoreq.2) provides good carrier holding and storage capability. On the other hand, li 2MoO3LiMoO2LiMoSxO1-x (where x is in the range of 0.ltoreq.x.ltoreq.1) and Li xMo2O4 (where x is in the range of 1.ltoreq.x.ltoreq.2) exhibit carrier mobilities on the order of about 10 -3cm2/Vs, exhibit excellent electron and ion transport kinetics, low impedance, and efficient transport of ions and electrons within their structure. The carrier mobility is on the order of 10 -4cm2/Vs compared to P3 HT. Based on this, it was found through intensive research that the addition of Li 2MoO3LiMoO2LiMoSxO1-x (where x is in the range of 0.ltoreq.x.ltoreq.1) and Li xMo2O4 (where x is in the range of 1.ltoreq.x.ltoreq.2) to the hole transport layer of P3HT (the volume ratio of P3HT to lithium molybdate salt is 50:1) can successfully improve the stability and photovoltaic performance of the perovskite solar cell.
(3) The doping mode of the invention provides more ideas and directions for improving the photoelectric performance of the perovskite solar cell.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
Fig. 1 is a J-V plot of the highest efficiency of the perovskite cells of the control group, example 1 (p3ht+li 2MoO3), example 2 (p3ht+limoo 2) as hole transport layer.
Fig. 2 is a schematic structural diagram of perovskite solar cell according to examples 1 to 4 of the present invention.
FIG. 3 is a graph showing the J-V curves of the highest efficiency when x is 0, 0.5, and 1.0, respectively, for the perovskite type solar cell of the control group and example 3 (P3HT+ LiMoS xO1-x, wherein x has a value of 0.ltoreq.x.ltoreq.1) as the hole transporting layer.
FIG. 4 shows the J-V curves of the highest efficiency of the perovskite solar cell of the control group and example 4 (P3HT+Li xMo2O4, wherein x has a value range of 1.ltoreq.x.ltoreq.2) as the hole transporting layer when x is 1, 1.2, 1.4, 1.6, respectively.
FIG. 5 shows the J-V curves of the highest efficiency when x is 1.6, 1.8, and 2.0, respectively, for the perovskite type solar cell of the control group and example 4 (P3HT+Li xMo2O4, wherein x has a value of 1.ltoreq.x.ltoreq.2) as the hole transporting layer.
FIG. 6 shows the J-V curves of the highest efficiency of the perovskite solar cell of the control group and example 4 (P3HT+Li xMo2O4, wherein x has a value ranging from 1.ltoreq.x.ltoreq.2) as the hole transporting layer when x is 1.55, 1.60, 1.65, respectively.
Fig. 7 is a box line graph of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency of the perovskite batteries of the control group, example 1 (p3ht+li 2MoO3), example 2 (p3ht+li 2MoO3) as the hole transport layer.
Fig. 8 is a box plot of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency when x is 0, 0.5, 1.0, respectively, for the perovskite solar cell of the control group and example 3 (p3ht+ LiMoS xO1-x, where x has a value range of 0.ltoreq.x.ltoreq.1) as the hole transport layer.
Fig. 9 is a box diagram of the perovskite solar cell of the control group and example 4 (p3ht+ LixMo 2O4, where x has a value range of 1.ltoreq.x.ltoreq.2) as the hole transporting layer, and the highest efficiency of open circuit voltage, short circuit current, fill factor, conversion efficiency when x is 1, 1.2, 1.4, 1.6, 1.8, 2.0, respectively.
Fig. 10 is a box plot of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency when x is 1.55, 1.60, 1.65, respectively, for the perovskite solar cell of the control group and example 4 (p3ht+li xMo2O4, where x has a value range of 1.ltoreq.x.ltoreq.2) as the hole transport layer.
Fig. 11 is a graph showing the long-term stability of perovskite type solar cells in which the optimum x value (0.5) in the control group and example 1 (p3ht+li2moo 3), example 2 (p3ht+limoo 2), and example 3 (p3ht+ LiMoS xO1-x) in which x is in the range of 0.ltoreq.x.ltoreq.1), and the optimum x value (1.6) in example 4p3ht+lixmo 2O4 (in which x is in the range of 1.ltoreq.x.ltoreq.2) are used as hole transport layers, respectively.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "solar cell" in the present invention refers to a semiconductor device that can efficiently absorb solar energy and convert it into electric energy.
In the invention, the method for growing the unoriented irregular small lithium molybdate crystal blocks by using the crucible descent method is a conventional technical means in the field, and is not an important point of the invention, and is not repeated herein.
In the examples of the present invention, the methods are conventional methods unless otherwise specified. The starting materials are commercially available from the public unless otherwise specified. By way of example, P3HT is purchased from sienna baote company.
The preparation method of the lithium molybdate in the embodiment of the invention comprises the following steps: li 2CO3 powder (purity 99.99%) MoO 3 powder (purity 99.99%) and S powder (purity 99.9%) were mixed in a beaker at a molar ratio of 1:1:0, 1:2:0, 0.5:1:x (x=0-1) and x:4:0 (x=1-2), respectively, deionized water was gradually added to the mixed powder while stirring was continued until the mixed solution was transparent, to obtain a lithium molybdate solution;
Heating the lithium molybdate solution to a temperature of (32+/-0.5) DEG C until no bubbles are generated any more, so that the solution is continuously and constantly evaporated, and a saturated lithium molybdate solution is obtained after evaporation;
And filtering and drying the saturated lithium molybdate solution to obtain white polycrystalline powder, namely lithium molybdate. The specific method for drying comprises the following steps: randomly selecting unoriented irregular small lithium molybdate crystal blocks grown by a crucible descent method as seed crystals, completely immersing the seed crystals into the filtered saturated lithium molybdate salt solution, stirring at a rotating speed of 24r/min, extracting the seed crystals from the saturated lithium molybdate salt solution after the seed crystals grow for 21 days, and drying.
In the above preparation method of lithium molybdate, when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is 1:1:0 and reacted for 3 hours, li 2MoO3 is prepared; when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is 1:2:0 and the reaction is carried out for 4 hours, liMoO 2 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 0.5:1:x (x=0-1) and the reaction is carried out for 3 hours, liMoS xO1-x (the value range of x is more than or equal to 0 and less than or equal to 1) is prepared; when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is x:4:0 (x=1-2) and the reaction is carried out for 2 hours, li xMo2O4 is prepared (the value range of x is more than or equal to 1 and less than or equal to 2).
The technical scheme of the invention is further described by the following examples.
Control perovskite solar cell (CsPbI 3)
1) Preparation of TiO 2 electron transport layer
The method comprises the following specific steps: 70 mu L of dilute hydrochloric acid and 700 mu L of isopropyl titanate are respectively added into 5mL of ethanol, then mixed together to obtain a TiO 2 solution, fully mixed and oscillated, and filtered for standby.
And statically dripping the TiO 2 solution obtained in the step on FTO layer glass, spin-coating for 30s at a rotating speed of 2000rpm, respectively heating at 150 and 250 and 350 for 10 minutes for annealing, and finally heating at 550 for 30 minutes to obtain the electron transport layer (TiO 2) film with the thickness of about 50 nm.
2) Preparation of perovskite absorber layer
CsI and DMAPbI 3 are prepared according to a molar ratio of 0.7:0.85, and are dissolved in 1mL of mixed solution of DMF: DMSO=19:1 (volume ratio) at a concentration of 1mol/mL, and the required precursor solution is obtained by fully stirring and dissolving. The diameter of the filter hole required by the precursor solution filtration is 220nm, the rotating speed of the spin-coating perovskite precursor solution is 4000rpm, and the spin-coating time is 35s. The perovskite film obtained was heated on a hot plate at 210for 5 minutes to obtain a perovskite absorption layer.
3) Preparation of hole transport layer (P3 HT)
The solution of the hole transport layer was prepared from P3HT in chlorobenzene at a concentration of 10 mg/mL. After full shaking and dissolution, the mixture is filtered through a 220nm filter hole for later use. The resulting P3HT solution was spin-coated onto the perovskite absorber layer at 3000rpm for 30s, and the resulting film was annealed at 100 for 1 hour.
4) Vapor deposition Ag electrode
An Ag electrode was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s and a vacuum degree of 1.0X10 -3 Pa or less, and the thickness of the electrode obtained by vapor deposition was 120nm.
The perovskite solar cell in the control group was identical in structure to example 1, except that the material of the hollow transport layer in the control group was P3HT only, and no lithium molybdate salt was contained.
The J-V performance curve of the cell was tested with a solar simulator under an AM1.5, 100mW/cm 2 light, as shown in FIG. 1, and the control blank condition gave a cell with a short circuit current density of 19.92mA/cm 2, an open circuit voltage of 1.14V, a fill factor of 0.775, and a photoelectric conversion efficiency of 17.60%.
Example 1 preparation of (P3HT+Li 2MoO3) perovskite solar cell
1) Preparation of TiO 2 electron transport layer
The method comprises the following specific steps: 70 mu L of dilute hydrochloric acid and 700 mu L of isopropyl titanate are respectively added into 5mL of ethanol, then mixed together to obtain a TiO 2 solution, fully mixed and oscillated, and filtered for standby.
And statically dripping the TiO 2 solution obtained in the step on FTO layer glass, spin-coating for 30s at a rotating speed of 2000rpm, respectively heating at 150 and 250 and 350 for 10 minutes for annealing, and finally heating at 550 for 30 minutes to obtain the electron transport layer (TiO 2) film with the thickness of 50 nm.
2) Preparation of perovskite absorber layer (i.e., perovskite absorber layer, hereinafter the same)
CsI and DMAPbI 3 are prepared according to a molar ratio of 0.7:0.85, and are dissolved in 1mL of mixed solution of DMF: DMSO=19:1 (volume ratio) at a concentration of 1mol/mL, and the required precursor solution is obtained by fully stirring and dissolving. The diameter of a filter hole required by the filtration of the precursor solution is 220nm, the rotating speed of the spin-coating perovskite precursor solution is 4000rpm, and the spin-coating time is 35s. The perovskite film obtained was heated on a hot plate at 210for 5 minutes to obtain a perovskite absorption layer having a thickness of 350 nnm.
3) Preparation of hole transport layer (P3HT+Li 2MoO3)
The solution of the hole transport layer is prepared by dissolving P3HT in chlorobenzene at 10mg/mL, dissolving Li 2MoO3 in deionized water at 0.5mol/mL, mixing the solution at the volume ratio of 50:1 after the solution is fully dissolved, obtaining the mixed P3HT+Li 2MoO3 solution, and filtering through a 220nm filter hole after the solution is fully oscillated and dissolved for later use. The resulting mixed P3HT+Li 2MoO3 solution was spin-coated onto the perovskite absorption layer at a spin-coating speed of 3000rpm for 30s, and the resulting film was annealed at 100deg.C for 1 hour to give a hole transport layer having a thickness of 80 nm.
4) Vapor deposition Ag electrode
An Ag electrode was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s and a vacuum degree of 1.0X10 -3 Pa or less, and the thickness of the electrode obtained by vapor deposition was 120nm.
The schematic structural diagram of the perovskite solar cell obtained in this embodiment is shown in fig. 2, and the schematic structural diagram is from bottom to top, and the schematic structural diagram is an FTO layer, a TiO 2 electron transport layer, a perovskite absorption layer, a hole transport layer (p3ht+li 2MoO3), and an electrode, where the thickness of the FTO layer is 450nm, the thickness of the TiO 2 electron transport layer is 50nm, the thickness of the perovskite absorption layer is 350nnm, the thickness of the hole transport layer is 80nm, and the thickness of the electrode is 120nm.
The J-V performance curves of the cells were tested with a solar simulator under AM1.5, 100mW/cm 2 light, as shown in FIG. 3, the perovskite cell device obtained using the hole transport layer material of example 1 (P3HT+Li 2MoO3) had a short circuit current density of 20.465mA/cm 2, an open circuit voltage of 1.166V, and a significant improvement in the photovoltaic performance of the perovskite cell device obtained using the hole transport layer material of example 1 (P3HT+Li 2MoO3) compared to the control P3HT having a short circuit current density of 19.65mA/cm 2, and an open circuit voltage of 1.078V.
Example 2 preparation of (P3HT+LiMoO 2) perovskite solar cell
1) Preparation of TiO 2 electron transport layer
The method comprises the following specific steps: 70 mu L of dilute hydrochloric acid and 700 mu L of isopropyl titanate are respectively added into 5mL of ethanol, then mixed together to obtain a TiO 2 solution, fully mixed and oscillated, and filtered for standby.
And statically dripping the TiO 2 solution obtained in the step on FTO layer glass, spin-coating for 30s at a rotating speed of 2000rpm, respectively heating at 150 and 250 and 350 for 10 minutes for annealing, and finally heating at 550 for 30 minutes to obtain the electron transport layer (TiO 2) film with the thickness of 50 nm.
2) Preparation of perovskite absorber layer
CsI and DMAPbI 3 are prepared according to a molar ratio of 0.7:0.85, and are dissolved in 1mL of mixed solution of DMF: DMSO=19:1 (volume ratio) at a concentration of 1mol/mL, and the required precursor solution is obtained by fully stirring and dissolving. The diameter of the filter hole required for solution filtration is 220nm, the rotating speed of the solution of the spin-coating perovskite precursor is 4000rpm, and the spin-coating time is 35s. The perovskite film obtained was heated on a hot plate at 210for 5 minutes to obtain a perovskite absorption layer having a thickness of 350 nnm.
3) Preparation of hole transport layer (P3 HT)
The solution of the hole transport layer is prepared by dissolving P3HT in chlorobenzene at 10mg/mL, dissolving LiMoO 2 in deionized water at 0.5mol/mL, mixing the solution at the volume ratio of 50:1 after the solution is fully dissolved, obtaining the mixed P3HT+LiMoO 2 solution, and filtering through a 220nm filter hole after the solution is fully oscillated and dissolved. The resulting mixed p3ht+limoo 2 solution was spin-coated onto the perovskite absorption layer at a spin-coating speed of 3000rpm for 30s, and the resulting film was annealed at 100 for 1 hour to obtain a hole transport layer having a thickness of 80 nm.
4) Vapor deposition Ag electrode
The electrode was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s and a vacuum degree of 1.0X10 -3 Pa or less, and the thickness of the electrode obtained by vapor deposition was 120nm.
The schematic structure of the perovskite solar cell obtained in this example is shown in fig. 2.
The J-V performance curves of the cells were tested with a solar simulator under AM1.5, 100mW/cm 2 light, as shown in FIG. 3, and the perovskite cell device obtained using the material obtained for the hole transport layer material of example 2 (P3HT+LiMoO 2) had a short circuit current density of 20.257mA/cm 2 and an open circuit voltage of 1.154V. Compared with the control group P3HT, the perovskite battery device obtained by the hole transport layer material of the embodiment 2 (P3HT+LiMoO 2) has the short-circuit current density of 19.65mA/cm 2 and the open-circuit voltage of 1.078V, and the photovoltaic performance of the perovskite battery device is remarkably improved.
Example 3 preparation of (P3HT+ LiMoS xO1-x) perovskite solar cell (wherein x has a value in the range 0.ltoreq.x.ltoreq.1)
1) Preparation of TiO 2 electron transport layer
The method comprises the following specific steps: 70 mu L of dilute hydrochloric acid and 700 mu L of isopropyl titanate are respectively added into 5mL of ethanol, then mixed together to obtain a TiO 2 solution, fully mixed and oscillated, and filtered for standby.
And statically dripping the TiO 2 solution obtained in the step on FTO layer glass, spin-coating for 30s at a rotating speed of 2000rpm, respectively heating at 150 and 250 and 350 for 10 minutes for annealing, and finally heating at 550 for 30 minutes to obtain the electron transport layer (TiO 2) film with the thickness of 50 nm.
2) Preparation of perovskite absorber layer
CsI and DMAPbI 3 are prepared according to a molar ratio of 0.7:0.85, and are dissolved in 1mL of mixed solution of DMF: DMSO=19:1 (volume ratio) at a concentration of 1mol/mL, and the required precursor solution is obtained by fully stirring and dissolving. The diameter of the filter hole required for solution filtration is 220nm, the rotating speed of the solution of the spin-coating perovskite precursor is 4000rpm, and the spin-coating time is 35s. The perovskite film obtained was heated on a hot plate at 210for 5 minutes to obtain a perovskite absorption layer having a thickness of 350 nnm.
3) Preparation of hole transport layer (P3 HT)
The solution of the hole transport layer is prepared by dissolving P3HT in chlorobenzene with the concentration of 10mg/mL, (P3HT+ LiMoS xO1-x, wherein the value range of x is not less than 0 and not more than 1, in the embodiment, x=0, 0.5 or 1.0) in deionized water with the concentration of 0.5mol/mL, mixing the solution in the volume ratio of 50:1 after the solution is fully dissolved, and obtaining the mixed (P3HT+ LiMoS xO1-x, wherein the value range of x is not less than 0 and not more than 1) solution, and filtering the solution through a 220nm filter hole for standby after the solution is fully oscillated and dissolved. The obtained mixed (P3HT+ LiMoS xO1-x, wherein the value range of x is more than or equal to 0 and less than or equal to 1) solution is spin-coated on a perovskite absorption layer, the spin-coating rotating speed is 3000rpm, the duration time is 30s, and the obtained film is annealed for 1 hour at 100 to obtain a hole transport layer with the thickness of 80 nm.
4) Vapor deposition Ag electrode
The electrode was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s and a vacuum degree of 1.0X10 -3 Pa or less, and the thickness of the electrode obtained by vapor deposition was 120nm.
A schematic structural diagram of the perovskite solar cell obtained in example 3 is shown in fig. 2.
The J-V performance curves of the cells were tested with a solar simulator under AM1.5, 100mW/cm 2 light, as shown in FIG. 3, in a perovskite cell device using example 3 (P3HT+ LiMoS xO1-x, where x has a value range of 0.ltoreq.x.ltoreq.1) as the hole transport layer, the perovskite solar cell fabricated by P3HT+ LiMoS xO1-x (x takes 0.5) exhibited a champion device short circuit current of 20.45mA/cm 2 and an open circuit voltage of 1.154V. Compared with the control group P3HT, the perovskite battery device obtained by taking the embodiment 3 (P3HT+ LiMoS xO1-x) as the hole transport layer material has the advantages that the short circuit current density is 19.65mA/cm < 2 >, the open circuit voltage is 1.078V, and the photovoltaic performance is remarkably improved.
1) Preparation of TiO 2 electron transport layer
The method comprises the following specific steps: 70 mu L of dilute hydrochloric acid and 700 mu L of isopropyl titanate are respectively added into 5mL of ethanol, then mixed together to obtain a TiO 2 solution, fully mixed and oscillated, and filtered for standby.
And statically dripping the TiO 2 solution obtained in the step on FTO layer glass, spin-coating for 30s at a rotating speed of 2000rpm, respectively heating at 150 and 250 and 350 for 10 minutes for annealing, and finally heating at 550 for 30 minutes to obtain the electron transport layer (TiO 2) film with the thickness of 50 nm.
2) Preparation of perovskite absorber layer
CsI and DMAPbI 3 are prepared according to a molar ratio of 0.7:0.85, and are dissolved in 1mL of mixed solution of DMF: DMSO=19:1 (volume ratio) at a concentration of 1mol/mL, and the required precursor solution is obtained by fully stirring and dissolving. The diameter of the filter hole required for solution filtration is 220nm, the rotating speed of the solution of the spin-coating perovskite precursor is 4000rpm, and the spin-coating time is 35s. The perovskite film obtained was heated on a hot plate at 210for 5 minutes to obtain a perovskite absorption layer having a thickness of 350 nnm.
3) Preparation of hole transport layer (P3 HT)
The solution of the hole transport layer is prepared by dissolving P3HT in chlorobenzene and Li xMo2O4 (wherein the value range of x is 1.ltoreq.x.ltoreq.2) in 10mg/mL, dissolving x=1.0, 1.2, 1.4, 1.5, 1.55, 1.6, 1.65, 1.8 or 2.0 in the embodiment in deionized water in the concentration of 0.5mol/mL, mixing the solution in the volume ratio of 50:1 after the solution is fully dissolved, and obtaining the mixed P3HT+Li xMo2O4 (wherein the value range of x is 1.ltoreq.x.ltoreq.2) solution, and filtering the solution through a 220nm filter hole for later use after the solution is fully oscillated and dissolved. The obtained mixed P3HT+Li xMo2O4 (wherein x is within the range of 1.ltoreq.x.ltoreq.2) solution is spin-coated on the perovskite absorption layer, the spin-coating speed is 3000rpm, the duration time is 30s, and the obtained film is annealed at 100 for 1 hour to obtain a hole transport layer with the thickness of 80 nm.
4) Vapor deposition Ag electrode
The electrode was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s and a vacuum degree of 1.0X10 -3 Pa or less, and the thickness of the electrode obtained by vapor deposition was 120nm.
The schematic structure of the perovskite solar cell obtained in this example is shown in fig. 2.
The J-V performance curves of the cells were tested with a solar simulator under AM1.5, 100mW/cm 2 light, as shown in FIGS. 4-6, using the perovskite cell device of example 4P3HT+Li xMo2O4 (where x has a value ranging from 1.ltoreq.x.ltoreq.2) as the hole transport layer, wherein the perovskite solar cell fabricated by P3HT+Li xMo2O4 (where x has a value ranging from 1.6) exhibited a crown short circuit current density of 20.50mA/cm 2 and an open circuit voltage of 1.159V, which was 1.078V, and the photovoltaic performance of the perovskite cell device obtained by example 4 (P3HT+Li xMo2O4) as the hole transport layer material was significantly improved, compared to the control group P3HT having a short circuit current density of 19.65mA/cm 2.
Fig. 7 is a box line graph of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency of the perovskite batteries of the control group, example 1 (p3ht+li 2MoO3), example 2 (p3ht+li 2MoO3) as the hole transport layer. It was found that the perovskite battery device obtained in example 1 (p3ht+li 2MoO3) as a hole transport layer material had a short-circuit current density of 20.465mA/cm 2, an open-circuit voltage of 1.166V, a fill factor of 0.783, and a photoelectric conversion efficiency of 18.684%; the perovskite battery device obtained by the material obtained by the hole transport layer material of example 2 (p3ht+limoo 2) had a short-circuit current density of 20.257mA/cm 2, an open-circuit voltage of 1.154V, a fill factor of 0.775, and a photoelectric conversion efficiency of 18.116%. Compared with the comparison group P3HT, the short-circuit current density is 19.65mA/cm 2, the open-circuit voltage is 1.078V, the filling factor is 0.748, the photoelectric conversion efficiency is 15.844%, and the photovoltaic performance of the perovskite battery device obtained by using the materials of the embodiment 1 (P3HT+Li 2MoO3) and the embodiment 2 (P3HT+LiMoO 2) as the hole transport layer is remarkably improved compared with the comparison group.
Fig. 8 is a box plot of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency when x is 0, 0.5, 1.0, respectively, for the perovskite solar cell of the control group and example 3 (p3ht+ LiMoS xO1-x, where x has a value range of 0.ltoreq.x.ltoreq.1) as the hole transport layer. It was found that the perovskite solar cell prepared by p3ht+ LiMoS xO1-x (x is 0.5) exhibited a champion photovoltaic performance, and the champion device prepared by p3ht+ LiMoS xO1-x (x is 0.5) had a short-circuit current density of 20.45mA/cm 2, an open-circuit voltage of 1.154V, a fill factor of 0.809, and a photoelectric conversion efficiency of 19.10%. Compared with the control group P3HT, the short-circuit current density is 19.65mA/cm 2, the open-circuit voltage is 1.078V, the filling factor is 0.748, and the photoelectric conversion efficiency is 15.844%. The photovoltaic performance of the perovskite battery device obtained by using the material of the hole transport layer of the embodiment 3P3HT+Li xMo2O4 (wherein the value range of x is 1-x-2) is remarkably improved compared with that of the control group.
Fig. 9 is a box diagram of the perovskite solar cell of the control group and example 4 (p3ht+ LixMo 2O4, where x has a value range of 1.ltoreq.x.ltoreq.2) as the hole transporting layer, and the highest efficiency of open circuit voltage, short circuit current, fill factor, conversion efficiency when x is 1, 1.2, 1.4, 1.6, 1.8, 2.0, respectively. It was found that the perovskite solar cell prepared by p3ht+li xMo2O4 (x is taken to be 1.6) exhibited a champion photovoltaic performance, and the champion device prepared by p3ht+li xMo2O4 (x is taken to be 1.6) had a short-circuit current density of 20.50mA/cm 2, an open-circuit voltage of 1.159V, a fill factor of 0.811, and a photoelectric conversion efficiency of 19.30%. Compared with the comparison group P3HT, the short-circuit current density is 19.65mA/cm 2, the open-circuit voltage is 1.078V, the filling factor is 0.748, the photoelectric conversion efficiency is 15.844%, and the photovoltaic performance of the perovskite battery device obtained by using the embodiment 4 (P3HT+ LiMoS xO1-x, wherein the value range of x is 0.ltoreq.x.ltoreq.1) as the hole transport layer material is remarkably improved compared with the comparison group.
Fig. 10 is a box plot of the highest efficiency open circuit voltage, short circuit current, fill factor, conversion efficiency when x is taken to be 1.55, 1.60, 1.65, respectively, for the perovskite solar cell of the control group and example 4 (p3ht+li xMo2O4, where x is taken to be 1.ltoreq.x.ltoreq.2) as the hole transport layer, and it is known that the perovskite solar cell prepared by p3ht+li xMo2O4 (x is taken to be 1.6) exhibits the champion photovoltaic performance, as compared with x=1.65, as best shown in fig. 9.
Fig. 11 shows the long-term stability of perovskite-type solar cells using example 1 (p3ht+li 2MoO3), example 2 (p3ht+limoo 2), example 3 (p3ht+ LiMoS xO1-x) wherein x has a value of 0.ltoreq.x.ltoreq.1, and example 4 (p3ht+li xMo2O4) wherein x has a value of 1.ltoreq.x.ltoreq.2) as a hole transport layer under a humidity of 30% or less. A perovskite type solar cell using the control group as a hole transport layer maintained 80% of initial efficiency at 960 hours at a humidity of 30% or less and a temperature of 25 ; the perovskite solar cell using example 1 (p3ht+li 2MoO3) as the hole transport layer was able to maintain 80% of the initial efficiency at 1470 hours at a temperature of 25 with humidity of 30% or less; the perovskite solar cell using example 2 (p3ht+limoo 2) as the hole transport layer was able to maintain 80% of the initial efficiency at 1170 hours at a temperature of 25 with humidity of 30% or less; the perovskite solar cell of the perovskite champion device using example 3 (p3ht+ LiMoS xO1-x, wherein x has a value of 0.ltoreq.x.ltoreq.1) (p3ht+ LiMoS xO1-x, wherein x has a value of 0.5) as the hole transporting layer was able to maintain 80% of the initial efficiency at a humidity of 30% or less and a temperature of 25 for 1860 hours; the perovskite champion device using example 4 (p3ht+li xMo2O4, wherein x has a value range of 1.ltoreq.x.ltoreq.2) (p3ht+li xMo2O4, wherein x has a value of 1.6) as the hole transport layer was able to maintain 80% of the initial efficiency at a humidity of 30% or less and a temperature of 25 for 2500 hours. Therefore, the perovskite solar cell of examples 1 to 4 as the hole transport layer showed a significant improvement in long-term stability at a humidity of 30% or less and a temperature of 25 compared with the control group, wherein the perovskite solar cell of example 4 (p3ht+li xMo2O4 wherein x has a value of 1.ltoreq.x.ltoreq.2) had the best long-term stability as the hole transport layer in (p3ht+li xMo2O4 wherein x has a value of 1.6).
From the above, it is clear that after Li 2MoO3 is introduced, the short-circuit current density of the solar cell device prepared by using p3ht+li 2MoO3 as the hole transport layer material is increased from 19.65mA/cm 2 to 20.465mA/cm 2, the open-circuit voltage is increased from 1.078V to 1.166V, and the photovoltaic performance is significantly improved compared with pure P3 HT. In addition, as can be seen from the box diagram of fig. 7, the efficiency of the device prepared by using p3ht+li 2MoO3 as the hole transport layer material reaches 18.684%, and compared with the 15.844% of the empty hole transport layer material, the effect of improvement is quite remarkable.
The application discloses a preparation method of an organic-inorganic hybrid hole transport material and application thereof in a solar cell, and particularly discloses a method and a plurality of ways for realizing the technical scheme. Any equivalent modifications and substitutions for the present application will occur to those skilled in the art, and are also within the scope of the present application. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present application without departing from the spirit and scope thereof. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. An organic-inorganic hybrid hole transport material characterized in that a lithium molybdate salt is doped in P3 HT;
The lithium molybdate salt includes: li 2MoO3LiMoO2LiMoSxO1-x (x is equal to or more than 0 and equal to or less than 1) or Li xMo2O4 (x is equal to or more than 1 and equal to or less than 2).
2. The organic-inorganic hybrid hole transport material according to claim 1, wherein the organic-inorganic hybrid hole transport material is p3ht+li 2MoO3P3HT+LiMoO2P3HT+LiMoSxO1-x (x is 0.ltoreq.x.ltoreq.1) or p3ht+li xMo2O4 (x is 1.ltoreq.x.ltoreq.2).
3. The organic-inorganic hybrid hole transport material according to claim 1, wherein the preparation method of the lithium molybdate salt is as follows:
mixing Li 2CO3 powder, moO 3 powder and S powder, gradually adding deionized water into the mixed powder, and continuously stirring until the mixed solution is transparent to obtain a lithium molybdate salt solution;
Heating the lithium molybdate solution until no bubbles are generated, and evaporating to obtain a saturated lithium molybdate solution;
And filtering and drying the saturated lithium molybdate solution to obtain white polycrystalline powder, namely lithium molybdate.
4. An organic-inorganic hybrid hole transport material according to claim 3, wherein after the molar ratio of Li 2CO3 powder, moO 3 powder to S powder is 1:1:0 and 3 hours of reaction, li 2MoO3 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 1:2:0 and the reaction is carried out for 4 hours, liMoO 2 is prepared; when the mole ratio of Li 2CO3 powder, moO 3 powder and S powder is 0.5:1:x (x=0-1), and after 3 hours of reaction, liMoS xO1-x is prepared (x is more than or equal to 0 and less than or equal to 1); when the molar ratio of Li 2CO3 powder, moO 3 powder and S powder is x:4:0 (x=1-2) and the reaction is carried out for 2 hours, li xMo2O4 is prepared (the value range of x is more than or equal to 1 and less than or equal to 2).
5. The organic-inorganic hybrid hole transport material according to claim 3, wherein the specific method of drying is: randomly selecting unoriented irregular small lithium molybdate crystal blocks grown by a crucible descent method as seed crystals, completely immersing the seed crystals into the filtered saturated lithium molybdate salt solution, stirring at a rotating speed of 24r/min, extracting the seed crystals from the saturated lithium molybdate salt solution after the seed crystals grow for 21 days, and drying.
6. An organic-inorganic hybrid hole transport material according to claim 3, wherein the particle size of the white polycrystalline powder is 100nm or less.
7. Use of an organic-inorganic hybrid hole transport material according to any one of claims 1 to 6 for the preparation of a hole transport layer.
8. A method for preparing a hole transport layer, characterized by being prepared from the organic-inorganic hybrid hole transport material according to any one of claims 1 to 6, comprising the steps of:
dissolving P3HT into chlorobenzene solution, and stirring thoroughly to obtain uniform P3HT solution;
doping lithium molybdate into the P3HT solution to obtain a hole transport layer solution;
Filtering the hole transport layer solution, and spin-coating the solution onto a perovskite absorption layer to obtain a hole transport layer film;
and heating the hole transport layer film to obtain the hole transport layer.
9. Use of an organic-inorganic hybrid hole transport material according to any one of claims 1 to 6 or a hole transport layer prepared according to the method of claim 8 in a solar cell.
10. The use according to claim 9, wherein the solar cell comprises, from bottom to top, an FTO layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and an electrode, wherein the FTO layer has a thickness of 450nm, the electron transport layer has a thickness of 10nm to 50nm, the perovskite absorption layer has a thickness of 300nm to 400nm, the hole transport layer has a thickness of 50nm to 100nm, and the electrode has a thickness of 120nm.
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