KR102354315B1 - Solar cell with improved stability against moisture and long-term stability - Google Patents

Abstract

The present invention relates to a solar cell having improved moisture stability and long-term stability, and more particularly, to a solar cell comprising: a substrate layer; an optoelectronic device disposed on the substrate layer; and an encapsulation layer disposed on the photoelectric element to seal the photoelectric element, wherein the encapsulation layer is a silica airgel film.

Description

A solar cell with improved moisture stability and long-term stability {SOLAR CELL WITH IMPROVED STABILITY AGAINST MOISTURE AND LONG-TERM STABILITY}

The present invention relates to a solar cell with improved water stability and long-term stability, and more particularly, to a solar cell including an encapsulation layer capable of improving water stability and long-term stability without lowering efficiency.

A solar cell is a core element of photovoltaic power generation that directly converts sunlight into electricity, and is currently being widely used for power supply to homes as well as space. Recently, it is used in aviation, meteorological, and communication fields, and solar vehicles and solar air conditioners are also receiving attention.

Although such a solar cell mainly uses a silicon semiconductor, there is a problem in that the cost of power generation is high due to the raw material price of the high-purity silicon semiconductor and the complexity of the solar cell manufacturing process using the same. That is, since the unit cost of power generation by conventional fossil fuels is 3 to 10 times higher, there is a limit in that the market is growing with the support of each government. For this reason, research and development of solar cells that do not use silicon has been activated, and from the 1990s, dye-sensitized solar cells (DSSC) using dyes, which are organic semiconductor materials, and polymer solar cells (Polymer) using conductive polymers Solar Cell) began to be studied in earnest. Although organic semiconductor-based solar cells such as DSSC and polymer solar cells have not reached the commercialization stage despite many efforts from academia and industry, recently, perovskite solar cells (perovskite solar cells) that combine the advantages of DSSC and polymer solar cells cell, PSC), the anticipation for next-generation solar cells is rising.

The perovskite solar cell is a fusion solar cell of a conventional DSSC and a polymer solar cell, and as it does not use a liquid electrolyte like DSSC, the reliability is improved. Efficiency is continuously improving through process improvement, material improvement, and structural improvement. Such a perovskite solar cell is composed of a substrate layer, a first electrode layer, an electron transport layer (or hole transport layer), a photoelectric device including a perovskite layer, a hole transport layer (or electron transport layer) and a second electrode layer.

Perovskite solar cells are being discussed as a substitute for silicon solar cells in the future due to their rapid increase in efficiency and price competitiveness in the process. However, commercialization is delayed due to stability problems, and in particular, it is urgent to secure stability against moisture.

On the other hand, the encapsulation layer is used to protect the optoelectronic device or device sensitive to external factors such as moisture or oxygen.

1 and 2 are views showing a solar cell 100 using glass as the encapsulation layer 30 and sealing the photoelectric device 20 using an epoxy 40 according to the prior art. 1 and 2 , in the related art, glass as the encapsulation layer 30 is disposed to face the substrate layer 10 on which the photoelectric device 20 is disposed, and then the photoelectric device 20 is externally disposed. After attaching the encapsulation layer 30 and the substrate layer 10 through the epoxy 40 to completely block the factors, UV curing was performed.

However, UV light used in the process of curing the epoxy 40 may cause damage to the perovskite layer 23 included in the optoelectronic device 20, which reduces device efficiency, so improvement measures are needed. .

Accordingly, an object of the present invention is to provide a solar cell having a new encapsulation layer capable of improving moisture stability and long-term stability without reducing the efficiency of the photoelectric device.

In order to achieve the above object, a solar cell according to an aspect of the present invention, a substrate layer; an optoelectronic device disposed on the substrate layer; and an encapsulation layer disposed on the optoelectronic device to seal the optoelectronic device, wherein the encapsulation layer is a silica airgel film.

Here, the silica airgel film may be coated by any one method selected from the group consisting of spin coating, slot die coating, spray coating and dipping coating through a solution containing silica.

And, the thickness of the silica airgel film may be 1 μm or less, and the transmittance may be 85 to 95%.

In addition, the silica airgel film may be a polar or non-polar surface-modified one.

In this case, the silica airgel film is trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDSZ), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (phenyltriethoxysilane, PTES), methyl Trimethoxysilane (methyltrimethoxylsilane, MTMS), and methyltriethoxysilane (methyltriethoxysilane, MTES) may be surface-modified by a mixture of at least one selected from the group consisting of and xylene.

In addition, the silica airgel film may be doped with any one or more elements selected from the group consisting of Cu, Na, Sn, Zn, K, Li and Ca.

In this case, the silica airgel film may be doped with any one selected from the group consisting of copper acetate, sodium acetate, tin acetate, zinc acetate, potassium acetate, lithium acetate and calcium acetate.

Meanwhile, the photoelectric device may include a perovskite layer.

And, the photoelectric device, the first electrode layer; an electron transport layer (ETL) or a hole transport layer (HTL) disposed on the first electrode layer; a perovskite layer disposed on the electron transport layer or the hole transport layer; a hole transport layer or an electron transport layer disposed on the perovskite layer; and a second electrode layer disposed on the hole transport layer or the electron transport layer.

In this case, the solar cell, the perovskite layer comprising a first perovskite layer and a second perovskite layer stacked on the first perovskite layer-perovskite tandem It may be a solar cell of the structure.

In addition, the solar cell may be a solar cell having a silicon-perovskite tandem structure in which the substrate layer includes a silicon solar cell.

According to the present invention, by using an encapsulation layer that is a silica airgel film without using glass and an epoxy adhesive as an encapsulation layer for sealing the photoelectric device, damage to the perovskite layer due to the use of UV light does not occur. Therefore, it is possible to improve the moisture stability and long-term stability of the solar cell without reducing the photoelectric device efficiency.

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the detailed description of the present invention to be described later, so that the present invention is described in such drawings should not be construed as being limited only to
1 is a plan view illustrating a solar cell in which a photoelectric device is sealed using a glass encapsulation layer and epoxy according to the prior art.
2 is a side view showing a solar cell in which a photoelectric device is sealed using a glass encapsulation layer and epoxy according to the prior art.
3 is a plan view illustrating a solar cell in which a photoelectric device is sealed using an encapsulation layer according to the present invention.
4 is a side view illustrating a solar cell in which a photoelectric device is sealed using an encapsulation layer according to the present invention.
5 is a view showing a silica airgel according to the present invention.
6 is a side view showing a solar cell having a perovskite-perovskite tandem structure including an encapsulation layer according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Accordingly, the configuration described in this specification is only the most preferred embodiment of the present invention and does not represent all of the technical idea of the present invention, so there are various equivalents and modifications that can be substituted for them at the time of the present application. It should be understood that

3 is a plan view showing a solar cell encapsulating a photoelectric device using an encapsulation layer according to the present invention, and FIG. 4 is a side view showing a solar cell encapsulating a photoelectric device using an encapsulation layer according to an embodiment of the present invention. and FIG. 5 is a view showing a silica airgel.

3 to 5 , the solar cell 100 according to the present invention includes a substrate layer 10; an optoelectronic device 20 disposed on the substrate layer 10; and an encapsulation layer 30 disposed on the optoelectronic device 20 to seal the optoelectronic device 20, wherein the encapsulation layer 30 is a silica airgel film.

According to the present invention, by using the encapsulation layer 30, which is a silica airgel film excellent in waterproofness and heat insulation, without using glass and epoxy adhesives as the encapsulation layer 30 for sealing the photoelectric device 20, the use of UV light Accordingly, damage to the perovskite layer 23 does not occur, and accordingly, moisture stability and long-term stability of the solar cell 100 can be improved without reducing the efficiency of the photoelectric device 20 .

Airgel is a compound word of “aero” meaning air and “gel” meaning a three-dimensional network structure. A highly porous nanostructure obtained by replacing the liquid in the gel structure with air while maintaining the gel structure formed during material synthesis. to be. Airgel is composed of nanoparticles with a size of 1 to 50 nm and is a white translucent solid with a very small specific gravity, has a porous structure, and has excellent thermal insulation, waterproof and sound insulation properties.

Silica airgel is an airgel made of silica. When the silica gel in a normal gel state is dried and dehydrated, it contracts by the capillary force of water to become a hard xerogel silica gel. When the gel is heated above the critical temperature of the liquid, the liquid Silver becomes gas, and even if this is removed, silicon dioxide remains in its original colloidal dispersion state.

For this silica airgel, for example, water glass is diluted to a specific gravity of 1.2, and an equal volume of 4.3N acetic acid is added thereto to make silica gel, and left for two days to form a jelly-like condensed product, washed well to remove salt, followed by an extractor Use 95% ethyl alcohol to extract water until 10% or less. It can be manufactured by sealing this in an autoclave with enough alcohol, heating to about 260 degreeC, and releasing vaporized alcohol. Of course, silica airgel can be prepared through various other manufacturing processes.

On the other hand, the silica airgel film, which is the encapsulation layer 30, is coated on the optoelectronic device 20 through various coating methods such as spin coating, slot die coating, spray coating and dipping coating using a solution containing silica. can be formed.

And, the thickness of the silica airgel film may be 1 μm or less, and the transmittance may be 85 to 95%.

If the thickness of the silica airgel film exceeds the above numerical range, the desired transmittance is not secured, there is a problem in that the light reception rate of the photoelectric device 20 may be deteriorated.

In this case, the transmittance of the silica airgel film may be the transmittance of light having a wavelength of 300 to 800 nm, the haze may be 0.3% or less, and the thermal conductivity may be 0.01 W/K·m or more.

In addition, the silica airgel film may be surface-modified to be polar or non-polar. Silica airgel has -OH groups formed on its surface, so it originally has polar properties, but by strengthening the polar properties through surface modification, the silica airgel can be efficiently coated on the surface of the polar optoelectronic device 20. can Conversely, by making the silica airgel have a non-polar property through surface modification, the silica airgel can be efficiently coated on the surface of the non-polar optoelectronic device 20 .

Here, the silica airgel film is trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDSZ), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (phenyltriethoxysilane, PTES), methyl Trimethoxysilane (methyltrimethoxylsilane, MTMS), and methyltriethoxysilane (methyltriethoxysilane, MTES) may be surface-modified by a mixture of at least one selected from the group consisting of and xylene.

Furthermore, in order to further improve the transmittance and thin film performance of the silica airgel film, it may be doped with any one or more elements selected from the group consisting of Cu, Na, Sn, Zn, K, Li and Ca, in this case, copper acetate, It may be doped with any one selected from the group consisting of sodium acetate, tin acetate, zinc acetate, potassium acetate, lithium acetate and calcium acetate.

Meanwhile, the substrate layer 10 may include a transparent material that allows light to pass therethrough. In addition, the substrate layer 10 may include a material that selectively transmits light of a desired wavelength. The substrate layer 10 may include, for example, transparent conductive oxide (TCO) such as silicon oxide, aluminum oxide, indium tin oxide (ITO), fluorine tin oxide (FTO), glass, quartz, or a polymer. , For example, the polymer is polyimide (polyimide), polyethylene naphthalate (polyethylenenaphthalate, PEN), polyethylene terephthalate (polyethyleneterephthalate, PET), polymethyl methacrylate (PMMA) and polydimethylsiloxane (PDMS) at least any one of may contain one.

The substrate layer 10 may have a thickness in a range of, for example, 100 μm to 150 μm, for example, a thickness of 125 μm. However, the material and thickness of the substrate layer 10 are not limited to those described above, and may be appropriately selected according to the technical spirit of the present invention.

In addition, a silicon solar cell itself may be used as the substrate layer 10 in addition to those described above, which will be described later.

In addition, the photoelectric device 20 may selectively use at least one of CIGS series, CZTS series, a-Si, CdTe, DSSC, OPV and perovskite, and preferably, the perovskite layer 23 ) may be included.

More preferably, the photoelectric device 20 according to the present invention includes a first electrode layer 21; an electron transport layer (ETL) or a hole transport layer (HTL) 22 disposed on the first electrode layer 21; a perovskite layer 23 disposed on the electron transport layer or hole transport layer 22; a hole transport layer or an electron transport layer 24 disposed on the perovskite layer 23; and a second electrode layer 25 disposed on the hole transport layer or the electron transport layer 24 .

In this case, the first electrode layer 21 may be formed by being stacked on the substrate layer 10 , or may be formed integrally with the substrate layer 10 .

Each of the first electrode layer 21 and the second electrode layer 25 may be formed of a light-transmitting conductive material. The light-transmitting conductive material may include, for example, a transparent conductive oxide, a carbonaceous conductive material, and a metallic material. Examples of the transparent conductive oxide include Indium Tin Oxide (ITO), Indium Cerium Oxide (ICO), Indium Tungsten Oxide (IWO), Zinc Indium Tin Oxide (ZITO), Zinc Indium Oxide (ZIO), Zinc Tin Oxide (ZTO), GITO (Gallium Indium Tin Oxide), GIO (Gallium Indium Oxide), GZO (Gallium Zinc Oxide), AZO (Aluminum doped Zinc Oxide), FTO (Fluorine Tin Oxide), ZnO, etc. may be used. As the carbonaceous conductive material, for example, graphene or carbon nanotubes may be used, and as the metallic material, for example, a metal (Ag) nanowire, a metal having a multilayer structure such as Au/Ag/Cu/Mg/Mo/Ti A thin film may be used. In the present specification, the term "transparent" refers to something that can transmit light to a certain degree or more, and is not necessarily interpreted as meaning complete transparency. The materials described above are not necessarily limited to the above-described embodiments, and may be formed of various materials, and various modifications are possible, such as a single-layer or multi-layer structure.

Meanwhile, although not shown, a bus electrode (not shown) may be further disposed on the second electrode layer 25 to lower the resistance of the second electrode layer 25 and to further facilitate charge transfer. The bus electrode may be formed of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, and/or a compound thereof.

In addition, the electron transport layer 22 is located on the first electrode layer 21 , and may function to easily transfer electrons generated in the perovskite layer 23 to the first electrode layer 21 . The electron transport layer 22 may include a metal oxide, for example, Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide , V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, SrTi oxide and the like can be used. The electron transport layer 22 according to the present invention may include TiO ₂ , SnO ₂ , WO ₃ or TiSrO ₃ having a compact structure. The electron transport layer 22 may further include an n-type or p-type dopant as needed.

A perovskite layer 23 may be disposed on the electron transport layer 22 . In the perovskite solar cell according to an embodiment of the present invention, a perovskite compound is adopted as a photoactive material that absorbs sunlight to generate a photoelectron-photohole pair. Perovskite has the advantage of having a direct band gap, a high light absorption coefficient of about 1.5 × 10 ⁴ cm ^-1 at 550 nm, excellent charge transfer characteristics, and excellent resistance to defects.

In addition, the 　perovskite compound has the advantage of being able to form the light absorber constituting the photoactive layer through an extremely simple, easy, inexpensive and simple process of solution application and drying, and spontaneously crystallizes by drying the applied solution. It is possible to form a light absorber of coarse crystal grains, and in particular, it has excellent conductivity for both electrons and holes.

Such a perovskite 　 compound may be represented by the structure of the following formula (1).

[Formula 1]

ABX ₃

(Here, A is a monovalent organic ammonium cation or metal cation, B is a divalent metal metal cation, and X is a halogen anion)

The perovskite compound is, for example, CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbI _x Cl _3-x , MAPbI ₃ , CH ₃ NH ₃ PbI _x Br _3-x , CH ₃ NH ₃ PbCl _x Br _3-x , HC(NH ₂ ) ₂ PbI ₃ , HC(NH ₂ ) ₂ PbI _x Cl _3-x , HC(NH ₂ ) ₂ PbI _x Br _3-x , HC(NH ₂ ) ₂ PbCl _x Br _3-x , ( CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI ₃ , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Cl _3-x , (CH ₃ NH ₃ )( HC(NH ₂ ) ₂ ) _1-y PbI _x Br _3-x , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbCl _x Br _3-x and the like may be used (0≤x, y≤1). Also, _{a compound in which A of ABX 3} is partially doped with Cs may be used.

Meanwhile, a hole transport layer 24 may be disposed on the perovskite layer 23 . Holes (holes) generated in the perovskite layer 23 may be transferred to the second electrode layer 25 through the hole transport layer 24 . The hole transport layer 24 may include a conductive polymer, for example, polyaniline, polypyrrole, polythiophene, poly-3,4-ethylenedioxythiophene-polystyrenesulfonate (PEDOT-PSS), poly- [bis (4- Phenyl)(2,4,6-trimethylphenyl)amine](PTAA), Spiro-MeOTAD: 2,2`,7`-tetrakis-(N,N-di-p-methoxyphenyl-amine )-9,9`spirobifluorene), polyaniline-camphorsulfonic acid (PANI-CSA), etc. may be used. The hole transport layer 24 may further include an n-type or p-type dopant as necessary.

In addition to the above-described interlayer structure and/or material, various layer structures and materials constituting the perovskite solar cell may be applied to the electron transport layer 22 / perovskite layer 23 / hole transport layer 24 as described above. , the electron transport layer 22 and the hole transport layer 24 may be formed by changing positions.

Meanwhile, FIG. 6 is a view showing a solar cell having a perovskite-perovskite tandem structure including an encapsulation layer according to the present invention.

Referring to FIG. 6 , in the solar cell 100 , the perovskite layer 23 is a first perovskite layer 23a and a second perovskite layer 23a stacked on the first perovskite layer 23a. It may be a solar cell having a perovskite-perovskite tandem structure including a rovskite layer 23b.

In this case, the first perovskite layer 23a and the second perovskite layer 23b may have different energy band gaps. By using materials having various energy band gaps as described above, light energy in a wide spectrum region can be effectively used.

For example, in a solar cell having a tandem structure, a single junction solar cell including an absorption layer having a relatively large band gap is located on a light receiving surface, and a single junction solar cell including an absorption layer having a relatively small band gap is located on the opposite surface of the light receiving surface. can be located Accordingly, the solar cell of the tandem structure absorbs light in the short wavelength region from the front side and absorbs light in the long wavelength region from the rear side, thereby shifting the threshold wavelength toward the long wavelength. As a result, the solar cell of the tandem structure has an advantage that the entire absorption wavelength region can be widely used.

Also, the solar cell may be a solar cell having a silicon-perovskite tandem structure.

In this case, the substrate layer 10 may be a silicon solar cell itself or may include a silicon solar cell.

Here, the silicon solar cell may be a generally known silicon solar cell, the structure or form is not limited, and can be freely applied as long as it can achieve the object of the present invention.

On the other hand, the embodiments of the present invention disclosed in the present specification and drawings are merely presented as specific examples to easily explain the technical contents of the present invention and help the understanding of the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those of ordinary skill in the art to which the present invention pertains that other modifications based on the technical spirit of the present invention can be implemented in addition to the embodiments disclosed herein.

10: substrate layer
20: photoelectric device
21: first electrode layer
22: electron transport layer or hole transport layer
23: perovskite layer
24: hole transport layer or electron transport layer
25: second electrode layer
30: encapsulation layer
40: epoxy
100: solar cell

Claims (11)

substrate layer;
an optoelectronic device disposed on the substrate layer; and
and an encapsulation layer disposed on the optoelectronic device to seal the optoelectronic device,
The encapsulation layer is a silica airgel film,
The silica airgel film,
A solar cell having a thickness of 1 μm or less and a transmittance of 85 to 95% of light having a wavelength of 300 to 800 nm. According to claim 1,
The silica airgel film is a solar cell that is coated by any one method selected from the group consisting of spin coating, slot die coating, spray coating and dipping coating through a solution containing silica. delete According to claim 1,
The silica airgel film is a solar cell that is surface-modified to be polar or non-polar. 5. The method of claim 4,
The silica airgel film is trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDSZ), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (phenyltriethoxysilane, PTES), methyltrimethyl A solar cell that is surface-modified by a mixture of xylene and at least one selected from the group consisting of methyltrimethoxylsilane (MTMS), and methyltriethoxysilane (MTES). According to claim 1,
The silica airgel film is a solar cell doped with any one or more elements selected from the group consisting of Cu, Na, Sn, Zn, K, Li and Ca. 7. The method of claim 6,
The silica airgel film is a solar cell doped with any one selected from the group consisting of copper acetate, sodium acetate, tin acetate, zinc acetate, potassium acetate, lithium acetate and calcium acetate. According to claim 1,
The photoelectric device is a solar cell comprising a perovskite layer. According to claim 1,
The photoelectric device may include a first electrode layer;
an electron transport layer (ETL) or a hole transport layer (HTL) disposed on the first electrode layer;
a perovskite layer disposed on the electron transport layer or the hole transport layer;
a hole transport layer or an electron transport layer disposed on the perovskite layer; and
A solar cell comprising a second electrode layer disposed on the hole transport layer or the electron transport layer. 10. The method of claim 9,
The solar cell is a perovskite-perovskite tandem structure in which the perovskite layer includes a first perovskite layer and a second perovskite layer stacked on the first perovskite layer solar cell. 10. The method of claim 9,
The solar cell is a solar cell having a silicon-perovskite tandem structure in which the substrate layer includes a silicon solar cell.

Images