CN117751698A - Mofs material, perovskite solar cell, photovoltaic module and photovoltaic system - Google Patents
Mofs material, perovskite solar cell, photovoltaic module and photovoltaic system Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 222
- -1 primary amine cation Chemical class 0.000 claims abstract description 98
- 238000002161 passivation Methods 0.000 claims abstract description 86
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- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 60
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- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 29
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- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 22
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
Abstract
The application relates to a Mofs material, a perovskite solar cell, a photovoltaic module and a photovoltaic system, and belongs to the technical field of solar cells. The repeated structural unit of the Mofs material is (I): wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is a primary amine cation. The Mofs material can be used as a passivation material of a hollow transmission layer in the perovskite solar cell, and can improve the conversion efficiency and the stability of the perovskite solar cell.
Description
The application relates to the technical field of solar cells, and in particular relates to a Mofs material, a perovskite solar cell, a photovoltaic module and a photovoltaic system.
The perovskite solar cell has two main structures, namely a formal structure (from bottom to top, a photoelectric glass-electron transport layer-perovskite absorption layer-hole transport layer-electrode) and a trans-structure (from bottom to top, a photoelectric glass-hole transport layer-perovskite absorption layer-electron transport layer-electrode). However, current perovskite solar cells have low energy conversion rates.
Disclosure of Invention
In view of the above problems, the present application provides a Mofs material, a perovskite solar cell, a photovoltaic module and a photovoltaic system, so as to improve the technical problem of low energy conversion rate of the perovskite solar cell.
In a first aspect, embodiments of the present application provide a Mofs material, where the repeating structural unit of the Mofs material is:
wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen;R 2 is a primary amine cation.
In the technical scheme, the Mofs material can be used as a passivation layer material in a perovskite solar cell, five-membered heterocycle in the Mofs material has p-pi conjugation capacity shared by aromatics, metal atoms are used as network nodes, halogen atoms and oxygen atoms of five-membered heterocycle dicarboxylic acid are used as bridges, metal halides and five-membered heterocycle dicarboxylic acid are coordinated and connected to form a three-dimensional anion frame, stronger electron cloud and weaker covalent bonds with poor conductivity can be alternately existing in the passivation layer, and the metal halide and the five-membered heterocycle dicarboxylic acid are matched with primary amine cations, so that hole carrier separation can be promoted, and the conversion efficiency and stability of the perovskite solar cell are improved.
In some embodiments, R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation. The methylamine cation can stabilize the framework of the passivation layer material, and further improve the stability of the perovskite solar cell.
In some embodiments, M is selected from one of Pb, sn, bi. The three metal elements have strong coordination capability, can form coordination with the metal elements in the perovskite main body layer in the perovskite solar cell, and can form chemical bond connection between the passivation layer and the perovskite main body layer.
In some embodiments, R 1 One selected from S, O, N. The three five-membered heterocyclic dicarboxylic acid structures are favorable for forming a three-dimensional anion frame, so that the passivation effect of a passivation layer formed by the Mofs material is better; meanwhile, the electronegativity of the S, O, N five-membered heterocycle has a certain difference, and the electric cloud density of the anion frame can be influenced to different degrees, so that different coordination modes of the anion frame are formed, the band gap of the Mofs material has a certain difference, and the requirements of different perovskite solar cells are met.
In some embodiments, X is selected from one of Cl, br, I. The metal halides formed by the three halogen elements are favorable for forming a three-dimensional anion frame, can be consistent with the halogen elements in the perovskite main body layer in the perovskite solar cell, and are favorable for improving the passivation effect of the passivation layer. Meanwhile, after different halogen elements are matched with metal ions, the Mofs material can be used as a passivation layer to have different band gaps so as to match the energy levels of perovskite solar cells of different systems.
In some embodiments, R 2 Selected from dimethylamine cations or trimethylamine cations. The methylamine cation can make up for the defects of a perovskite main body layer in the perovskite solar cell, thereby improving the performance of the perovskite solar cell.
In some embodiments, M is Pb, R1 is S, X is Cl or Br, R 2 Is dimethylamine. If the metal cation in the perovskite host layer in the perovskite solar cell is Pb 2+ Can more easily form coordination with metal element Pb in Mofs material so as to make the combination capability between perovskite layer and passivation layer better, thereby improving the performance of perovskite battery.
In some embodiments, M is Sn, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine. If the metal cation in the perovskite host layer in the perovskite solar cell is Sn 2+ Can more easily form coordination with metal element Sn in Mofs material, so that the combination capability between the perovskite layer and the passivation layer is better, thereby improving the performance of the perovskite battery.
In some embodiments, M is Bi, R1 is S, X is Cl or Br, R 2 Is dimethylamine. If the metal cation in the perovskite host layer in the perovskite solar cell is Bi 2+ The complex can be formed with the metal element Bi in the Mofs material more easily, so that the combination capability between the perovskite layer and the passivation layer is better, and the performance of the perovskite battery is improved.
In some embodiments, the Mofs material meets at least one of the following: the aperture of the Mofs material isThe Mofs material is a hexagonal system; the space group of the Mofs material is P6mm; mofThe unit cell parameters of the s material are: α=β=90°, γ=120°. The aperture, crystal system, space group and unit cell parameters of the Mofs material meet the conditions, and the complex structure unit of the Mofs material is matched with the complex structure unit of the Mofs material so as to determine the coordination mode of the Mofs material, and the passivation effect of the material is good.
In a second aspect, an embodiment of the present application provides a perovskite solar cell, including a hole transport layer, a passivation layer and a perovskite main body layer that are sequentially stacked, where a material of the passivation layer includes a Mofs material, and a repeating structural unit of the Mofs material is:
wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is a primary amine cation.
In the technical scheme, the passivation layer is arranged between the hole transport layer and the perovskite main body layer, and the Mofs material contained in the passivation layer meets the repeated structural units, so that the conversion efficiency and the stability of the perovskite solar cell can be improved.
In some embodiments, R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation. Further improving the stability of the perovskite solar cell.
In some embodiments, M is selected from one of Pb, sn, bi. The coordination capacity of the perovskite solar cell is high, the perovskite solar cell can coordinate with metal elements in a perovskite main body layer in the perovskite solar cell, and chemical bond connection can be formed between the passivation layer and the perovskite main body layer, so that the binding force between the passivation layer and the perovskite main body layer is improved, and the stability of the perovskite solar cell is improved.
In some embodiments, R1 is selected from one of S, O, N. Can be further matched with perovskite solar cells, thereby improving the conversion efficiency of the perovskite solar cells.
In some embodiments, X is selected from one of Cl, br, I. Can be further matched with perovskite solar cells, thereby improving the conversion efficiency of the perovskite solar cells.
In some embodiments, R 2 Selected from dimethylamine cations or trimethylamine cations. The pores of the Mofs material can be relatively large, so that the hole transport capacity of the passivation layer is improved, and the conversion efficiency of the perovskite solar cell is improved.
In some embodiments, the Mofs material meets at least one of the following: the aperture of the Mofs material isThe Mofs material is a hexagonal system; the space group of the Mofs material is P6mm; the unit cell parameters of the Mofs material are: α=β=90°, γ=120°. The complex structure unit of the Mofs material is matched with the complex structure unit of the Mofs material so as to determine the coordination mode of the Mofs material, and the passivation effect of the material is good, so that the conversion efficiency and the stability of the perovskite solar cell can be improved.
In some embodiments, the perovskite host layer material has the formula ABC 3 Wherein A comprises at least one of methylamine cation, formamidine cation and cesium ion; b includes Pb 2+ 、Sn 2+ 、Bi 2+ At least one of (a) and (b); c includes at least one of Cl-, br-, and I-. As the material of the perovskite main body layer, the perovskite solar cell can be matched with the passivation layer and the hole transmission layer to play a role in passivating the hole transmission layer, so that the conversion efficiency and the stability of the perovskite solar cell are improved.
In some embodiments, M is Pb, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Dimethylamine, B in the perovskite main layer material being Pb 2+ . Can make metal cation Pb in perovskite main body layer 2+ Form coordination with metal element Pb in Mofs material to make the combination ability between perovskite layer and passivation layer better, thus raise the performance of perovskite battery.
In some embodiments, in the repeating structural units of the Mofs material, M is Sn, R1 is S, X is Cl or Br, R2 is dimethylamine, and B in the perovskite host layer material is Sn 2+ . Can make metal cations Sn in perovskite main body layer 2+ Coordination is formed with metal element Sn in the Mofs material so as to ensure that the bonding capability between the perovskite layer and the passivation layer is better, thereby improving the performance of the perovskite battery.
In some embodiments, M is Bi, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Dimethylamine, B in the perovskite main layer material is Bi 2+ . Can make the metal cation Bi in the perovskite main body layer 2+ Form coordination with the metal element Bi in the Mofs material so as to ensure better bonding capability between the perovskite layer and the passivation layer, thereby improving the performance of the perovskite battery.
In some embodiments, the material of the hole transport layer is an inorganic metal compound. The metal ions in the inorganic metal compound tend to form unstable metal cations having a higher valence after being irradiated with light, and the metal cations are brought into contact with the perovskite host layer, thereby affecting the stability of the perovskite host layer. In the application, the passivation layer composed of the Mofs material is arranged between the hole transport layer formed by the inorganic metal compound and the perovskite main body layer, so that high-valence metal cations can be complexed with the Mofs material and converted into low-valence metal cations, influence on the perovskite main body layer is avoided, and the conversion efficiency and stability of the perovskite solar cell are improved.
In some embodiments, the material of the hole transport layer comprises at least one of nickel oxide, copper iodide, copper thiocyanate. The material has good hole transport effect, and can be matched with Mofs material for use, so that the passivation effect of the hole transport layer is better.
In some embodiments, the material of the hole transport layer is nickel oxide. The hole transport layer is nickel oxide, and Ni in the hole transport layer 3+ Hole transport of the cell is enhanced while it is near the perovskite host layerNi of the contact surface 3+ Complexing with Mofs material can avoid the influence on perovskite main body layer to a certain extent, further improves the conversion efficiency and stability of perovskite solar cell.
In some embodiments, the passivation layer has a thickness of 100nm or less. The perovskite solar cell can be better in stability.
In some embodiments, the passivation layer has a thickness of 10nm to 40nm. The stability of the perovskite solar cell is improved, and meanwhile, the conversion efficiency of the perovskite solar cell can be improved.
In a third aspect, embodiments of the present application provide a photovoltaic module comprising the perovskite solar cell provided by any one of the embodiments of the second aspect.
In a fourth aspect, embodiments of the present application provide a photovoltaic system, including the photovoltaic module provided in the third aspect.
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic layer structure of a perovskite solar cell module provided in some embodiments of the present application;
FIG. 2 is an XRD pattern of the Mofs material provided herein;
FIG. 3 is a schematic diagram of a first structure of a Mofs material according to embodiment a of the present application;
fig. 4 is a second schematic structural diagram of the Mofs material provided in embodiment a of the present application;
fig. 5 is a schematic diagram of a third structure of the Mofs material provided in embodiment a of the present application.
Icon: 110-a transparent substrate; 120-a first electrode; 130-a hole transport layer; 140-passivation layer; a 150-perovskite host layer; 160-a charge transport layer; 170-a second electrode.
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Unless defined otherwise, 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 application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description and claims of the present application and in the description of the figures above are intended to cover non-exclusive inclusions.
In the description of the embodiments of the present application, the technical terms "first," "second," etc. are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, which means that three relationships may exist, for example, a and/or B may mean: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" refers to two or more (including two), and similarly, "plural sets" refers to two or more (including two), and "plural sheets" refers to two or more (including two).
In the description of the embodiments of the present application, the orientation or positional relationship indicated by the technical terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. are based on the orientation or positional relationship shown in the drawings, and are merely for convenience of describing the embodiments of the present application and for simplifying the description, rather than indicating or implying that the apparatus or element referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the embodiments of the present application.
In the description of the embodiments of the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured" and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally formed; or may be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the embodiments of the present application will be understood by those of ordinary skill in the art according to the specific circumstances.
Currently, the more widely the application of solar cells is seen from the development of market situation. The application of the solar battery has entered the departments of industry, business, agriculture, communication, household appliances, public facilities and the like from the military field and the aerospace field, and the solar battery can be used in remote areas, mountains, deserts, islands and rural areas in a scattered manner, so that the expensive power transmission line is saved. With the continuous expansion of the application field of solar cells, the market demand of the solar cells is also continuously expanding.
Perovskite solar cells are one type of solar cells, and are solar cells using perovskite type organic metal halide semiconductors as light absorbing materials, and belong to the third generation of solar cells, also called new concept solar cells.
The perovskite solar cell has two main structures, namely a formal structure (from bottom to top, a photoelectric glass-electron transport layer-perovskite main body layer-hole transport layer-electrode) and a trans-structure (from bottom to top, a photoelectric glass-hole transport layer-perovskite main body layer-electron transport layer-electrode). The trans-structure is receiving a great deal of attention because it can be processed at low temperature and has a simpler device structure and gives consideration to stability, and is one of the important routes for realizing commercial photovoltaic modules.
Nickel oxide (NiOx) is an ideal hole transport layer in the trans-structure of perovskite solar cells due to its ideal band gap, low processing cost, high transmittance in the incident light band, and strong processability. Ni in nickel oxide 3+ Hole transport of the cell is enhanced, but if Ni 3+ Appears on the surface of the nickel oxide layer, i.e. is in direct contact with the perovskite absorption layer, since the main material of the perovskite main body layer is ABC 3 Wherein A is typically a small-sized organic cation (e.g., CH 3 NH 3 + (MA)，CH 2 (NH 2 ) 2 (FA)) containing H; b is typically a transition metal divalent ion; c is a halogen ion. With the main material of the perovskite main body layer being CH 2 (NH 2 ) 2 PbI 3 For illustration, ni 3+ With main material of CH 2 (NH 2 ) 2 PbI 3 After the perovskite main body layer is directly contacted, the perovskite absorption layer is degraded, and the degradation mechanism is as follows:
CH 2 (NH 2 ) 2 PbI 3 →PbI 2 ·CH 2 (NH 2 ) 2 I
CH 2 (NH 2 ) 2 I+Ni 3+ O x →CH 2 (NH 2 ) 2 + +I 2 +NI 2+ O x H
the degradation of the perovskite main body layer can reduce the stability and open circuit voltage of the perovskite solar cell, thereby affecting the energy conversion efficiency, so that a certain passivation treatment is required to be carried out on the nickel oxide layer. The current common approach is to separate the perovskite host layer from the hole transport layer mainly by doping an auxiliary organic macromolecular layer, such as PTAA (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine) material.
The inventor provides a new material for passivating the hole transport layer, wherein the material is a Mofs material, and the repeated structural units of the Mofs material are as follows:
wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is a primary amine cation.
In the perovskite battery, the Mofs material can be used as a passivation layer material of a hole transport layer, five-membered heterocycle in the Mofs material has p-pi conjugation capacity shared by aromatics, a metal atom is used as a network node, a halogen atom and an oxygen atom of five-membered heterocycle dicarboxylic acid are used as bridges, and metal halide and five-membered heterocycle dicarboxylic acid are coordinated and connected to form a three-dimensional anion frame, so that stronger electron cloud and weaker covalent bond with conductivity can be alternately existing in the passivation layer and matched with primary amine cations, and hole carrier separation can be promoted, thereby improving the conversion efficiency and stability of the perovskite solar battery.
Where M is Pb (M in all repeating structural units is Pb), or M is Sn (M in all repeating structural units is Sn), or M is Bi (M in all repeating structural units is Bi), or M is Pb and Sn (M in some repeating structural units is Pb, M in some repeating structural units is Sn), or M is Pb and Bi (M in some repeating structural units is Pb, M in some repeating structural units is Bi), or M is Sn and Bi (M in some repeating structural units is Sn, M in some repeating structural units is Bi), or M is Pb, sn and Bi (M in some repeating structural units is Pb, M in some repeating structural units is Sn, M in some repeating structural units is Bi).
R 1 Is O (R in all repeating structural units 1 All are O), or R 1 For S (R in all repeating structural units 1 All S), or R 1 Is N (R in all repeating structural units 1 All N), or R 1 Is O and S (R in some repeating structural units 1 Is O, R in some repeating structural units 1 S), or R 1 Is O and N (R in some repeating structural units 1 Is O, R in some repeating structural units 1 N), or R 1 Is S and N (R in some repeating structural units 1 For S, R in some repeating structural units 1 N), or R 1 For O, S and N (R in some repeating structural units 1 Is O, R in some repeating structural units 1 For S, R in some repeating structural units 1 N).
In some embodiments, R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation. For example: r is R 2 Is a methylamine cation (R in all repeating structural units 2 All methylamine cations), or R 2 Is dimethylamine cation (R in all the repeating structural units 2 All dimethylamine cations), or R 2 Is a trimethylamine cation (R in all repeating structural units 2 All trimethylamine cations), or R 2 Is a methylamine cation and a dimethylamine cation (R in some repeating structural units 2 R in some repeating structural units being methylamine cations 2 Dimethylamine cation), or R 2 Is a methylamine cation and a trimethylamine cation (R in some repeating structural units 2 R in some repeating structural units being methylamine cations 2 Trimethylamine cation), or R 2 Is dimethylamine cation and trimethylamine cation (R in some repeating structural units 2 As dimethylamine cation, R in some repeating structural units 2 Trimethylamine cation), or R 2 Is methylamine cation, dimethylamine cation and trimethylamine cation (R in some repeating structural units 2 R in some repeating structural units being methylamine cations 2 As dimethylamine cation, R in some repeating structural units 2 Is trimethylamine cation). The methylamine cation can stabilize the framework of the passivation layer material, and further improve the stability of the perovskite solar cell.
In the application, the alkyl chains of the methylamine cations are provided with hydrogen atoms, so that hydrogen bonds C-H … O can be formed with O of the anion frame in the repeated structural unit, and the structural stability of the Mofs material is enhanced; at the same time, methylamine cations and R 1 (O, S, N) at least one of the components has a charge effect, so that methylamine cations are not easy to separate from the system, and the stability is enhanced; and the amine positive charges in the methylamine positive ions can be bonded with the charge of the perovskite to connect the crystal lattice, when the perovskite carries out hole carrier separation under the sunlight, according to energy level band gap matching, the carriers move to one side of the electron transport layer, and the holes move to the hole transport layer, and the passivation layer has the effect of accelerating the transfer of the holes to the main body frame of the passivation layer material by taking the methylamine positive ions as the hinges.
In some embodiments, R 2 Selected from dimethylamine cations or trimethylamine cations. The methylamine cation can make up perovskite solar energyAnd the perovskite main body layer in the cell is defective, so that the performance of the perovskite solar cell is improved.
In some embodiments, M is selected from one of Pb, sn, bi. The three metal elements have strong coordination capability, can form coordination with the metal elements in the perovskite main body layer in the perovskite solar cell, and can form chemical bond connection between the passivation layer and the perovskite main body layer.
In some embodiments, R 1 One selected from S, O, N. The three five-membered heterocyclic dicarboxylic acid structures are favorable for forming a three-dimensional anion frame, so that the passivation effect of a passivation layer formed by the Mofs material is better; meanwhile, the electronegativity of the S, O, N five-membered heterocycle has a certain difference, and the electric cloud density of the anion frame can be influenced to different degrees, so that different coordination modes of the anion frame are formed, the band gap of the Mofs material has a certain difference, and the requirements of different perovskite solar cells are met.
In some embodiments, X is selected from one of Cl, br, I. The metal halides formed by the three halogen elements are favorable for forming a three-dimensional anion frame, can be consistent with the halogen elements in the perovskite main body layer in the perovskite solar cell, and are favorable for improving the passivation effect of the passivation layer. Meanwhile, after different halogen elements are matched with metal ions, the Mofs material can be used as a passivation layer to have different band gaps so as to match the energy levels of perovskite solar cells of different systems.
In some embodiments, M is Pb, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine. The repeated structural units of the Mofs material are as follows:
wherein X is Cl or Br.
Mofs material is { [ (PbX) (TDC)]·[(CH 3 ) 2 NH 2 ]} n If the metal in the perovskite host layer in a perovskite solar cellThe cation being Pb 2+ Can more easily form coordination with metal element Pb in Mofs material so as to make the combination capability between perovskite layer and passivation layer better, thereby improving the performance of perovskite battery.
In some embodiments, M is Sn, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine. The repeated structural units of the Mofs material are as follows:
wherein X is Cl or Br.
Mofs material is { [ (SnX) (TDC)]·[(CH 3 ) 2 NH 2 ]} n If the metal cation in the perovskite host layer in the perovskite solar cell is Sn 2+ Can more easily form coordination with metal element Sn in Mofs material, so that the combination capability between the perovskite layer and the passivation layer is better, thereby improving the performance of the perovskite battery.
In some embodiments, M is Bi, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine. The repeated structural units of the Mofs material are as follows:
wherein X is Cl or Br.
Mofs material is { [ (BiX) (TDC)]·[(CH 3 ) 2 NH 2 ]} n If the metal cation in the perovskite host layer in the perovskite solar cell is Bi 2+ The complex can be formed with the metal element Bi in the Mofs material more easily, so that the combination capability between the perovskite layer and the passivation layer is better, and the performance of the perovskite battery is improved.
In some embodiments, the Mofs material meets at least one of the following: the aperture of the Mofs material isThe Mofs material is a hexagonal system; the space group of the Mofs material is P6mm; the unit cell parameters of the Mofs material are: α=β=90°, γ=120°. The aperture, crystal system, space group and unit cell parameters of the Mofs material meet the conditions, and the complex structure unit of the Mofs material is matched with the complex structure unit of the Mofs material so as to determine the coordination mode of the Mofs material, and the passivation effect of the material is good.
With the main material of the perovskite main body layer being CH 2 (NH 2 ) 2 PbI 3 The Mofs material is { [ (PbCl) (TDC)]·[(CH 3 ) 2 NH 2 ]} n The material of the passivation layer is nickel oxide NiO x For example, the protection mechanism of the passivation layer is as follows:
{[(PbCl)(TDC)]·[(CH 3 ) 2 NH 2 ]} n +Ni 3+ O x →{[(PbCl)(TDC)]·[(CH 3 ) 2 NH]} n +Ni 2+ O x H
at this time, the nickel oxide interface passivation layer material is a periodic metal organic framework material (Mofs) formed by coordination of lead chloride and 2, 5-thiophene dicarboxylic acid, is a three-dimensional network anion-cation counter-balance structure, and can be divided into an anion part and a cation part. The anion part is a material main part, and is mainly formed by coordination and connection of lead chloride and 2, 5-thiophene dicarboxylic acid into a three-dimensional anion frame ({ [ (PbCl) (TDC) ] - ) The three-dimensional network anion frame structure with negative charge and nanometer size is formed by connecting lead atoms as network nodes, cl atoms and oxygen atoms of 2, 5-thiophene dicarboxylic acid as bridges, and the anion frame with carboxyl can well lead Ni on the surface of nickel oxide 3+ Oxidation to Ni 2+ Ni is reduced 3+ Degradation of the perovskite host layer; the cationic part is mainly organic amine small molecule [ (CH) with positive charge 3 ) 2 NH 2 ] + Such [ (CH) 3 ) 2 NH 2 ] + The positive charges are regularly distributed in the nanoscale pores of the anion framework, so that the hole extraction capacity of the nickel oxide can be enhanced.
In the application, the nickel oxide interface passivation layer material can also play a role of a 'barrier layer', and isolate the nickel oxide layer from direct contact with the perovskite main body layer. In the continuous power generation process of the perovskite solar cell, the heterojunction interface of the nickel oxide layer inevitably contains Ni 3+ When the perovskite is directly contacted with the perovskite, degradation catalysis is generated on the perovskite. The passivation layer material provided by the application can avoid the phenomenon, is a Mofs material formed by coordination of carboxylic acids and lead chloride, and can strongly passivate Ni by carboxyl 3+ And a chemical bond is formed with the surface of the nickel oxide layer, so that the heterojunction effect is enhanced, and meanwhile, the passivation layer material is rich in amine cations of lead chloride, so that the passivation layer material can be well attached to a perovskite main body layer, and the lattice force and the chemical stability of the perovskite main body layer are enhanced. Meanwhile, the five-membered heterocycle has p-pi conjugation capacity shared by aromatics, stronger electron cloud and weaker covalent bond of conductivity are alternately present in the passivation layer to further enhance the photoproduction hole separation capacity, and the five-membered heterocycle has better effect on improving the open-circuit voltage and FF of the perovskite solar cell.
After the Mofs material is introduced, the following specific description is given to the preparation method of the Mofs material:
in the application, a mixed solvent thermal method is adopted to prepare the Mofs material. Mixing metal halide and five-membered heterocyclic dicarboxylic acid, adding the mixture into a polytetrafluoroethylene lining container, adding a mixed solvent containing an amine source, adding acid liquor, and uniformly mixing to obtain mixed precursor liquid, wherein the pH value of the mixed precursor liquid is kept between 2 and 4. Then preserving heat for 40-50 h at 100-140 ℃, then cooling, and standing for 4-5 days to obtain the Mofs material. As an example, the temperature of the incubation may be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ or 140 ℃, which may also be any value of the above ranges; the time of heat preservation can be 40h, 42h, 44h, 46h, 48h or 50h, and can also be any value in the range; the time for standing after cooling may be 4 days, 4.2 days, 4.4 days, 4.6 days, 4.8 days or 5 days, and it may be any value within the above range.
Wherein the metal halide can be at least one of Pb halide, sn halide and Bi halide; the metal in the metal halide corresponds to M in the repeating structural unit of the Mofs material. The five-membered heterocyclic dicarboxylic acid may be at least one of 2, 5-thiophenedicarboxylic acid, 2, 5-furandicarboxylic acid, 1H-pyrrole-2, 5-dicarboxylic acid. The heteroatom in the five-membered heterocyclic dicarboxylic acid corresponds to R1 in the repeating structural unit of the Mofs material.
Alternatively, the molar ratio of metal halide to five membered heterocyclic dicarboxylic acid is 1: (1-3). Illustratively, the molar ratio of metal halide to five-membered heterocyclic dicarboxylic acid is 1:1, 1:1.5, 1:2, 1:2.5, or 1:3, which may also be any value within the above ranges.
The amine source in the mixed solvent corresponds to R2 in the repeated structural unit of the Mofs material, and if R2 is methylamine, the amine source can be N, N-dimethylformamide or/and N, N-dimethylacetamide; if R2 is dimethylamine, the amine source can be N, N-dimethylformamide or/and N, N-dimethylacetamide; if R2 is trimethylamine, the amine source may be acetonitrile or/and N, N-dimethylacetamide. For example: the mixed solvent can be a mixture of N, N-dimethylacetamide, deionized water and acetonitrile; alternatively, the volume ratio of N, N-dimethylacetamide, deionized water and acetonitrile is (2-6): (2-4): (0.5-1.5), as an example, the volume ratio of N, N-dimethylacetamide, deionized water and acetonitrile is 2:2:0.5, 2:3:0.5, 2:2:1, 2:2:1.5, 4:2:0.5, 4:3:0.5, 4:2:1, 4:2:1.5, 6:2:0.5, 6:3:0.5, 6:2:1 or 6:2:1.5, which may also be any value within the above range; the molar volume ratio of the metal halide to the mixed solvent is 1mmol (6 to 10 mL), and as an example, the molar volume ratio of the metal halide to the mixed solvent may be 1 mmol/6 mL, 1 mmol/7 mL, 1 mmol/8 mL, 1 mmol/9 mL, 1 mmol/10 mL, and it may be any value within the above range.
The acid liquid can be sulfuric acid, perchloric acid and the like; for example, the acid solution is perchloric acid, the molar ratio of metal halide to perchloric acid is 1 (3-5), and as an example, the molar ratio of metal halide to perchloric acid is 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, which may also be any value within the above ranges.
If the repeating structural unit of the Mofs material is:
wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation.
The preparation method of the Mofs material comprises the following steps: mixing metal halide (such as Pb halide, sn halide or Bi halide, wherein halogen element is F, cl, br or I) and five-membered heterocyclic dicarboxylic acid (such as 2, 5-thiophene dicarboxylic acid, 2, 5-furan dicarboxylic acid or 2, 5-pyrrole dicarboxylic acid), adding into a polytetrafluoroethylene lining container, adding a mixed solvent containing N, N-dimethylacetamide, adding acid solution, uniformly mixing to obtain mixed precursor liquid, and keeping the pH value of the mixed precursor liquid at 2-4. Then preserving heat for 40-50 h at 110-150 ℃, then cooling, and standing for 4-5 days to obtain the Mofs material.
If M in the repeated structural unit of the Mofs material is at least two of Pb, sn and Bi, the common preparation method is as follows: m in all the repeating structural units is a metal element (e.g., pb) and then is left to stand in a solution of N 'N-dimethylacetamide or N' N-dimethylformamide containing another metal ion (e.g., sn) for a period of time (e.g., 10 hours, the solution may be maintained at 40 to 60 ℃ to accelerate diffusion) so that part of Pb is replaced with Sn.
If R in the repeating structural unit of Mofs material 1 At least two of O, S, N, the general preparation methods are: in the preparation, the desired repeating units are mixed together with metal halides, e.g. after fixing the ratio of metal halides to five-membered heterocyclic dicarboxylic acids, R is different 1 Partial five-membered heterocyclic dicarboxylic acidMixing according to the proportion of the required repeating units.
If X in the repeated structural units of the Mofs material is at least two of halogens, the common preparation method is as follows: the metal halides of different metals and different halogens are mixed according to the requirement, the ratio of the sum to the five-membered heterocyclic dicarboxylic acid is fixed, and the five-membered heterocyclic dicarboxylic acid can be prepared in one step by a solvent method.
If R in the repeating structural unit of Mofs material 2 At least two primary amine cations are commonly prepared by the following steps: preparation of R in all repeating structural units 2 Is a primary amine cation (such as dimethylamine cation), then is soaked in organic liquid of the organic amine cation type to be replaced, and can replace part of dimethylamine cation after being soaked for a certain time.
If M is selected from one of Pb, sn and Bi in the repeating structural unit of Mofs material, R 1 Selected from one of S, O, N, X is selected from one of Cl, br and I, R 2 Selected from dimethylamine cations or trimethylamine cations. In general, in the selection of raw materials for preparing Mofs materials, the metal chloride is a single metal chloride (for example, lead chloride), and the five-membered heterocyclic dicarboxylic acid is selected from one of 2, 5-thiophene dicarboxylic acid, 2, 5-furan dicarboxylic acid and 2, 5-pyrrole dicarboxylic acid, and the mixed solvent contains N, N-dimethylacetamide and acetonitrile.
In some embodiments, if the repeat structural units of the Mofs material are:
wherein X is Cl or Br.
The preparation method of the Mofs material comprises the following steps: mixing lead chloride or lead bromide and 2, 5-thiophene dicarboxylic acid (the mol ratio of the lead chloride to the 2, 5-thiophene dicarboxylic acid is 1:2), adding the mixture into a polytetrafluoroethylene lining container, adding a mixed solvent (the mixed solvent is N, N-dimethylacetamide, deionized water and acetonitrile with the volume ratio of 4:3:1 in sequence), adding perchloric acid (the mol ratio of the lead chloride to the perchloric acid is 1:4), and stirring at 25 ℃ for 30min at 800rpm to obtain uniformly mixed precursor liquid. Sealing the polytetrafluoroethylene lining filled with the mixed precursor liquid into a stainless steel container, heating at 120 ℃ for 48 hours, then cooling to 25 ℃ at a constant speed within 72 hours, and standing for 120 hours to obtain the Mofs material. The specific reaction formula is as follows:
After the above description of the Mofs material and the preparation method thereof, the application of the Mofs material is described below, and the Mofs material is mainly used as a passivation material of a hollow transport layer in a perovskite solar cell.
Fig. 1 is a schematic layer structure of a perovskite solar cell module provided in the present application, referring to fig. 1, the perovskite solar cell includes a transparent substrate 110, a first electrode 120, a hole transport layer 130, a passivation layer 140, a perovskite body layer 150, a charge transport layer 160, and a second electrode 170, which are sequentially disposed from bottom to top.
The transparent substrate 110 may be a glass substrate, or a transparent flexible substrate (e.g., PI, PET, PEN, PVA).
The material of the first electrode 120 may be a metal conductive material (e.g., at least one of Au, ag, cu), and the first electrode 120 may also be a metal conductive oxide (e.g., fluorine-doped tin oxide, indium tin oxide), and the first electrode 120 is a transparent electrode for light incidence. Alternatively, the thickness of the first electrode 120 layer is 50nm to 600nm.
The material of the hole transport layer 130 is an inorganic metal compound. The metal ions in the inorganic metal compound tend to form unstable metal cations having a higher valence after being irradiated with light, and after contacting the perovskite host layer 150, the metal cations affect the stability of the perovskite host layer 150. Alternatively, the thickness of the hole transport layer 130 is 10nm to 50nm.
The passivation layer 140 is made of the foregoing Mofs material. Optionally, the passivation layer 140 has a thickness of 100nm or less. As an example, the thickness of the passivation layer 140 may be 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100nm, which may also be any value within the above range. In some embodiments, the passivation layer 140 has a thickness of 10nm to 40nm.
The perovskite main body layer 150 material has a chemical formula of ABC 3 Wherein A comprises at least one of methylamine cation, formamidine cation and cesium ion; b includes Pb 2+ 、Sn 2+ 、Bi 2+ At least one of (a) and (b); c includes Cl - 、Br - 、I - At least one of them. As the material of the perovskite main body layer 150, the perovskite main body layer can be matched with the passivation layer 140 and the hole transport layer 130 to perform the passivation effect on the hole transport layer 130, thereby improving the conversion efficiency and the stability of the perovskite solar cell. Alternatively, the perovskite host layer 150 has a thickness of 300nm to 1000nm.
The material of the charge transport layer 160 may be at least one or a mixture of the following materials and derivatives thereof: imide compounds, quinone compounds, fullerenes and derivatives thereof, 2', 7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ](PTAA), calcium titanate (CaTiO) 3 ) Lithium fluoride (LiF), calcium fluoride (CaF) 2 ) Poly (3, 4-ethylenedioxythiophene) polystyrene sulphonic acid (PEDOT: PSS), poly (3-hexylthiophene) (P3 HT), triptycene nucleated triphenylamine (H101), 3, 4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N- (4-aniline) carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides (the metal element is selected from Mg, ni, cd, zn, in, pb, mo, W, sb, bi, cu, hg, ti, ag, mn, fe, V, sn, zr, sr, ga, or Cr), silicon oxide (SiO) 2 ) Strontium titanate (SrTiO) 3 ) Copper thiocyanate (CuSCN). Alternatively, the thickness of the charge transport layer 160 is 15nm to 100nm.
The material of the second electrode 170 may be a metallic conductive material (e.g., at least one of Au, ag, cu), and the first electrode 120 may also be a metallic conductive oxide (e.g., conductive glass or/and indium tin oxide). Alternatively, the thickness of the second electrode 170 layer is 50nm to 200nm.
In the application, the passivation layer 140 composed of the Mofs material is disposed between the hole transport layer 130 and the perovskite main body layer 150 formed by the inorganic metal compound, so that high-valence metal cations and the Mofs material can be complexed, and are converted into low-valence metal cations, thereby avoiding the influence on the perovskite main body layer 150 and improving the conversion efficiency and stability of the perovskite solar cell.
The Mofs material contained in the passivation layer 140 satisfies the above-mentioned repeated structural unit, on one hand, the hole transport layer 130 and the perovskite main body layer 150 can be separated, on the other hand, the five-membered heterocycle in the Mofs material has p-pi conjugation capability shared by aromatics, metal atoms are taken as network nodes, halogen atoms and oxygen atoms of the five-membered heterocycle dicarboxylic acid are taken as bridges, and the metal halides and the five-membered heterocycle dicarboxylic acid are coordinately connected to form a three-dimensional anion frame, so that stronger electron cloud and a covalent bond with weaker conductivity can be alternately present in the passivation layer 140 and matched with primary amine cations, and separation of hole carriers can be promoted, thereby improving the conversion efficiency and stability of the perovskite solar cell.
In some embodiments, the material of hole transport layer 130 includes at least one of nickel oxide, copper iodide, copper thiocyanate. The material has good hole transport effect, and can be matched with Mofs material for use, so that the passivation effect of the hole transport layer 130 is better.
In some embodiments, the material of the hole transport layer 130 is nickel oxide. The hole transport layer 130 is nickel oxide, and Ni inside the hole transport layer 130 3+ Hole transport of the cell is enhanced while Ni, which is close to the surface where the perovskite body layer 150 contacts 3+ Complexing with Mofs material can avoid the influence on perovskite main body layer 150 to a certain extent, further improves the conversion efficiency and stability of perovskite solar cell.
In some embodiments, M is Pb, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Dimethylamine, pb in the perovskite main body layer 150 material B 2+ . The metal cation Pb in the perovskite host layer 150 can be caused to 2+ Form coordination with the metal element Pb in the Mofs material so as to make the bonding capability between the perovskite layer and the passivation layer 140 better, thereby improving the performance of the perovskite battery.
In some embodiments, in the repeating structural units of the Mofs material, M is Sn, R 1 Is S, X is Cl or Br, R 2 Dimethylamine, B in the perovskite main body layer 150 material is Sn 2+ . The metal cations Sn in the perovskite host layer 150 may be made 2+ Coordination is formed with the metal element Sn in the Mofs material so as to make the bonding capability between the perovskite layer and the passivation layer 140 better, thereby improving the performance of the perovskite battery.
In some embodiments, M is Bi, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Dimethylamine, B in the perovskite main layer 150 material being Bi 2+ . The metal cations Bi in the perovskite host layer 150 can be made to 2+ Form coordination with the metal element Bi in the Mofs material so as to make the bonding capability between the perovskite layer and the passivation layer 140 better, thereby improving the performance of the perovskite battery.
The perovskite solar cell can be assembled into a photovoltaic module, and then the photovoltaic module can be prepared into a photovoltaic system.
Having described the structure of the perovskite solar cell, the following specifically describes a method for manufacturing a perovskite solar cell module:
with continued reference to fig. 1, the preparation method includes the following steps:
(1) A group of FTO conductive glass with the specification of 100mm multiplied by 100mm is etched by using infrared laser according to the figure 1, the width of P1 is 20-50 mu M, the whole glass is etched into a plurality of sub-cells, the series resistance of different sub-cells is more than 10MΩ, and the upper and lower 5-20 mm are respectively used as the welding area of the component.
(2) The etched conductive glass surface is washed with acetone and isopropanol in sequence for a plurality of times, immersed in deionized water, subjected to ultrasonic treatment for 5-20 min, and dried in an inert atmosphere to serve as the first electrode 120.
(3) Placing the product obtained in the step (2) into a magnetron sputtering device, and depositing a layer of inorganic metal compound material as the hole transport layer 130.
(4) The Mofs material is placed in a solvent (for example, ethyl acetate, cyclohexane, isopropanol and absolute ethyl alcohol) to obtain a Mofs material suspension with the concentration of 3 mg/mL-10 mg/mL, and then the Mofs material suspension is deposited on the surface of the hole transport layer 130 in a spraying mode, and is annealed at the temperature of 80-150 ℃ for 5-30 min.
(5) Printing the material of the perovskite main body layer 150 on the passivation layer 140 by adopting an ink-jet printing method, and annealing for 5-30 min at the temperature of 80-150 ℃.
(6) Placing the product obtained in the step (5) into vacuum thermal evaporation equipment, and vacuumizing to 2X 10 - 4 Pa～10×10 -4 Pa, a charge transport layer 160 is deposited.
(7) And continuing to deposit the metal conductive material or the metal conductive oxide in the vacuum thermal evaporation equipment, and then taking out.
(8) And (3) carrying out laser etching on the product obtained in the step (7) according to the figure 1, wherein the width of the P2 is 100-200 mu m, the product is deeply etched to the FTO conductive glass layer, and the interval between the P2 and the P1 is 10-30 mu m.
(9) Placing the product obtained in the step (8) in vacuum thermal evaporation equipment again, and vacuumizing to 2×10 - 4 Pa～10×10 -4 Pa, continuing to deposit the metal conductive material or the metal conductive oxide to form a second electrode 170, and then cooling and taking out.
(10) And (3) carrying out P second green laser etching on the product obtained in the step (9) according to the figure 1, wherein the width of the P3 is 10-30 mu m, the P3 is deeply etched to the FTO conductive glass layer, and the interval between the P3 and the P2 is 10-30 mu m (the positions of etching lines are P1, P2 and P3 shown in the figure 1 in sequence).
(11) And (3) carrying out infrared edge cleaning on the product obtained in the step (10), namely respectively etching 5-20 mm at two sides of the component, and finally obtaining the perovskite solar cell component.
One or more embodiments are described in more detail below with reference to the examples below. Of course, these examples do not limit the scope of one or more embodiments.
Example a
Preparing Mofs material:
mixing lead chloride and 2, 5-thiophene dicarboxylic acid (TDCA) according to a molar ratio of 1:2, adding the mixture into a polytetrafluoroethylene lining, adding a mixed solvent according to a volume ratio of lead chloride to mixed solvent=1 mmol to 8mL (mixed solvent is used for mixing N, N-Dimethylacetamide (DMAC) with deionized water according to a volume ratio of acetonitrile=4:3:1), adding perchloric acid according to a molar ratio of lead chloride to perchloric acid=1:4, and stirring at a speed of 800rpm for 30min at 25 ℃ to obtain uniform mixed precursor liquid. Sealing the polytetrafluoroethylene lining filled with the mixed precursor liquid into a stainless steel container, heating for 48 hours at 120 ℃, then cooling to 25 ℃ at uniform speed within 72 hours, and standing for 120 hours to obtain the Mofs material.
Example b
This embodiment differs from embodiment a in that: the lead chloride as raw material is replaced by lead bromide, and other preparation methods and raw materials are the same.
Fig. 2 is an XRD pattern of the Mofs material provided in the present application, wherein fig. 2 (left hand side) is an XRD pattern of the Mofs material provided in example a, and fig. 2 (right hand side) is an XRD pattern of the Mofs material provided in example b. The crystallographic data and structural parameters of the Mofs materials provided in examples a and b are shown in table 1.
TABLE 1 crystallographic data and structural parameters of Mofs materials
The structure of the Mofs material provided in example a was determined by single crystal X-ray diffraction. FIG. 3 is a schematic diagram of a first structure of a Mofs material according to embodiment a of the present application; fig. 4 is a second schematic structural diagram of the Mofs material provided in embodiment a of the present application; fig. 5 is a schematic diagram of a third structure of the Mofs material provided in embodiment a of the present application. Referring to FIGS. 3-5, the three-dimensional (3D) anionic framework of the compound is formed from a variable one-dimensional inorganic (PbCl) n n+ The chain (FIG. 3 (b)) is constructed by interconnecting 2, 5-Thiophene Dicarboxylate (TDC) (FIG. 3 (a)). Analysis of the crystal structure shows (Table 1) that the compound is P6 in the hexagonal 6 space point group 1 Each asymmetric unit of the compound comprises a lead ion, a chlorine atom and a TDC molecule, and the cavity comprises a charge-balancing dimethylamine cation. The central metal lead ion adopts an eight-atom coordination mode, and two chlorine atoms and six carboxyl oxygen atoms respectively from four different TDCs coordinate to form twisted PbO 6 Cl 2 Dodecahedron unit (fig. 3 (c)). The bond length of Pb-O bond of the compound is 2.507 (7) to 2.8885 (1)Within the range of the bond angle of O-Pb-O between 49.13 (19) and 161.58 (17), but having a Pb-O bond (Pb (1) -O (3), 2.8885 (1) ) The bond length is higher than that of the common Pb-O bond, which indicates that the bond strength between the two is weaker, therefore, the half-oriented seven-coordinated PbO is used 5 Cl 2 The pentagonal bipyramid polyhedron or highly distorted 7+1 coordination mode describes that the coordination of lead ions in the compound is more suitable, and the bond lengths of Pb-Cl bonds are 2.892 (2), respectivelyAnd 3.045 (3)。
The three-dimensional anionic framework of the compound can be found to have protonated dimethylamine cation [ (CH) around the three-dimensional pore canal of the compound 3 ) 2 NH 2+ ](FIG. 4 (a)). From the analysis of the reaction raw materials, [ (CH) 3 ) 2 NH 2+ ]The only possible source of (a) is from the decomposition of DMAC (N, N-dimethylacetamide) in an acidic environment at high temperatures. The compound is similar to a flower cluster three-dimensional anion frame, pbO is bridged from two different directions by TDC 6 Cl 2 A polyhedral one-dimensional chain, in which a crystal view along the c-axis shows a one-dimensional triangular channel (2.8x2.8) (FIG. 5 (a)) such triangular channels along the c-axis are defined by [ (CH) 3 ) 2 NH 2+ ]Orderly filled according to conservation of charge, and [ (CH) 3 ) 2 NH 2+ ]And the presence of C-H. O, N-H.O and C-H.Cl hydrogen bonds between TDC helps to further promote structural stabilization of the compound. Thus, based on the above analysis, the formula of the Mofs material provided in example a is: { [ (PbCl) (TDC) ]·[(CH 3 ) 2 NH 2 ]} n (n represents only periodic repetition) of the repeating structural unit:
the formula of the Mofs material provided in example b is: { [ (PbBr) (TDC)]·[(CH 3 ) 2 NH 2 ]} n (n represents only periodic repetition).
Example 1
Preparation of perovskite solar cell (see fig. 1):
(1) A group of FTO conductive glass with the specification of 100mm multiplied by 100mm is etched by using infrared laser, the width of P1 is 30 mu M, the whole glass is etched into 10 sub-cells, the series resistance of the different sub-cells is more than 10MΩ, and the upper and lower 10mm are used as the welding areas of the components.
(2) Washing the etched conductive glass surface with acetone and isopropanol for 2 times, soaking in deionized water, ultrasonic treating for 10min, drying in a forced air drying oven, and placing in a glove box (N) 2 Atmosphere), as the first electrode 120.
(3) The cleaned conductive glass was placed in a magnetron sputtering apparatus, and a hole transport layer 130 was deposited, with a nickel oxide layer having a thickness of about 15nm.
(4) And (3) depositing the prepared ethyl acetate ultrasonic suspension of 5mg/mL Mofs material on the surface of the nickel oxide layer in a spraying manner, and then annealing at 100 ℃ for 10min to obtain a passivation layer 140 with a film thickness of about 15nm.
(5) Printing FAPbI on passivation layer 140 using inkjet printing 3 The perovskite bulk layer 150, having a thickness of about 500nm, was annealed at 100℃for 10 minutes.
(6) Placing the substrate with the perovskite body layer 150 into a vacuum thermal evaporation device, and vacuumizing to 4×10 -4 Pa, 30nm c60 is deposited as the component charge transport layer 160.
(7) After the charge transport layer 160 was deposited in the vacuum thermal evaporation apparatus, it was continuously deposited with 10nm Ag on the surface and then broken into vacuum and taken out.
(8) And (3) performing laser etching, wherein the width of the P2 is 150 mu m, and the depth etching is performed on the FTO layer, and the interval between the P2 and the P1 is 20 mu m.
(9) Placing the substrate into evaporation equipment again, and vacuumizing to 4×10 -4 And (3) continuously depositing a layer of Ag with the thickness of about 80nm after Pa, and then cooling and taking out.
(10) P second green laser etches P3, P3 width is 15 μm, depth etches to FTO layer, P3 and P2 interval is 20 μm.
An infrared clean is then used on the assembly, i.e. 10mm on each side of the assembly.
Other perovskite solar cells differ from example 1 in that: the perovskite host layer 150 material, the hole transport layer 130 material, the passivation layer 140 material, and the passivation layer 140 thickness are as specified in table 2.
The perovskite solar cell performance was tested, the test results are shown in table 2, and the test method is as follows:
the photovoltaic characteristic curve of the module under irradiation of the light source is measured by using a four-channel digital source meter (Keithley 2440) at normal temperature and pressure by using a standard light source with a sunlight analog light source of AM1.5G to obtain an open-circuit voltage Voc, a short-circuit current density Jsc and a filling factor FF (Fill Factor) of the module, thereby obtaining the energy conversion efficiency Eff (Efficiency) of the module.
After the test is finished, the battery is placed in an atmosphere (the relative humidity is 65-80%, the ambient temperature is about 15-30 ℃), the energy conversion efficiency is tested again after the battery is placed in the atmosphere for at least 500 hours, and the ratio of the component efficiency to the initial value efficiency after the battery is placed in the atmosphere for 500 hours is calculated and is used as the performance parameter of the stability of the component.
Table 2 parameters and performance of perovskite solar cells
As can be seen from table 2, in the perovskite solar cell, the provision of the Mofs material passivation layer 140 provided in the present application between the hole transport layer 130 and the perovskite main body layer 150 can improve the energy conversion efficiency of the perovskite solar cell, the effect of placing the component for 500 hours, and the stability of the cell.
As can be seen from comparison of examples 1 to 3 and examples 12 to 15, the perovskite host layer 150 is made of FAPbI 3 The material of the hole transport layer 130 is NiO x At this time, the material of the passivation layer 140Is { [ (PbBr) (TDC)]·[(CH 3 ) 2 NH 2 ]} n (n represents only periodic repetition) the perovskite solar cell can be made to perform better.
Examples 3-5 comparison shows that the perovskite host layer 150 is made of FAPbI 3 The material of the hole transport layer 130 is NiO x When the passivation layer 140 is made of { [ (PbI) (TDC) ]·[(CH 3 ) 2 NH 2 ]} n (n represents only periodic repetition), the thickness of the passivation layer 140 may make the overall performance of the perovskite solar cell better when it is 15nm to 30 nm.
Comparison of example 3, example 6 and example 7 shows that the perovskite host layer 150 is made of FAPbI 3 The passivation layer 140 is made of { [ (PbI) (TDC)]·[(CH 3 ) 2 NH 2 ]} n (n represents only periodic repetition) the passivation effect on the nickel oxide hole transport layer 130 is better.
As is clear from comparison of examples 3 and 8 to 11, the perovskite solar cell can be made to have better performance when the metal element in the perovskite host layer 150 is identical to the metal element in the material of the passivation layer 140.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Claims (20)
- The Mofs material is characterized in that the repeated structural units of the Mofs material are as follows:wherein the method comprises the steps ofM is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is a primary amine cation.
- The Mofs material according to claim 1, wherein R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation.
- The Mofs material according to claim 2, wherein the repeat structural units of the Mofs material meet at least one of the following conditions:a) M is selected from one of Pb, sn and Bi;b)R 1 one selected from S, O, N;c) X is selected from one of Cl, br and I;d)R 2 selected from dimethylamine cations or trimethylamine cations.
- A Mofs material according to claim 3, wherein the repeat structural units of the Mofs material meet one of:e) M is Pb, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine;f) M is Sn, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine;g) M is Bi, R 1 Is S, X is Cl or Br, R 2 Is dimethylamine.
- The Mofs material according to any one of claims 1 to 4, wherein the Mofs material meets at least one of:h) The aperture of the Mofs material isi) The Mofs material is a hexagonal system;j) The space group of the Mofs material is P6mm;k) The unit cell parameters of the Mofs material are as follows: α=β=90°, γ=120°.
- The perovskite solar cell is characterized by comprising a hole transport layer, a passivation layer and a perovskite main body layer which are sequentially stacked, wherein the material of the passivation layer comprises a Mofs material, and the repeated structural unit of the Mofs material is as follows:wherein M is at least one of Pb, sn and Bi; r is R 1 Is at least one of O, S, N; x is halogen; r is R 2 Is a primary amine cation.
- The perovskite solar cell of claim 6, wherein R 2 Is at least one of methylamine cation, dimethylamine cation and trimethylamine cation.
- The perovskite solar cell of claim 7, wherein the repeating structural units of the Mofs material meet at least one of the following conditions:a) M is selected from one of Pb, sn and Bi;b)R 1 one selected from S, O, N;c) X is selected from one of Cl, br and I;d)R 2 selected from dimethylamine cations or trimethylamine cations.
- The perovskite solar cell of claim 6, wherein the Mofs material meets at least one of:e) The aperture of the Mofs material isf) The Mofs material is a hexagonal system;g) The space group of the Mofs material is P6mm;h) The unit cell parameters of the Mofs material are as follows: α=β=90°, γ=120°.
- The perovskite solar cell according to any one of claims 6 to 9, wherein the perovskite host layer material has the chemical formula ABC 3 Wherein A comprises at least one of methylamine cation, formamidine cation and cesium ion; b includes Pb 2+ 、Sn 2+ 、Bi 2+ At least one of (a) and (b); c includes Cl - 、Br - 、I - At least one of them.
- The perovskite solar cell of claim 10, wherein M is Pb, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Is dimethylamine, B in the perovskite main layer material is Pb 2+ 。
- The perovskite solar cell of claim 10, wherein M is Sn, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Is dimethylamine, B in the perovskite main body layer material is Sn 2+ 。
- The perovskite solar cell of claim 10, wherein M is Bi, R in the repeating structural units of the Mofs material 1 Is S, X is Cl or Br, R 2 Is dimethylamine, B in the perovskite main layer material is Bi 2+ 。
- The perovskite solar cell according to any one of claims 6 to 9, wherein the material of the hole transport layer is an inorganic metal compound.
- The perovskite solar cell of claim 14, wherein the material of the hole transport layer comprises at least one of nickel oxide, copper iodide, copper thiocyanate.
- The perovskite solar cell of claim 15, wherein the hole transport layer material is nickel oxide.
- The perovskite solar cell of claim 15 or 16, wherein the passivation layer has a thickness of 100nm or less.
- The perovskite solar cell of claim 17, wherein the passivation layer has a thickness of 10nm to 40nm.
- A photovoltaic module comprising a perovskite solar cell according to any one of claims 6 to 18.
- A photovoltaic system comprising the photovoltaic module of claim 19.
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