CN110085687B - Composite electrode and preparation method and application thereof - Google Patents
Composite electrode and preparation method and application thereof Download PDFInfo
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- CN110085687B CN110085687B CN201910346286.1A CN201910346286A CN110085687B CN 110085687 B CN110085687 B CN 110085687B CN 201910346286 A CN201910346286 A CN 201910346286A CN 110085687 B CN110085687 B CN 110085687B
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a composite electrode and a preparation method and application thereof, belongs to a solar thin film battery, and solves the problems of extremely low utilization rate and easy deliquescence of the existing solar thin film battery in the prior art. A composite electrode of the present invention includes: the structure layer, the graphene oxide layer, the silver nano layer and the surface attachment layer; the structure layer is the intermediate layer of the composite electrode, and the two surfaces of the structure layer are sequentially provided with a tightly attached graphene oxide layer, a silver nano layer and a surface attachment layer from inside to outside. In the composite electrode, the graphene material with lower cost is used, so that the manufacturing cost of the electrode is obviously reduced on the premise of ensuring the good conductivity of the electrode; according to the composite electrode, the graphene oxide is firstly spin-coated on the silver nano particles, so that the silver nano wires can be formed on the surface of the graphene, and the composite electrode has good light transmittance and good conductivity.
Description
Technical Field
The invention relates to the technical field of solar flexible batteries, in particular to a composite electrode and a preparation method and application thereof.
Background
Traditional crystalline silicon solar cell is owing to constitute by silicon, and the battery principal part is fragile, easily produces stealthy crackle, has one deck toughened glass as the protection mostly, causes heavy, carries inconvenience, and the shock resistance is poor, and the cost is high, and efficiency reduces more or less. The solar thin film battery overcomes the defects and has the advantages of small mass, extremely thin thickness (several microns), flexibility, simple manufacturing process and the like.
However, the solar thin film cell still has some disadvantages: poor light transmission and extremely low solar energy utilization rate; CIGS cells are susceptible to deliquescence.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a composite electrode, a method for preparing the same, and an application thereof, so as to solve the problems of the existing solar thin film battery, such as low utilization rate and easy deliquescence.
The purpose of the invention is mainly realized by the following technical scheme:
in a technical solution of the present invention, a composite electrode includes: the structure layer, the graphene oxide layer, the silver nano layer and the surface attachment layer;
the structure layer is the intermediate layer of the composite electrode, and the two surfaces of the structure layer are sequentially provided with a tightly attached graphene oxide layer, a silver nano layer and a surface attachment layer from inside to outside.
In the technical scheme of the invention, the structural layer is an ITO film.
In the technical scheme of the invention, the surface attachment layer of the light facing surface of the composite electrode is a POE layer;
the surface adhesion layer of the backlight surface of the composite electrode is a PDMS layer.
In the technical scheme of the invention, the structural layer, the graphene oxide layer, the silver nano layer and the surface attachment layer of the composite electrode are all made of transparent materials and have the same size and shape.
In the technical scheme of the invention, the preparation method of the composite electrode is used for preparing the composite electrode in the technical scheme;
the preparation method comprises the following steps:
s1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
s2, spin-coating GO solution on both sides of the ITO film;
s3, spin-coating AgNWs solution on both sides of the ITO film spin-coated with the GO solution;
s4, spin-coating liquid POE on the light-facing surface of the ITO film which is spin-coated with the GO solution and the AgNWs solution;
s5, spin-coating liquid PDMS on the back light surface of the ITO film which is spin-coated with the GO solution and the AgNWs solution;
and S6, drying the whole body in an argon atmosphere, and finishing the preparation of the composite electrode.
In the technical scheme of the invention, in the step S1, the GO solution is prepared by a HUMMERS oxidation method.
In a technical solution of the present invention, a composite electrode includes: the graphene layer is arranged on the current collector;
the silver nano layer is arranged on the backlight surface of the graphene layer, the surface attachment layer is arranged on the backlight surface of the silver nano layer, and the current collector is arranged on the light-facing surface of the graphene layer;
the current collector comprises a silver nano-net and a graphene disc; the silver nano-net covers the light-facing surface of the graphene layer, and the graphene disks are uniformly distributed on the silver nano-net and are electrically connected with the outside through wires.
In the technical scheme of the invention, the preparation method of the composite electrode is used for preparing the composite electrode in the technical scheme;
the preparation method comprises the following steps:
s1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
s2, spin-coating GO solution on one surface of the PET layer;
s3, spin-coating AgNWs solution on the PET layer which is spin-coated with GO solution;
s4, spin-coating liquid PDMS on the PET layer which is spin-coated with the GO solution and the AgNWs solution;
s5, after the whole is dried in an argon atmosphere, taking down the PET layer and keeping the Ag-RGO film;
s6, spinning GO solution on the other PET layer with grid lines engraved in the inner concave, pressing one surface of the spun GO solution on an Ag-RGO film, and taking down the PET layer after the whole body is dried in an argon atmosphere;
s7, spin-coating GO solution disks on the silver nano-net, keeping the GO solution disks uniformly distributed on the silver nano-net, and after the whole body is dried in an argon atmosphere, completing the preparation of the composite electrode.
In the technical scheme, the CIGS battery unit comprises a surface electrode layer, a buffer layer, an absorption layer, a back electrode layer, a stress layer and a base layer which are sequentially arranged;
the surface electrode layer is a composite electrode in the technical scheme;
the buffer layer is an indium selenide layer and an indium sulfide layer;
the back electrode layer is a molybdenum-containing electrode;
the base layer is a PEI layer;
the stress layer is used for buffering the thermal stress difference between the back electrode layer and the base layer.
In the technical scheme of the invention, the stress layer is an Ag film; the molybdenum electrode is doped with sodium.
According to the technical scheme, the solar thin film cell is rectangular and comprises a protective film, a structural film, a CIGS cell unit and a back film which are compacted from top to bottom;
the CIGS battery unit is the CIGS battery unit in the technical scheme;
the size of the structural film and the CIGS cell is the same;
the size of the back film is larger than the CIGS cell unit;
the protective film comprises a main body and side portions, the size of the main body is the same as that of the CIGS battery unit, the side portions are arranged on four sides of the main body and are integrated with the main body into a whole, and the side portions are sealed and tightly cover the side faces of the structural film and the CIGS battery unit and are tightly pressed with the back film.
In the technical scheme of the invention, the protective film is an ETFE film; the structural film is an EEA film; the back film is a double-layer film, one layer contacting with the CIGS battery unit is an aluminum plastic film, and the other layer is a PET film;
the main body of the ETFE film is stuck to the EEA film through POE glue; the EEA film and the CIGS battery unit are adhered through EVA adhesive; the CIGS battery unit and the aluminum plastic film are adhered through PVB glue;
the edge of the ETFE film is adhered to the side face of the structural film, the side face of the CIGS battery unit and the back film through POE glue.
The technical scheme of the invention can at least realize one of the following effects:
1. in the composite electrode, the graphene material with lower cost is used, so that the manufacturing cost of the electrode is obviously reduced on the premise of ensuring the good conductivity of the electrode;
2. according to the composite electrode, the graphene oxide is firstly spin-coated on the silver nano particles, so that the silver nano wires can be formed on the surface of the graphene, and the composite electrode has good light transmittance and good conductivity;
3. in the composite electrode, the GO and AgNWs form an Ag-rGO (silver nano and reduction-graphene oxide) composite material with better conductivity between the graphene oxide layer and the silver nano layer, so that the conductivity of the electrode can be further improved, and the internal resistance is reduced;
4. the buffer layer of the CIGS battery unit adopts an indium sulfide material, so that the carrier concentration can be improved on the premise of not obviously influencing the whole light transmittance, and the photoelectric conversion efficiency is improved;
5. the back electrode layer of the CIGS battery unit is doped with sodium, so that electrons can be provided for the back electrode, and the CIGS battery unit can form stable voltage and current.
6. According to the solar thin film cell, the edge is arranged on the protective film to carry out side surface packaging on the solar thin film cell, so that the side surface packaging structure and the protective film form an integrated structure, a special side surface packaging material is not required, and the packaging structure of the solar thin film cell is simplified.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
Fig. 1 is a schematic diagram of a CIGS cell structure provided in example 3 of the present invention;
fig. 2 is a schematic diagram of an encapsulation structure of a flexible solar thin film cell provided in embodiment 4 of the present invention;
fig. 3 is a cross-sectional view of an encapsulation structure of a flexible solar thin film cell provided in embodiment 4 of the present invention;
fig. 4 is a schematic structural diagram of a package tool provided in embodiment 5 of the present invention.
Reference numerals:
1-POE layer; 2-a silver nanolayer; a 3-graphene oxide layer; 4-an ITO film; 5-a PDMS layer; 6-a buffer layer; 7-an absorbing layer; 8-a back electrode layer; 9-a stress layer; 10-a base layer; 101-ETFE membrane; 102-POE glue; 103-EEA film; 104-EVA glue; 105-CIGS cell unit; 106-PVB glue; 107-aluminum plastic film; 108-PET film.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example 1
As shown in fig. 1, an embodiment of the present invention provides a composite electrode, including: the structure layer, the graphene oxide layer 3, the silver nano layer 2 and the surface adhesion layer; the structural layer is the intermediate layer of the composite electrode, and the two surfaces of the structural layer are sequentially provided with a graphene oxide layer 3, a silver nano layer 2 and a surface adhesion layer which are closely adhered from inside to outside. Compared with the electrode material of the traditional rare earth compound, the graphene has lower cost on the premise of lower body resistance and contact resistance, so that the manufacturing cost of the electrode can be obviously reduced on the premise of ensuring good conductive performance of the electrode by replacing a part of rare earth compound with the graphene. In addition, Ag-rGO silver nano and reduction-graphene oxide composite materials with better conductivity can be formed between the graphene oxide layer 3 and the silver nano layer 2 by GO and AgNWs, so that the conductivity of the electrode can be further improved, and the internal resistance is reduced.
In the embodiment of the invention, the structural layer is used as the structural main body of the composite electrode, and considering that the embodiment of the invention is mainly applied to the flexible solar thin film cell, the structural layer has good structural performance besides good light transmittance. Therefore, in the embodiment of the invention, the structural layer is the ITO film. The ITO film is a conductive film with relatively comprehensive performance. The transparency is good and the gloss is good; the air tightness and the fragrance retention are good; moderate moisture resistance and reduced moisture permeability at low temperatures. The ITO film has excellent mechanical performance, the toughness is the best of all thermoplastic plastics, and the tensile strength and the impact strength are much higher than those of common films; and the steel has good stiffness and stable size, and is suitable for secondary processing. The ITO film also has excellent heat resistance, cold resistance, and good chemical resistance and oil resistance.
Considering that the whole solar cell needs to be encapsulated when the embodiment of the invention is used, both sides of the composite electrode need to have good phase with other related materials. In the embodiment of the invention, the surface adhesion layer of the light facing surface of the composite electrode is a POE layer 1; the surface adhesion layer of the backlight surface of the composite electrode is a PDMS layer 5. During packaging, the protective film is usually made of a water-blocking material, the composite electrode needs to be well bonded with the protective film, and the POE has good weather resistance and ultraviolet aging resistance and has good bonding force and light transmittance, so that the POE layer 1 is used as a surface attachment layer of a light-facing surface. The backlight surface of the composite electrode is not required to be bonded with a water-blocking material, so the PDMS layer 5 with better light transmittance is used as a surface attachment layer of the backlight surface.
Embodiments of the present invention are generally used as a surface electrode layer of the CIGS cell 105, so the entire composite electrode needs to have good electrical conductivity and light transmittance, and the structural layer, the graphene oxide layer 3, the silver nanolayer 2, and the surface adhesion layer of the composite electrode are all made of transparent materials. For convenience of processing, the structural layer of the composite electrode, the graphene oxide layer 3, the silver nano-layer 2 and the surface attachment layer are the same in size and shape.
Example 2
The embodiment of the invention provides a preparation method of a composite electrode, which is used for preparing the composite electrode in the embodiment 1;
the preparation method comprises the following steps:
s1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution by a HUMMERS oxidation method;
s2, spin-coating GO solution on both sides of the ITO film 4;
s3, spin-coating AgNWs solution on both sides of the ITO film 4 which is spin-coated with the GO solution;
s4, spin-coating liquid POE on the light-facing surface of the ITO film 4 which is spin-coated with the GO solution and the AgNWs solution;
s5, spin-coating liquid PDMS on the back light surface of the ITO film 4 which is spin-coated with the GO solution and the AgNWs solution;
and S6, drying the whole body in an argon atmosphere, and finishing the preparation of the composite electrode.
The method comprises the steps of spin-coating graphene oxide on silver nanoparticles, so that silver nanowires can be formed on the surface of graphene, and the graphene has good light transmittance and good conductivity. In the process of waiting for drying, GO and AgNWs can perform redox reaction between the graphene oxide layer 3 and the silver nano layer 2 to form an Ag-rGO silver nano and reduction-graphene oxide composite material with better conductivity, so that the conductivity of the electrode can be further improved, and the internal resistance is reduced.
Example 3
An embodiment of the present invention provides a composite electrode similar to that of embodiment 1, including: the graphene layer is arranged on the current collector; the silver nano layer is arranged on the backlight surface of the graphene layer, the surface attachment layer is arranged on the backlight surface of the silver nano layer, and the current collector is arranged on the light-facing surface of the graphene layer; the current collector comprises a silver nano-net and a graphene disc; the silver nano-net covers the light-facing surface of the graphene layer, and the graphene disks are uniformly distributed on the silver nano-net and are electrically connected with the outside through wires.
The core idea of both example 3 and example 1 is to provide a silver nanolayer on a graphene layer and to form a more conductive Ag-RGO compliant structure on the surface where the two are in contact. In addition, the embodiment of the invention is also provided with a current collector structure of the silver nano-net and the graphene disc, so that the generated current can be conveniently led out, and the volume resistance of the graphene is obviously lower than that of the existing metal or alloy current collector, so that the internal resistance of the electrode can be further reduced, and the energy conversion rate of the battery can be improved.
In order to prevent the current collector from influencing the light transmittance of the electrode, in the embodiment of the invention, the area of the silver nano-net is not greater than 1/3 of the total area of the composite electrode, and the total area of the graphene disc is not greater than 1/4 of the total area of the composite electrode.
Example 4
The embodiment of the invention provides a preparation method of a composite electrode, which is used for preparing the composite electrode in the embodiment 3;
the preparation method comprises the following steps:
s1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
s2, spin-coating GO solution on one surface of the PET layer;
s3, spin-coating AgNWs solution on the PET layer which is spin-coated with GO solution;
s4, spin-coating liquid PDMS on the PET layer which is spin-coated with the GO solution and the AgNWs solution;
s5, after the whole is dried in an argon atmosphere, taking down the PET layer and keeping the Ag-RGO film;
s6, spinning GO solution on the other PET layer with grid lines engraved in the inner concave, pressing one surface of the spun GO solution on an Ag-RGO film, and taking down the PET layer after the whole body is dried in an argon atmosphere;
s7, spin-coating GO solution disks on the silver nano-net, keeping the GO solution disks uniformly distributed on the silver nano-net, and after the whole body is dried in an argon atmosphere, completing the preparation of the composite electrode.
Example 5
As shown in fig. 1, an embodiment of the present invention provides a CIGS cell 105, which includes a surface electrode layer, a buffer layer 6, an absorption layer 7, a back electrode layer 8, a stress layer 9, and a base layer 10, which are sequentially disposed; the surface electrode layer is the composite electrode in example 1 or example 3; the buffer layer 6 is an indium selenide layer and an indium sulfide layer; the back electrode layer 8 is a molybdenum-containing electrode doped with sodium; the base layer 10 is a PEI layer; the stress layer 9 is an Ag film for buffering the thermal stress difference between the back electrode layer 8 and the base layer 10.
In the embodiment of the present invention, the buffer layer 6 includes one indium selenide layer and three indium sulfide layers, the indium selenide layer is located on one side close to the light absorption layer 7, and each indium sulfide layer and each indium selenide layer contain sodium.
In this embodiment, "sodium" may be pure metal sodium, sodium ion, or sodium in a compound. For example, Na may be used2Se、Na2S、Na2SeO3Or NaNbO3Sodium in (1), preferably Na2Se、Na2And S. Since S and Se are contained in the indium sulfide layer and the indium selenide layer, respectively, Na is used2Se and Na2S does not introduce new impurities.
Compared with the prior art, the solar cell buffer layer 6 provided by the embodiment can adjust the band gap and the charge carrier concentration of the buffer layer 6 by doping sodium in the indium sulfide layer and the indium selenide layer, so that the electron transition from the light absorption layer 7 to the surface electrode layer through the buffer layer 6 is optimized, the short-circuit current of the cell is increased, and the conversion efficiency of the cell is improved.
Specifically, the buffer layer 6 in the present embodiment has a 4-layer structure, and the buffer layer 6 of the multilayer structure has a finer band gap energy than the buffer layer 6 of the single-layer structure. The finer band gap energy enables electrons and/or holes formed by external sunlight to be easily transmitted to the electrode layer and the window layer, so that the power generation efficiency of the solar cell is improved; on the other hand, the thickness of the buffer layer 6 is reduced.
In the direction from the base layer 10 to the surface electrode layer, the doping amount of Na in the back electrode layer 8 increases in a gradient manner, that is, the back electrode layer 8 may have at least two layers, and in two adjacent electrode sublayers, the Na doping amount of the electrode sublayer close to the surface electrode layer is higher than that of the electrode sublayer far from the surface electrode layer. Specifically, the Na doping amount in the multilayer electrode sublayers can be increased in a gradient manner in an equal difference and equal ratio manner. In practical applications, although the back electrode layer 8 has a small thickness, when the doping amount gradient of Na in the back electrode layer 8 increases, Na atoms are not uniformly distributed in the back electrode layer 8 even after the back electrode layer is stored for a long time. In this way, since Na is doped in the back electrode layer Mo layer, since both Na and Mo belong to metals, and the compatibility of both Na and Mo is good, Na doping can be realized on the basis that the uniformity of the back electrode layer 8 is not substantially affected, and Na can be diffused from the back electrode layer 8 to the absorber layer 7, thereby improving the energy conversion efficiency of the solar cell. In addition, since pure metal sodium is doped in the back electrode layer 8 of the CIGS solar cell, new impurity elements are not introduced in the doping process, thereby ensuring the performance of the CIGS solar cell. Meanwhile, because the doping amount of Na in the back electrode layer 8 is increased in a gradient manner from the base layer 10 to the surface electrode layer, under the condition that the total Na doping amount is not changed, compared with the back electrode layer 8 with the same Na doping amount, the metallic Na-doped CIGS solar cell provided by the embodiment has a larger Na doping amount in the electrode sublayer close to the absorption layer 7, so that the Na concentration difference between the electrode sublayer and the absorption layer 7 is increased, and further, the infiltration amount and the infiltration depth of Na into the absorption layer 7 can be increased, and the utilization rate of Na can be increased; in addition, since the Na doping amount in the electrode sublayer near the foundation layer 10 is small, the infiltration amount and infiltration depth of Na into the foundation layer 10 can be reduced.
In general, the Na doping affects the bonding tightness between the back electrode layer 8 and the base layer 10 to a certain extent, the doping amount of Na in the back electrode layer 8 increases in a gradient manner from the base layer 10 to the surface electrode layer, and the doping amount of Na in the electrode sublayer close to the base layer 10 is smaller, so that the lattice matching between the base layer 10 and the electrode sublayer can be improved, the physicochemical stress between the base layer and the electrode sublayer can be reduced, and the influence of Na doping on the bonding tightness between the base layer and the electrode sublayer can be reduced as much as possible.
Illustratively, the back electrode layer 8 may be a three-layer structure, and the back electrode layer 8 sequentially includes a first electrode sub-layer, a second electrode sub-layer and a third electrode sub-layer from the surface electrode layer to the base layer 10, where the Na doping amount of the first electrode sub-layer > the Na doping amount of the second electrode sub-layer > the Na doping amount of the third electrode sub-layer.
In order to further improve the infiltration amount and the infiltration depth of the Na infiltration absorption layer 7 and reduce the infiltration amount and the infiltration depth of the Na infiltration base layer 10, the thickness ratio of the first electrode sublayer, the second electrode sublayer and the third electrode sublayer can be controlled within the range of 2-2.5: 1-1.2: 2-2.5, the Na doping amount of the first electrode sublayer is that the thickness of the first electrode sublayer and the third electrode sublayer is larger than that of the second electrode sublayer. This is because the Na doping amount and thickness of the first electrode sublayer are large, and sufficient Na atoms can be provided to penetrate into the absorption layer 7, and the Na doping amount and thickness of the third electrode sublayer are small, so that the third electrode sublayer with a large Na doping amount is as far as possible from the base layer 10, and Na in the third electrode sublayer does not substantially penetrate into the base layer 10; meanwhile, due to the difference between the arrangement of the second electrode sublayer and the Na doping amount, the back electrode layer 8 is made of three different types of materials, so as to form an interface between the two different types of materials, and the interface can have a certain barrier effect on the diffusion of Na and other impurity elements due to the difference of diffusion behaviors, so that the infiltration amount and the infiltration depth of Na penetrating into the absorption layer 7 are further increased, and the infiltration amount and the infiltration depth of Na penetrating into the base layer 10 are reduced.
In order to prepare a flexible base CIGS solar thin film cell, a polyimide film is adopted as a flexible substrate, meanwhile, in order to balance the problem of mismatch of thermal expansion coefficients between the polyimide film and a back electrode layer 8, in the embodiment of the invention, a stress layer 9 is arranged between a base layer 10 and the back electrode layer 8 and is used for absorbing the thermal stress difference between the base layer 10 and the back electrode layer 8, and the exemplary stress layer 9 is an Ag film with high thermal conductivity and plasticity.
Example 4
As shown in fig. 2 and 3, in the embodiment of the present invention, a solar thin film cell is provided, the solar thin film cell is rectangular, and includes a protective film, a structural film, a CIGS cell 105 and a back film which are pressed from top to bottom. The size of the structural film and CIGS cell 105 are the same; the size of the back film is larger than the CIGS cell 105; the protective film comprises a main body and side portions, the size of the main body is the same as that of the CIGS battery unit, the side portions are arranged on four sides of the main body and are integrated with the main body into a whole, and the side portions are sealed and tightly cover the structural film and the side faces of the CIGS battery unit 105 and are tightly pressed with the back film. In the solar thin film cell, the body of the protective film, the structural film and the CIGS cell 105 are the core of the main lamination package, and the size needs to be equal; the edge of the protective film is used for packaging the side edge, so that the width of the edge is equal to that of the corresponding side edge, the length of the edge is greater than the thickness of the solar thin film cell, and the excess part is used for being bonded with the back film to realize the fixation of the edge and the internal packaging.
The solar thin-film cell provided by the embodiment of the invention is equivalent to the way that the protective film is used for packaging the main illumination surface and the side surface of the solar thin-film cell at the same time, a special side packaging material is not needed, the solar thin-film cell is simplified, and in addition, the protective film is a whole, so that the bonding surface of the solar thin-film cell is reduced, the risk of water permeation of the solar thin-film cell can be reduced, the service life of the solar thin-film cell is further prolonged, and the requirement of the solar thin-film cell on the use environment is reduced.
In order to obtain the photoelectric conversion efficiency of the solar thin-film battery as large as possible on the premise of ensuring the water blocking function of the solar thin-film battery, in the embodiment of the invention, the protective film is an ETFE film 101; the structural film is an EEA film 103; the back film is a double layer film, one layer in contact with the CIGS cell is an aluminum plastic film 107, and the other layer is a PET film 108.
The ETFE film 101 is a transparent water-blocking film, considering that the ETFE film is used for flexible packaging, the structural strength of the ETFE film is obviously superior to that of common fluororesin transparent films such as PFA, FEP and the like, although the relevant performance of the PCTFE film is slightly better than that of the ETFE film 101, the phase property of the PCTFE film and other materials is poor, the bonding with the structural film after lamination is not facilitated, and the light transmission, the structural strength, the packaging effect and the water-blocking effect are comprehensively considered, in the embodiment of the invention, the ETFE film 101 is used as the protective film.
The EEA film 103 is a type of polyolefin film, and is characterized by excellent toughness and flexibility, and good light transmittance, and in the embodiment of the present invention, the solar thin film battery needs to have good deformation performance, so that the use of the EEA film 103 as a structural film mainly providing structural performance has good effect, and has strong resistance to stress rupture, impact, and bending fatigue. In addition, the EEA film 103 has no corrosive degradation products, and can ensure that the solar thin film cell is not corroded and damaged due to internal degradation.
In addition to ensuring structural strength, the backing film must also have good water-blocking properties, and must also have good adhesive properties as the primary object of bonding other layers. The aluminum plastic film 107 adhesive has good phase property, and can ensure long-time and high-durability adhesive property, thereby ensuring the durability of the solar thin film cell. The PET film 108 has good structural strength and excellent water blocking performance, and can still maintain original various performances in extreme environments such as damp heat, dry heat and the like, so that the PET film is very suitable for being used as an outer layer film of a back film.
In addition to optimizing the design of the films of each layer, embodiments of the present invention also optimize the design of the adhesive between the layers. Specifically, the main body of the ETFE film 101 is adhered to the EEA film 103 through POE adhesive 102; the EEA film 103 and the CIGS battery unit 105 are adhered through EVA glue 104; the CIGS battery unit is adhered to the aluminum plastic film 107 through PVB glue 106; the edge of the ETFE film 101, the side of the structural film, the side of the CIGS cell 105, and the back film are bonded together with POE adhesive 102.
The POE glue 102 has good weather resistance and ultraviolet aging resistance, good adhesion and light transmittance, good phase property with the materials in the embodiment of the invention, firm and stable adhesion and certain water resistance, so that the POE glue 102 is used for adhering the ETFE film 101 in the embodiment of the invention.
The EVA glue 104 is also a transparent adhesive, and has the disadvantage of higher water vapor transmission rate and water absorption rate, and the advantage of lower cost, compared with the POE glue 102. In the embodiment of the present invention, since the ETFE film 101 and the POE adhesive 102 are present to perform double-layer water blocking, a good water blocking effect can be achieved, and therefore, from the viewpoint of cost saving, the EEA film 103 and the CIGS cell 105 are adhered by the EVA adhesive 104.
The PVB adhesive 106 is also one of photovoltaic materials, the light transmittance is slightly inferior to that of the POE adhesive 102, the cost is relatively low, the back film also needs to have good waterproof performance and is not suitable for the EVA adhesive 104, the PVB adhesive 106 can be used in the back film due to good weather resistance, and the back film also needs to have high light transmittance, so the cost is also considered that the PVB adhesive 106 is used for the back film instead of the POE adhesive 102.
In order to ensure that the solar thin film cell can be normally used, current of two electrodes of the CIGS cell unit 105 needs to be led out, in the embodiment of the invention, the surface electrode layer and the back electrode layer 8 of the CIGS cell unit are respectively and electrically connected with the cell electrodes arranged on the back film through wires, and the wires are arranged at the connecting surface between the edge and the back film, namely the wires are sandwiched by the edge and the back film.
In the embodiment of the present invention, the light incident surface is required to have good light transmittance because of the solar cell, and specifically, the ETFE film 101, the EEA film 103, the POE adhesive 102, and the EVA adhesive 104 are all transparent materials.
Example 5
As shown in fig. 4, an encapsulation tool for a flexible solar thin film cell is used for processing the solar thin film cell in example 4; the packaging tool comprises a first tool and a second tool, wherein the first tool and the second tool are at least provided with a group of parallel surfaces, one surface is a plane, and the other surface is provided with a square groove; the size of the groove of the first tool is equal to the size of the EEA film 103, the EVA glue 104 and the CIGS cell unit 105 of the solar thin film cell; the size of the groove of the second tool is equal to the whole size of the solar thin film battery. The solar thin film cell in example 4 corresponds to a CIGS cell 105 and a structural film enclosed by a protective film and a back film. In the embodiment of the invention: the first tooling is used to complete the lamination of the structural film and the CIGS cell 105, including only the lamination bond between layers; the second tooling is used to complete lamination of the protective and back film clad structural film and the CIGS cell 105, including layer-to-layer lamination bonds and edge-to-side bonds.
The embodiment of the invention is mainly used for realizing the solar thin film cell in the embodiment 4, corresponding materials are sequentially placed in the grooves for lamination processing to prepare the solar thin film cell in the embodiment 4, the lamination combination of the solar thin film cell is realized through the square groove of the packaging tool, the dislocation among layers is prevented, the packaging quality of the solar thin film cell is ensured, and the yield is improved.
In order to prevent the laminated material from adhering to the packaging tool, in the embodiment of the invention, the material of the packaging tool is the same as that of the pressure head of the laminating machine, the pressure head of the laminating machine is generally made of a material which is not easy to adhere by the laminated material, and the material of the packaging tool is the same as that of the pressure head for the same reason so as to prevent the laminated object from adhering to the packaging tool.
Example 6
A packaging method of a flexible solar thin film battery is provided, the packaging method uses the packaging tool in embodiment 5 to package the flexible solar thin film battery, and the flexible solar thin film battery in embodiment 4 is manufactured;
the packaging method specifically comprises the following steps:
s1, processing the CIGS cell 105, wherein the size of the CIGS cell 105 should be determined according to the design size, and belongs to preset parameters, and similarly, the sizes of the ETFE film 101, the POE adhesive 102, the EEA film 103, the EVA adhesive 104, and the PVB adhesive 106 also belong to preset parameters, and need to be determined according to the processing target, it should be noted that the length of the edge of the ETFE film 101 is greater than the thickness of the solar thin film cell, the sizes of the aluminum plastic film 107 and the PET film 108 need to be greater than the size of the CIGS cell 105, and an excessively long portion of the edge of the ETFE film 101 can be completely bonded with the aluminum plastic film 107;
s2, placing the groove of the first tool upwards, placing the EEA film 103, the EVA adhesive 104 and the CIGS battery unit 105 in the groove in sequence, aligning all the materials when placing the materials, and placing the materials in the groove of the first tool to ensure that the EEA film 103 and the CIGS battery unit 105 can be laminated to form an integral structure;
s3, placing the first tool in a laminating machine, and performing high-temperature pressing to form an integral structure;
s4, cooling the first tool to room temperature, and taking out the integrated structure pressed in the step S3;
s5, placing the groove of the second tool upwards, sequentially placing an ETFE film 101, POE glue 102, the integral structure of the previous step, PVB glue 106, an aluminum plastic film 107 and a PET film 108 in the groove, wherein the main body of the ETFE film 101 is tightly contacted and aligned with the bottom surface of the groove of the second tool, and the other parts of the ETFE film are aligned with the main body of the ETFE film 101; the edge of the ETFE membrane 101 is closely contacted and aligned with the side wall of the second tool groove, and POE glue 102 is added to the inner side of the edge of the ETFE membrane 101;
s6, placing the second tool in a laminating machine, and performing high-temperature pressing to form an integral structure;
s7, cooling the second tool to room temperature, and taking out the integrated structure pressed in the step S6;
and S8, cutting the back film into a preset size, and finishing the packaging of the flexible solar thin film battery.
According to the embodiment of the invention, the traditional one-step lamination packaging is optimized into two-step lamination packaging, so that not only can a good lamination effect between layers of the solar thin film battery be ensured, but also the side edge packaging effect of a packaging structure can be ensured, the packaged solar thin film battery can form a whole, further the light transmittance and the battery efficiency are improved, the side edge is prevented from deliquescence to a certain extent, the service life of the solar thin film battery is prolonged, and the service environment adaptability of the solar thin film battery is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (13)
1. A composite electrode, comprising: the structure layer, the graphene oxide layer (3), the silver nano layer (2) and the surface adhesion layer;
the structure layer is the middle layer of the composite electrode, the structure layer is an ITO film (4), and the two surfaces of the structure layer are sequentially provided with a graphene oxide layer (3), a silver nano layer (2) and a surface adhesion layer which are closely adhered from inside to outside; the surface adhesion layer of the light facing surface of the composite electrode is a POE layer (1); the surface attachment layer of the backlight surface of the composite electrode is a PDMS layer (5);
the preparation method of the composite electrode comprises the following steps:
step S1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
step S2, spin-coating GO solution on both sides of the ITO film (4);
step S3, spin-coating AgNWs solution on both sides of the ITO film (4) which is spin-coated with GO solution;
step S4, spin-coating liquid POE on the light-facing surface of the ITO film (4) which is spin-coated with the GO solution and the AgNWs solution;
step S5, spin-coating liquid PDMS on the back light surface of the ITO film (4) which is spin-coated with GO solution and AgNWs solution;
s6, after the whole body is dried in an argon atmosphere, the preparation of the composite electrode is finished;
the Ag-rGO silver nano and reduction-graphene oxide composite material is formed between the graphene oxide layer (3) and the silver nano layer (2) by GO and AgNWs.
2. The composite electrode according to claim 1, wherein the structural layer, the graphene oxide layer (3), the silver nanolayer (2) and the surface attachment layer of the composite electrode are all made of transparent materials and have the same size and shape.
3. A method of making a composite electrode, wherein the method is used to make a composite electrode according to any one of claims 1 to 2;
the preparation method comprises the following steps:
step S1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
step S2, spin-coating GO solution on both sides of the ITO film (4);
step S3, spin-coating AgNWs solution on both sides of the ITO film (4) which is spin-coated with GO solution;
step S4, spin-coating liquid POE on the light-facing surface of the ITO film (4) which is spin-coated with the GO solution and the AgNWs solution;
step S5, spin-coating liquid PDMS on the back light surface of the ITO film (4) which is spin-coated with GO solution and AgNWs solution;
and step S6, after the whole body is dried in the argon atmosphere, the preparation of the composite electrode is completed.
4. The method according to claim 3, wherein in step S1, the GO solution is prepared by a HUMMERS oxidation method.
5. A composite electrode, comprising: the graphene layer is arranged on the current collector;
the silver nano layer is arranged on the backlight surface of the graphene layer, the surface adhesion layer is arranged on the backlight surface of the silver nano layer, and the current collector is arranged on the light-facing surface of the graphene layer;
the current collector comprises a silver nano-net and a graphene disc; the silver nano-net covers the light-facing surface of the graphene layer, and the graphene disks are uniformly distributed on the silver nano-net and are electrically connected with the outside through wires;
the preparation method of the composite electrode comprises the following steps:
step S1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
step S2, spin-coating GO solution on one surface of the PET layer;
step S3, spin-coating AgNWs solution on the PET layer which is spin-coated with GO solution;
step S4, spin-coating liquid PDMS on the PET layer which is spin-coated with GO solution and AgNWs solution;
s5, after the whole is dried in an argon atmosphere, taking down the PET layer and keeping the Ag-RGO film;
step S6, spinning GO solution on another PET layer with grid lines engraved in the inner concave, pressing one surface of the spun GO solution on an Ag-RGO film, and taking down the PET layer after the whole body is dried in the argon atmosphere;
s7, spin-coating GO solution disks on the silver nano-net, keeping the GO solution disks uniformly distributed on the silver nano-net, and after the whole body is dried in an argon atmosphere, completing the preparation of the composite electrode.
6. A method of making a composite electrode, wherein the method is used to make a composite electrode according to claim 5;
the preparation method comprises the following steps:
step S1, preparing a graphene oxide GO solution and a silver nanoparticle AgNWs solution;
step S2, spin-coating GO solution on one surface of the PET layer;
step S3, spin-coating AgNWs solution on the PET layer which is spin-coated with GO solution;
step S4, spin-coating liquid PDMS on the PET layer which is spin-coated with GO solution and AgNWs solution;
s5, after the whole is dried in an argon atmosphere, taking down the PET layer and keeping the Ag-RGO film;
step S6, spinning GO solution on another PET layer with grid lines engraved in the inner concave, pressing one surface of the spun GO solution on an Ag-RGO film, and taking down the PET layer after the whole body is dried in the argon atmosphere;
s7, spin-coating GO solution disks on the silver nano-net, keeping the GO solution disks uniformly distributed on the silver nano-net, and after the whole body is dried in an argon atmosphere, completing the preparation of the composite electrode.
7. The method of claim 6, wherein in step S1, the GO solution is prepared by a HUMMERS oxidation method.
8. A CIGS cell (105) comprising, in order, a surface electrode layer, a buffer layer (6), an absorber layer (7), a back electrode layer (8), a stress layer (9) and a base layer (10);
the surface electrode layer is a composite electrode according to any one of claims 1 to 2 or 5;
the buffer layer (6) is an indium selenide layer and an indium sulfide layer;
the back electrode layer (8) is a molybdenum-containing electrode;
the base layer (10) is a PEI layer;
the stress layer (9) is used for buffering the thermal stress difference between the back electrode layer (8) and the base layer (10).
9. CIGS cell as claimed in claim 8, characterised in that said stress layer (9) is a Ag film, said molybdenum electrode being doped with sodium.
10. A solar thin film cell, characterized in that the solar thin film cell is rectangular and comprises a protective film, a structural film, a CIGS cell unit (105) and a back film which are compacted from top to bottom;
the CIGS cell (105) is the CIGS cell of claim 8 or 9;
the structural film and the CIGS cell (105) are the same size;
the back film is larger than the CIGS cell (105);
the protective film comprises a main body and edges, the size of the main body is the same as that of the CIGS battery unit (105), the edges are arranged on four sides of the main body and are integrated with the main body into a whole, and the edges tightly cover the structural film and the side faces of the CIGS battery unit (105) in a sealing mode and are tightly pressed with the back film.
11. The solar thin film cell of claim 10, wherein the protective film is an ETFE film (101); the structural film is an EEA film (103); the back film is a double-layer film, one layer in contact with the CIGS battery unit (105) is an aluminum plastic film (107), and the other layer is a PET film (108).
12. The solar thin film cell of claim 11, wherein the main body of the ETFE film (101) and the EEA film (103) are bonded by a POE adhesive (102); the EEA film (103) and the CIGS battery unit (105) are adhered through EVA glue (104); the CIGS battery unit (105) and the aluminum plastic film (107) are adhered through PVB glue (106).
13. The solar thin-film cell of claim 12, wherein the edge of the ETFE film (101) and the side of the structural film, the side of the CIGS cell (105) and the back film are bonded by POE adhesive (102).
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