CN114023889A - Perovskite solar cell array, preparation method thereof and photovoltaic module - Google Patents

Perovskite solar cell array, preparation method thereof and photovoltaic module Download PDF

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CN114023889A
CN114023889A CN202111300837.4A CN202111300837A CN114023889A CN 114023889 A CN114023889 A CN 114023889A CN 202111300837 A CN202111300837 A CN 202111300837A CN 114023889 A CN114023889 A CN 114023889A
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layer
electrode
sub
perovskite
sublayer
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陈晨
李白茹
徐孟雷
杨洁
张昕宇
金浩
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Zhejiang Jinko Solar Co Ltd
Jinko Solar Co Ltd
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Zhejiang Jinko Solar Co Ltd
Jinko Solar Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K30/81—Electrodes
    • 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
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • 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

Abstract

The application provides a perovskite solar cell group, a preparation method thereof and a photovoltaic module, wherein the perovskite solar cell group is separated by a plurality of grooves to form a plurality of electrically connected sub-cells, and each sub-cell comprises a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer which are arranged in a stacked mode; and the two adjacent sub-cells are electrically connected with the conductive membrane layer formed on the surface of the first electrode sublayer through the second electrode sublayer. The perovskite solar cell set provided by the application is electrically connected with the second electrode sublayer in the subcell and the first electrode sublayer of the adjacent subcell through the conductive diaphragm layer, so that the series resistance between the cells can be effectively reduced, and the performance of the device is improved.

Description

Perovskite solar cell array, preparation method thereof and photovoltaic module
Technical Field
The application relates to the technical field of photovoltaic cells, in particular to a perovskite solar cell group, a preparation method thereof and a photovoltaic module.
Background
At present, perovskite battery submodule pieces are mainly prepared through cutting, however, in the laser cutting process, due to the fact that the density of a hole transmission layer and a perovskite layer is high, the binding force with a bottom electrode is high, the perovskite layer and/or the hole transmission layer can be remained in a partial area in the cutting process, the remained part is difficult to be completely stripped from a conducting layer, the top electrode and the bottom electrode are not sufficiently connected, the contact resistance between batteries is high, and the photoelectric efficiency of the perovskite solar battery is not favorably improved.
Disclosure of Invention
In view of this, the application provides a perovskite solar cell group, a preparation method thereof and a photovoltaic module, which can reduce contact resistance between cells and are beneficial to improving photoelectric efficiency of perovskite solar cells.
In a first aspect, the present application provides a method of fabricating a perovskite solar cell, the method comprising:
forming a first electrode layer on a substrate, and cutting the first electrode layer to form N-1 first grooves, wherein the N-1 first grooves divide the first electrode layer into N first electrode sublayers, and N is a natural number more than or equal to 2;
forming a membrane layer on the partial surface of N-1 first electrode sublayers far away from the substrate;
sequentially forming a hole transport layer, a perovskite layer and an electron transport layer on the surfaces of the N first electrode sublayers, wherein the hole transport layer fills the first grooves;
cutting the hole transport layer, the perovskite layer and the electron transport layer which are arranged in a stacked mode to form N-1 second grooves until the membrane layer positioned on the surface of each first electrode sublayer is exposed in the corresponding second groove or stripped;
forming a second electrode layer on the surface of the electron transport layer, which is far away from the substrate, and filling the second electrode layer into the second grooves, wherein the second electrode layer is connected with each first electrode sublayer;
and cutting the hole transport layer, the perovskite layer, the electron transport layer and the second electrode layer which are arranged in a stacked manner to form N-1 third grooves to obtain N sub-batteries which are electrically connected with each other, wherein each sub-battery comprises a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer which are arranged in a stacked manner.
In a possible embodiment in combination with the first aspect, the membrane layer has a thickness of 100nm to 1000 nm.
In one possible embodiment in combination with the first aspect, the membrane layer is a conductive membrane layer comprising at least one of a conductive metal membrane layer or a conductive polymer membrane layer.
With reference to the first aspect, in a possible implementation manner, the material of the conductive polymer membrane layer includes at least one of polyaniline, polypyrrole, and polythiophene.
In one possible embodiment, in combination with the first aspect, the membrane layer is a colored membrane layer, and the material of the colored membrane layer includes at least one of PbSe, PbS, PbTe, LiF, and KBr.
In combination with the first aspect, in a possible embodiment, a ratio of the width of the membrane layer to the width of the second trench is 0.5 to 1.
In combination with the first aspect, in one possible embodiment, it satisfies at least one of the following features:
(1) the width of the first groove is 30-200 mu m;
(2) the width of the second groove is 30-200 mu m;
(3) the width of the third groove is 30-100 mu m;
(4) the grooves are formed by laser cutting.
In combination with the first aspect, in one possible embodiment, it satisfies at least one of the following features:
(1) the material of the hole transport sublayer comprises an organic material or an inorganic material;
(2) the organic matter material comprises at least one of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] and poly 3-hexylthiophene;
(3) the inorganic material comprises CuI, CuSCN, NiO and TiO2、SnO2And the like;
(4) the perovskite sublayer comprises methylamine lead iodide, (Cs)x(FA)1-xPbI3、(FA)x(MA)1-xPbI3、(FA)x(MA)1-xPbIyCl1-y、(FAPbI3)x(MAPbBr3)1-xWherein x is more than 0 and less than 1, and y is more than 0 and less than 1;
(5) the electron transport sublayer is made of ZnO and TiO2、SnO2、NiO、MoO3At least one of fullerene derivative (PCBM) and C60;
(6) the substrate is a conductive glass substrate.
In a possible embodiment in combination with the first aspect, the contact resistance between the sub-cells is 2 Ω cm2～4Ω*cm2。
In a second aspect, the present application provides a perovskite solar cell, comprising a plurality of sub-cells electrically connected to each other and separated by a plurality of trenches, each sub-cell comprising a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer, which are stacked;
and the two adjacent sub-cells are electrically connected with the conductive membrane layer formed on the surface of the first electrode sublayer through the second electrode sublayer.
In a possible embodiment, in combination with the second aspect, the thickness of the conductive separator layer is between 100nm and 1000 nm.
In combination with the second aspect, in one possible embodiment, the conductive membrane layer includes at least one of a conductive metal membrane layer or a conductive polymer membrane layer.
With reference to the second aspect, in a possible embodiment, the material of the conductive polymer membrane layer includes at least one of polyaniline, polypyrrole, and polythiophene.
In a possible embodiment, in combination with the second aspect, the inter-subcell contact resistance is 2 Ω cm2～4Ω*cm2。
In a third aspect, the present application provides a photovoltaic module comprising a plurality of solar cell strings, wherein the solar cell strings comprise the perovskite solar cell array prepared by the preparation method of the first aspect or the perovskite solar cell array of the second aspect.
The technical scheme of the application has at least the following beneficial effects:
according to the technical scheme, in the perovskite solar cell, the thickness of the hole transport layer is very thin, the density is high, the hole transport layer can be completely cut off by high laser energy, the first electrode layer at the bottom of the hole transport layer is easily damaged in the cutting process, and the indirect electric shock resistance of the cell is greatly improved. By forming the diaphragm layer on the partial surface of the first electrode sublayer, which is far away from the substrate, because the density of the diaphragm layer is lower than that of the hole transport layer, when the second groove is formed by cutting, whether the hole transport layer is completely cut off can be quickly judged according to the diaphragm layer, and the influence of the residual hole transport layer on the electric connection between the electrodes is avoided. The laser cutting depth is quickly and visually reflected through the membrane layer, and when the membrane layer is exposed, cutting can be stopped, so that the first electrode layer is prevented from being damaged by excessive cutting. Therefore, the contact resistance between the sub-batteries can be reduced, and the photoelectric conversion efficiency of the battery can be improved.
Drawings
For a clearer explanation of the embodiments or technical solutions of the prior art of the present application, the drawings needed for the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a process flow diagram of a method of fabricating a perovskite solar cell provided herein;
FIG. 2 is a schematic view of the structural change state of a perovskite solar cell set provided herein;
FIG. 3 is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
FIG. 4 is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
FIG. 5a is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
FIG. 5b is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
FIG. 6a is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
FIG. 6b is a schematic view of yet another structural change state of a perovskite solar cell set provided herein;
fig. 7a is a schematic view of an encapsulated state of a photovoltaic module provided by the present application;
fig. 7b is a schematic view of another packaging state of the photovoltaic module provided by the present application.
Detailed Description
For better understanding of the technical solutions of the present application, the following detailed descriptions of the embodiments of the present application are provided with reference to the accompanying drawings.
It should be understood that the embodiments described are only a few embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
At present, perovskite battery submodule pieces are mainly prepared through cutting, however, in the laser cutting process, due to the fact that the density of a hole transmission layer and a perovskite layer is high, the binding force with a bottom electrode is high, the perovskite layer and/or the hole transmission layer can be remained in a partial area in the cutting process, the remained part is difficult to be completely stripped from a conducting layer, the top electrode and the bottom electrode are not sufficiently connected, the contact resistance between batteries is high, and the photoelectric efficiency of the perovskite solar battery is not favorably improved.
The embodiment of the application provides a preparation method of a perovskite solar battery pack, which comprises the following steps:
step S10, forming a first electrode layer on a substrate, and cutting the first electrode layer to form N-1 first grooves, wherein the N-1 first grooves divide the first electrode layer into N first electrode sublayers, and N is a natural number greater than or equal to 2;
step S20, forming a membrane layer on the partial surface of N-1 first electrode sub-layers far away from the substrate;
step S30, sequentially forming a hole transport layer, a perovskite layer and an electron transport layer on the surfaces of the N first electrode sublayers, wherein the hole transport layer fills the first grooves;
step S40, cutting the hole transport layer, the perovskite layer and the electron transport layer which are stacked to form N-1 second grooves until the membrane layer positioned on the surface of each first electrode sublayer is exposed in the corresponding second groove or stripped;
step S50, forming a second electrode layer on the surface of the electron transport layer away from the substrate, and filling the second electrode layer into the second trench, where the second electrode layer is connected to each of the first electrode sublayers;
step S60, cutting the hole transport layer, the perovskite layer, the electron transport layer and the second electrode layer which are stacked to form N-1 third grooves to obtain N sub-batteries which are electrically connected with each other, wherein each sub-battery comprises a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer which are stacked.
In the above scheme, the diaphragm layer is formed on the surface of the first electrode sublayer, which is away from the substrate, and because the density of the diaphragm layer is lower than that of the hole transport layer, when the second trench is formed by cutting, whether the hole transport layer is completely cut off can be quickly judged according to the diaphragm layer, so that the residual hole transport layer is prevented from influencing the electrical connection between the electrodes.
Understandably, in the perovskite solar cell, the thickness of the hole transport layer is very thin, the density is high, the hole transport layer can be completely cut off only by high laser energy, and the first electrode layer at the bottom of the hole transport layer is easily damaged in the cutting process, so that the indirect electric resistance of the cell is greatly improved. In addition, the hole transport layer and the first electrode layer are both made of transparent materials, so that the hole transport layer and the first electrode layer are difficult to distinguish in a cutting process, the hole transport layer is easy to remain, or the first electrode layer at the bottom of the hole transport layer is damaged in a cutting transition mode. Therefore, the conductive diaphragm layer is formed between the hole transport layer and the first electrode layer, the laser cutting depth is quickly and visually reflected through the conductive diaphragm layer, cutting can be stopped when the conductive diaphragm layer is exposed, and the first electrode layer is prevented from being damaged by excessive cutting.
In other embodiments, the separator layer may be peeled off such that the first electrode layer is directly in contact with the second electrode layer, which not only ensures complete cutting of the hole transport layer, but also avoids damage to the first electrode layer. The peeling means that the separator layer is separated or peeled off from the first electrode sublayer by an external force from the surface edge of the first electrode sublayer.
The present solution is specifically described below with reference to the following examples:
as shown in fig. 1 and 2, in step S10, a first electrode layer 10 is formed on a substrate 200, and N-1 first trenches P1 are formed by cutting the first electrode layer 10, where the N-1 first trenches P1 separate the first electrode layer 10 into N first electrode sublayers 10a, where N is a natural number greater than or equal to 2.
The substrate 200 may be a glass substrate, and the width, length, height and specific material of the glass substrate are not particularly limited, and may be selected by a person skilled in the art according to actual needs. For example, the width, length, and height may be dimensions suitable for large area perovskite solar cells.
The thickness of the substrate 200 may be 1.0mm to 2.5mm, so as to ensure sufficient bearing capacity, and reduce the absorption of the glass substrate to light, so that more light can enter the solar cell, and the absorption utilization rate of the cell to light is increased.
The first electrode layer 10 may be formed on the glass substrate 200 by a chemical vapor deposition method or a magnetron sputtering method. It should be noted that the size of the first electrode layer 10 is not particularly limited, and may be selected by those skilled in the art according to actual needs.
In some embodiments, the first electrode layer 10 may be a transparent electrode layer, and the thickness of the first electrode layer 10 may be 100nm to 1000nm, and specifically, may be 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 800nm, 1000nm, or the like, which is not limited herein.
The first electrode layer 10 may be a fluorine-doped tin oxide (FTO) electrode, so that the absorption of the transparent first electrode layer 10 to ultraviolet light is enhanced, and the entry of ultraviolet light into the electron transport layer is further reduced; the material of the first electrode layer 10 may also be tin-doped indium oxide (ITO), titanium-doped indium oxide (ITiO) electrode, cerium-doped indium oxide (ICO) electrode, tungsten-doped indium oxide (IWO) electrode, aluminum-doped zinc oxide (AZO) electrode, boron-doped zinc oxide (BZO) electrode, or the like, which is not limited herein.
In the present embodiment, N-1 first trenches P1 are formed on the first electrode layer 10 by laser cutting, and the N-1 first trenches P1 are disposed at equal intervals. The first electrode layer 10 is divided into a plurality of first electrode sublayers 10a by the first trenches P1, and the width of the first trenches P1 is 30 μm to 200 μm, and may be 30 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, 130 μm, 150 μm, 180 μm, or 200 μm, but is not limited thereto. The width of the first trench P1 is too wide, so that the effective light irradiation area of the whole cell is reduced, and the photoelectric conversion efficiency of the cell is affected. The width of the first trench P1 is too narrow, and the stability of the electrical connection between each first electrode sub-layer and the adjacent sub-cell is degraded.
It should be noted that the first electrode sub-layers 10a are disconnected from each other, that is, the first trenches P1 form insulating strips, so that the first electrode sub-layers 10a are independently disposed. In practical application, sunlight is irradiated from the glass substrate to reach the first electrode sub-layer 10a, and the first electrode sub-layer 10a is a negative electrode of each sub-cell.
As shown in fig. 2, in step S20, a membrane layer 20 is formed on N-1 partial surfaces of the first electrode sub-layers 10a away from the substrate 200.
The separator layer 20 may be formed on the upper surface of the first electrode sublayer 10a by an evaporation process. The evaporation process is to evaporate or sublimate the deposition material into gaseous particles, the gaseous particles are rapidly conveyed from the evaporation source to the surface of the substrate, and the gaseous particles are attached to the surface of the substrate to form a solid film. In other embodiments, the membrane layer may be formed by a process such as electroplating or electroless plating. The membrane layer can protect the first electrode sublayer and prevent the first electrode sublayer from being damaged in a subsequent laser cutting process.
In some embodiments, the thickness of the membrane layer 20 is 100nm to 1000nm, and specifically may be 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1000nm, and the like, which is not limited herein. The membrane layer 20 may be a conductive membrane layer including at least one of a conductive metal membrane layer or a conductive polymer membrane layer. In particular, the conductive metal separator layer may be selected from a silver layer, a copper layer, a gold layer, a platinum layer, and the like.
Specifically, the material of the conductive polymer membrane layer includes at least one of polyaniline, polypyrrole, and polythiophene, and those skilled in the art may also adopt polymer membranes of other materials as required. The strength and hardness of the conductive polymer membrane layer are lower than those of the conductive metal membrane layer, but the light transmittance of the conductive metal membrane layer is lower, and the peeling difficulty is higher than that of the conductive polymer membrane layer. Taking the example of forming the conductive polymer membrane layer on the upper surface of the first electrode sublayer, polyaniline can be high-temperature evaporated on the surface of the first electrode sublayer, in a specific evaporation process, a prefabricated mold can be used to be erected on the surface of each first electrode sublayer arranged at intervals, and then a plurality of membrane layers with uniform intervals are formed by evaporation.
It will be appreciated that the conductive polymer membrane layer formed on the first electrode sub-layer is relatively easy to peel off after subsequent laser cutting due to its relatively good flexibility.
In other embodiments, the separator layer may also be a colored separator layer, i.e. the separator layer is not made of a transparent material, has a certain color, and the colored separator layer may or may not be conductive. The material of the colored diaphragm layer comprises at least one of PbSe, PbS, PbTe, LiF and KBr. Similarly, the membrane layer may be formed by an evaporation process. After the colored membrane layer is formed on the upper surface of the transparent first electrode sublayer, whether the hole transport layer is completely cut off can be judged according to the color of the membrane layer during subsequent laser cutting, namely, the hole transport layer is completely cut when the colored membrane layer is completely removed.
It is understood that the residual hole transport layer and the perovskite layer may cause an excessive contact resistance between the cells, which is not favorable for improving the photoelectric conversion efficiency of the cells. When the diaphragm layer is cut by laser until the diaphragm layer is exposed in the second groove, the hole transport layer is basically cut, and at the moment, the diaphragm layer with lower density is stripped, so that the first electrode sublayer at the bottom of the diaphragm layer is not damaged by the laser, the complete cutting of the hole transport layer can be ensured, the second electrode formed subsequently is in direct contact with the first electrode sublayer, and the contact resistance is reduced.
Preferably, the membrane layer 20 may be a colored conductive polymer membrane layer to facilitate the release process.
As an optional technical solution of the present application, a ratio of the width of the diaphragm layer 20 to the width of the second trench P2 is 0.5 to 1, and specifically may be 0.5, 0.6, 0.7, 0.8, 0.9, or 1, which is not limited herein. That is, the width of the diaphragm layer 20 is less than or equal to the width of the second trench P2. In the present embodiment, the membrane layer 20 is located at one end of the nth first electrode sub-layer 10a near the adjacent (N-1) th first electrode sub-layer 10 a.
As shown in fig. 3, in step S30, a hole transport layer 30, a perovskite layer 40, and an electron transport layer 50 are sequentially formed on the surfaces of the N first electrode sublayers 10a, wherein the hole transport layer 30 fills the first trenches P1.
The material of the hole transport layer 30 includes an organic material or an inorganic material. The organic matter material comprises 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA) and poly-3-hexylthiophene (P3 HT). The inorganic material comprises CuI, CuSCN, NiO and TiO2、SnO2And the like.
The thickness of the hole transport layer 30 may be 10nm to 60nm, and specifically, may be 10nm, 15nm, 20nm, 30nm, 40nm, 50nm, or 60nm, and the like, which is not limited herein. The thickness of the hole transport layer 30 is small, when laser grooving is performed, if the hole transport layer is to be completely removed, the first electrode layer is easily damaged, and if the hole transport layer 30 is left, the contact resistance between the sub-cells is increased, which is not beneficial to improving the photoelectric conversion efficiency of the cell.
The perovskite layer 40 is made of methylamine lead iodide, (Cs)x(FA)1-xPbI3、(FA)x(MA)1-xPbI3、(FA)x(MA)1-xPbIyCl1-y、(FAPbI3)x(MAPbBr3)1-xWherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
The thickness of the perovskite layer 40 may be 300nm to 1000nm, and specifically, may be 300nm, 400nm, 500nm, 600nm, 800nm, 900nm, 1000nm, or the like, which is not limited herein. The perovskite layer 40 is connected to the hole transport layer 30, the perovskite layer 40 can absorb sunlight and generate electron-hole pairs, and the hole transport layer 30 can transport the electron-hole pairs from the perovskite layer 40 to the first electrode sublayer 10 a.
The thickness of the electron transport layer 50 may be 10nm to 50nm, and specifically may be 10nm, 15nm, 20nm, 30nm, 40nm, 45nm, or 50nm, and the like, which is not limited herein.
The electron transport layer 50 is made of ZnO or TiO2、SnO2、NiO、MoO3At least one of fullerene derivative (PCBM) and C60.
The specific formation method of the perovskite layer 40, the hole transport layer 30, and the electron transport layer 50 is not particularly limited, and the perovskite layer may be formed by a chemical vapor deposition method, a magnetron sputtering method, a printing method, a slit coating method, or a spray coating method, but is not limited thereto.
As shown in fig. 4, in step S40, the hole transport layer 30, the perovskite layer 40 and the electron transport layer 50 which are stacked are cut to form N-1 second grooves P2 until the separator layer 20 on the surface of each of the first electrode sublayers 10a is exposed in a corresponding one of the second grooves P2 or peeled off;
the second groove P2 cuts off the electron transport layer 50, the perovskite layer 40 and the hole transport layer 30 of the cell, and one end of the second groove P2 is connected to the first electrode sublayer 10a and the other end of the second groove P2 is used for connecting to the second electrode layer, whereby a current path can be formed to complete the series connection of the cells.
The distance between the first trench P1 and the second trench P2 in the horizontal direction is not less than 5 μm. By controlling the distance between the first groove P1 and the second groove P2, the phenomenon that the first groove P1 and the second groove P2 are overlapped to cause short circuit of the battery can be avoided, and the qualified rate of the battery is improved. It should be noted that the pitch mentioned in the present embodiment refers to the distance between the center lines of the two grooves in the horizontal direction.
The width of the second trench P2 may be 30 μm to 200 μm, and specifically may be 30 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, 130 μm, 150 μm, 180 μm, or 200 μm, and the like, which is not limited herein.
When the separator layer 20 is a conductive metal separator layer, the hole transport layer on the surface of the conductive metal separator layer only needs to be completely cut off by laser grooving, and the separator layer 20 on the surface of the first electrode sublayer 10a may remain or be peeled off or partially peeled off.
When the membrane layer 20 is a conductive polymer membrane layer, it may be stripped away during the slotting process when the conductive polymer membrane layer is exposed within the second trenches P2, so that the subsequently formed second electrode layer can be in direct contact with the first electrode sublayer.
When the separator layer 20 is a non-conductive colored separator layer, whether the separator layer 20 on the surface of the first electrode sublayer is completely cut can be judged according to the color, and when the colored separator layer is completely cut, the hole transport layer 30 and the perovskite layer 40 on the surface of the colored separator layer are also necessarily completely cut.
As shown in fig. 5a and 5b, in step S50, a second electrode layer 60 is formed on the surface of the electron transport layer 50 away from the substrate 200, and the second electrode layer 60 is filled into the second trench P2, wherein the second electrode layer 60 is connected to each of the first electrode sublayers 10 a.
The second electrode layer 60 may be a metal electrode layer and is a positive electrode of the battery, and the material of the second electrode layer 60 may be gold, silver, aluminum, copper, or other metals, which can be selected by those skilled in the art according to actual needs, and is not limited herein. The second electrode layer 60 is connected to the electron transport layer 50, and the second electrode layer 60 is filled into the second trench P2, so that the second electrode layer 60 can be connected to the first electrode sublayer 10 a.
As shown in fig. 5a, after the conductive separator layer 20 is formed on the upper surface of the first electrode sublayer 10a, the second electrode layer 60 can be connected to the first electrode sublayer 10a through the conductive separator layer 20, so as to increase conductivity and reduce inter-contact resistance.
As shown in fig. 5b, after the conductive separator layer 20 or the colored separator layer 20 is formed on the upper surface of the first electrode sublayer 10a, the separator layer 20 may be peeled off, so that the second electrode layer 60 can be directly connected to the first electrode sublayer 10a in a contact manner, thereby preventing the residual hole transport layer from affecting the contact connection between the electrodes and reducing the contact resistance.
The thickness of the second electrode layer 60 is 50nm to 200nm, and specifically, may be 50nm, 60nm, 80nm, 100nm, 130nm, 150nm, 180nm, or 200nm, and the like, which is not limited herein.
As shown in fig. 6a and 6b, in step S60, the hole transport layer 30, the perovskite layer 40, the electron transport layer 50 and the second electrode layer 60 which are stacked are cut to form N-1 third trenches P3, so as to obtain N sub-cells which are electrically connected with each other, wherein each sub-cell comprises a first electrode sub-layer 10a, a hole transport sub-layer 30a, a perovskite sub-layer 40a, an electron transport sub-layer 50a and a second electrode sub-layer 60a which are stacked.
The plurality of sub-cells are connected in series, that is, the second electrode sub-layer of the previous sub-cell is connected with the first electrode sub-layer of the next sub-cell.
As an alternative solution of the present application, the width of the third trench P3 is 30 μm to 100 μm, and may be 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 88 μm, 95 μm, or 100 μm, and the like, which is not limited herein. The N-1 third grooves P3 are arranged at equal intervals. The bottom of the third trench P3 is connected to the first electrode sublayer 10 a. The third groove P3 cuts the second electrode layer 60 of the cell, cutting the large area cell into a plurality of small area sub-cells.
The third trench P3 is spaced apart from the second trench P2 by not less than 5 μm in the horizontal direction. Through controlling the distance between the first groove and the second groove, the battery short circuit caused by the coincidence of the first groove and the second groove can be avoided, and the qualified rate of the battery is favorably improved.
The width of the sub-battery is 5mm to 8mm, and specifically, it may be 5mm, 6mm, 6.5mm, 7mm, 7.5mm, or 8mm, etc., which is not limited herein.
It is understood that light is incident from the transparent first electrode sublayer 10a, and after the perovskite in the perovskite layer 40 absorbs photon energy higher than the forbidden bandwidth, an electron-hole pair is generated, i.e., an electron in the valence band transits from the ground state to the excited state and is excited to the conduction band. Holes in the valence band are transported into the second electrode sublayer 60a through the hole transport layer 30. And the electrons excited in the conduction band are injected into the conduction band of the electron transport layer 50 having a lower energy level and transport the electrons to the first electrode sublayer 10 a. The electrons are then transported from the first electrode sublayer 10a to the second electrode sublayer 60a via an external circuit, and recombine with the holes in the second electrode sublayer 60 a.
The perovskite solar cell set consists of a plurality of sub-cells, and the size of each sub-cell can be selected by a person skilled in the art according to actual needs. Under the action of the first groove P1, the second groove P2 and the third groove P3, the transmission of electrons and holes is facilitated, the serial connection among the sub-battery units is realized, the total current intensity of the battery is increased, and the utilization rate of the battery to light energy is improved.
Referring to fig. 6a and 6b, a perovskite solar cell is separated by a plurality of trenches to form a plurality of sub-cells electrically connected to each other, each sub-cell includes a first electrode sub-layer 10a, a hole transport sub-layer 30a, a perovskite sub-layer 40a, an electron transport sub-layer 50a, and a second electrode sub-layer 60a, which are stacked;
in some embodiments, the second electrode sublayer is in direct contact with the first electrode sublayer to form an electrical connection between two adjacent subcells.
In other embodiments, the two adjacent subcells are electrically connected to the conductive separator layer 20 formed on the surface of the first electrode sublayer 10a through the second electrode sublayer 60 a.
The thickness of the conductive membrane layer 20 is 100nm to 1000nm, and may be, but not limited to, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1000 nm. The conductive membrane layer 20 includes at least one of a conductive metal membrane layer or a conductive polymer membrane layer. Specifically, the conductive metal separator layer 20 may be selected from a silver layer, a copper layer, a gold layer, a platinum layer, and the like.
Specifically, the material of the conductive polymer membrane layer may be at least one of polyaniline, polypyrrole, and polythiophene. The strength and hardness of the conductive polymer membrane layer are lower than those of the conductive metal membrane layer, but the light transmittance of the conductive metal membrane layer is lower, and the peeling difficulty is higher than that of the conductive polymer membrane layer.
The material of the hole transport sublayer 30a includes an organic material or an inorganic material. The organic matter material comprises 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA) and poly-3-hexylthiophene (P3 HT). The inorganic material comprises CuI, CuSCN, NiOx and TiO2、SnO2And the like.
The thickness of the hole transport sublayer 30a may be 10nm to 60nm, and specifically may be 10nm, 15nm, 20nm, 30nm, 40nm, 50nm, or 60nm, and the like, which is not limited herein. The thickness of the hole transport layer 30 is small, when laser grooving is performed, if the hole transport layer is to be completely removed, the first electrode layer is easily damaged, and if the hole transport layer 30 is left, the contact resistance between the sub-cells is increased, which is not beneficial to improving the photoelectric conversion efficiency of the cell.
The perovskite sub-layer 40a is made of methylamine lead iodide, (Cs)x(FA)1-xPbI3、(FA)x(MA)1-xPbI3、(FA)x(MA)1-xPbIyCl1-y、(FAPbI3)x(MAPbBr3)1-xWherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
The thickness of the perovskite sub-layer 40a may be 300nm to 1000nm, and specifically may be 300nm, 400nm, 500nm, 600nm, 800nm, 900nm, 1000nm, or the like, which is not limited herein. The perovskite layer 40 is connected to the hole transport layer 30, the perovskite layer 40 can absorb sunlight and generate electron-hole pairs, and the hole transport layer 30 can transport the electron-hole pairs from the perovskite layer 40 to the first electrode sublayer 10 a.
The thickness of the electron transport sublayer 50a may be 10nm to 50nm, and specifically may be 10nm, 15nm, 20nm, 30nm, 40nm, 45nm, or 50nm, and the like, which is not limited herein.
The electron transport sublayer 50a is made of ZnO or TiO2、SnO2、NiO、MoO3At least one of fullerene derivative (PCBM) and C60.
The thickness of the second electrode sublayer 60a is 50nm to 200nm, and specifically, may be 50nm, 60nm, 80nm, 100nm, 130nm, 150nm, 180nm, or 200nm, and the like, which is not limited herein.
The second electrode sub-layer 60a may be a metal electrode layer and is a positive electrode of a battery, and the material of the second electrode sub-layer 60a may be metal such as gold, silver, aluminum, copper, etc., and those skilled in the art may select the metal according to actual needs, which is not limited herein.
In a third aspect, the present application also provides a photovoltaic module comprising a perovskite solar cell stack, as shown in fig. 7a and 7b, the perovskite solar cell stack comprising a plurality of perovskite solar sub-cells arranged in series and a cover plate 300.
The cover plate 300 may be a transparent or opaque cover plate, such as a glass cover plate, a plastic cover plate.
In one embodiment, the perovskite solar cell array may be coated with a packaging material on the periphery or each second electrode sub-layer 60a, and then the cover plate 300 is covered on the perovskite solar cell array, and then the perovskite solar cell array is vacuumized and then subjected to a light curing process.
In another embodiment, the polyisobutylene adhesive tape may be attached to the periphery of the perovskite solar cell assembly, and the cover plate 300 may be covered on the perovskite solar cell assembly and then sealed by using a laminator.
And the first electrode sublayer and the last electrode sublayer of the perovskite solar battery are respectively provided with a positive electrode and a negative electrode.
Specifically, the positive electrode of the perovskite solar battery pack can be a positive electrode drainage strip, and the negative electrode can be a negative electrode drainage strip, so that electric energy is output.
Perovskite solar cell examples 1 to 13(S1-S13) and comparative examples 1 to 3(D1-D3) were prepared according to the method described in the above first aspect, and the specific process parameters are shown in table 1, and the test results of the prepared perovskite solar cell are shown in table 2:
TABLE 1 relevant preparation Process parameters for perovskite solar cell stacks
Figure BDA0003338332010000131
Figure BDA0003338332010000141
TABLE 2 test results for perovskite solar cell sets
Figure BDA0003338332010000142
As can be seen from embodiments 1 to 13, a diaphragm layer is formed on the surface of the first electrode sublayer, and the thickness, width, and material of the diaphragm layer are controlled within a predetermined range, which is beneficial to protecting the first electrode sublayer from being damaged by laser, improving the connection between the first electrode sublayer and the second electrode sublayer, improving the electron collecting capability, effectively reducing the contact resistivity between subcells, improving the open-circuit voltage of the solar cell, and improving the fill factor and the photoelectric conversion efficiency.
In the perovskite solar cell of comparative example 1, the thickness of the diaphragm layer formed on the surface of the first electrode sublayer is too thick, so that the cost is increased, the time required for laser grooving is longer, the peeling difficulty of the diaphragm layer is increased, and the reduction of the production cost is not facilitated.
In the perovskite solar cell set of comparative example 2, since the width of the diaphragm layer formed on the surface of the first electrode sublayer is small, most of the first electrode sublayer cannot be covered, the first electrode sublayer at the bottom of the first electrode sublayer cannot be fully protected in the grooving process, so that part of the first electrode sublayer is damaged by laser, poor contact is easily caused between the first electrode sublayer and the second electrode sublayer, the indirect electric contact resistivity of the cell is greatly improved, and the open-circuit voltage, the filling factor and the photoelectric conversion efficiency of the solar cell are reduced.
Compared with the perovskite solar cell module in the comparative example 3, because the diaphragm layer is not formed on the surface of the first electrode sublayer, in the laser grooving process, the hole transport layer can be completely cut off only by high laser energy due to high density of the hole transport layer, and in the cutting process, the first electrode sublayer at the bottom of the hole transport layer is easily damaged, so that the indirect electric contact resistivity of the cell is greatly improved.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.

Claims (15)

1. A method of fabricating a perovskite solar cell, the method comprising:
forming a first electrode layer on a substrate, and cutting the first electrode layer to form N-1 first grooves, wherein the N-1 first grooves divide the first electrode layer into N first electrode sublayers, and N is a natural number more than or equal to 2;
forming a membrane layer on the partial surface of N-1 first electrode sublayers far away from the substrate;
sequentially forming a hole transport layer, a perovskite layer and an electron transport layer on the surfaces of the N first electrode sublayers, wherein the hole transport layer fills the first grooves;
cutting the hole transport layer, the perovskite layer and the electron transport layer which are arranged in a stacked mode to form N-1 second grooves until the membrane layer positioned on the surface of each first electrode sublayer is exposed in the corresponding second groove or stripped;
forming a second electrode layer on the surface of the electron transport layer, which is far away from the substrate, and filling the second electrode layer into the second grooves, wherein the second electrode layer is connected with each first electrode sublayer;
and cutting the hole transport layer, the perovskite layer, the electron transport layer and the second electrode layer which are arranged in a stacked manner to form N-1 third grooves to obtain N sub-batteries which are electrically connected with each other, wherein each sub-battery comprises a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer which are arranged in a stacked manner.
2. The method according to claim 1, wherein the thickness of the separator layer is 100nm to 1000 nm.
3. The method of manufacturing according to claim 1, wherein the membrane layer is a conductive membrane layer comprising at least one of a conductive metal membrane layer or a conductive polymer membrane layer.
4. The method according to claim 3, wherein the conductive polymer membrane layer is made of at least one of polyaniline, polypyrrole, and polythiophene.
5. The preparation method according to claim 1, wherein the membrane layer is a colored membrane layer, and the material of the colored membrane layer comprises at least one of PbSe, PbS, PbTe, LiF and KBr.
6. The method according to claim 1, wherein a ratio of the width of the membrane layer to the width of the second trench is 0.5 to 1.
7. The production method according to any one of claims 1 to 6, characterized in that it satisfies at least one of the following characteristics:
(1) the width of the first groove is 30-200 mu m;
(2) the width of the second groove is 30-200 mu m;
(3) the width of the third groove is 30-100 mu m;
(4) the grooves are formed by laser cutting.
8. The method of claim 1, wherein at least one of the following characteristics is satisfied:
(1) the material of the hole transport sublayer comprises an organic material or an inorganic material;
(2) the organic matter material comprises at least one of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] and poly 3-hexylthiophene;
(3) the inorganic material comprises CuI, CuSCN, NiO and TiO2、SnO2And the like;
(4) the perovskite sublayer comprises methylamine lead iodide, (Cs)x(FA)1-xPbI3、(FA)x(MA)1-xPbI3、(FA)x(MA)1-xPbIyCl1-y、(FAPbI3)x(MAPbBr3)1-xWherein x is more than 0 and less than 1, and y is more than 0 and less than 1;
(5) the electron transport sublayer is made of ZnO and TiO2、SnO2、NiO、MoO3At least one of fullerene derivative (PCBM) and C60;
(6) the substrate is a conductive glass substrate.
9. The method of claim 1, wherein the inter-subcell contact resistance is 2 Ω cm2～4Ω*cm2。
10. The perovskite solar cell is characterized by comprising a plurality of sub-cells which are separated by a plurality of grooves and electrically connected with each other, wherein each sub-cell comprises a first electrode sub-layer, a hole transport sub-layer, a perovskite sub-layer, an electron transport sub-layer and a second electrode sub-layer which are arranged in a stacked mode;
and the two adjacent sub-cells are electrically connected with the conductive membrane layer formed on the surface of the first electrode sublayer through the second electrode sublayer.
11. The perovskite solar cell of claim 10, wherein the conductive separator layer has a thickness of 100nm to 1000 nm.
12. The perovskite solar cell of claim 10, wherein the conductive membrane layer comprises at least one of a conductive metal membrane layer or a conductive polymer membrane layer.
13. The perovskite solar cell of claim 12, wherein the conductive polymer membrane layer comprises at least one of polyaniline, polypyrrole, and polythiophene.
14. The perovskite solar cell set of claim 10, wherein the inter-subcell contact resistance is 2 Ω cm2～4Ω*cm2。
15. A photovoltaic module comprising a plurality of strings of solar cells, the strings of solar cells comprising perovskite solar cells produced by a method of producing perovskite solar cells according to any one of claims 1 to 10 or perovskite solar cells according to any one of claims 11 to 14.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117080288A (en) * 2023-09-20 2023-11-17 宁德时代新能源科技股份有限公司 Photovoltaic thin film component, solar cell, power utilization device, preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117080288A (en) * 2023-09-20 2023-11-17 宁德时代新能源科技股份有限公司 Photovoltaic thin film component, solar cell, power utilization device, preparation method and application
CN117080288B (en) * 2023-09-20 2024-02-23 宁德时代新能源科技股份有限公司 Photovoltaic thin film component, solar cell, power utilization device, preparation method and application

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