CN116457951A - Solar cell metallization method and solar cell - Google Patents
Solar cell metallization method and solar cell Download PDFInfo
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- CN116457951A CN116457951A CN202380007906.3A CN202380007906A CN116457951A CN 116457951 A CN116457951 A CN 116457951A CN 202380007906 A CN202380007906 A CN 202380007906A CN 116457951 A CN116457951 A CN 116457951A
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Abstract
The application belongs to the technical field of solar cells, and particularly relates to a solar cell metallization method and a solar cell. The metallization method of the solar cell comprises the following steps: forming a fine grid first layer on the front side of the battery with a first conductive paste, the first conductive paste containing aluminum; forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive slurry, wherein the second conductive slurry contains silver and does not contain aluminum; and sintering the fine grid first layer and the fine grid second layer to obtain the fine grid. The second conductive paste which does not contain aluminum powder is matched with the first conductive paste to form a fine grid pattern, and because the paste does not contain aluminum powder, the overall silver content of the paste is high, so that the volume resistance can be reduced. And sintering the first layer of the fine grid and the second layer of the fine grid to realize metallized ohmic contact, so as to obtain the fine grid.
Description
Technical Field
The application belongs to the technical field of solar cells, and particularly relates to a solar cell metallization method and a solar cell.
Background
Crystalline silicon solar cells have been widely used in recent years, the conversion efficiency is continuously improved, and the production cost is continuously reduced. Currently crystalline silicon solar cells account for more than eight percent of the total solar cell market. In crystalline silicon solar cells, TOPCon passivation contact cells are novel high-conversion efficiency cells, the conversion efficiency can reach more than 24%, the compatibility with conventional production lines is good, the passivation contact layer provides good surface passivation for an n+ surface, metal contact recombination is greatly reduced, and the open-circuit voltage and short-circuit current of the cells are improved. An antireflection film (mostly a silicon nitride film layer) is arranged on a silicon substrate of the silicon solar cell, a grid line pattern is arranged on the antireflection film, and a front electrode formed by front conductive silver paste is arranged in the grid line pattern. In a common manufacturing process of a silicon solar cell, firstly, an antireflection film is plated on a silicon substrate by a method such as vapor deposition, then front-side conductive paste is printed by a screen printing mode, the front-side conductive paste is made to corrode the antireflection film by sintering, and ohmic contact is formed between the front-side conductive paste and the silicon substrate; after sintering, the conductive paste forms grid line type front electrode on the surface of the silicon substrate.
For example, the prior literature discloses a metallization method of an N-type solar cell, a module and a system, and the technical scheme of the patent is that an N-type crystalline silicon substrate is processed, and a p+ doped region and a front surface passivation antireflection film which are sequentially arranged from inside to outside are formed on the front surface of the N-type crystalline silicon substrate; forming an n+ doped region and a back surface passivation film on the back surface of the N-type crystalline silicon substrate sequentially from inside to outside; forming a groove-shaped structure penetrating through the passivation anti-reflection film on the front surface of the N-type crystalline silicon substrate, and printing a back electrode on the back surface of the N-type crystalline silicon substrate by using silver paste; and then printing aluminum paste on the groove-shaped structure to form a front fine grid, then printing aluminum-doped silver paste or silver paste to form a front main grid, and sintering to obtain the N-type solar cell. The invention also needs to open the groove of the passivation anti-reflection film before printing the front surface sizing agent, has complex process, and needs to increase process equipment if laser is used for open the groove, the invention has the advantages that the production cost is increased, the fine grid is aluminum paste, the generated line resistance is higher, aluminum spines are easy to generate in the aluminum paste, the metal recombination is increased, and finally the photoelectric conversion efficiency is reduced.
The front side of the N-type cell is a boron (B) doped Si semiconductor. The direct formation of the Ag and boron (B) doped Si semiconductor has poor ohmic contact, and the typical contact resistivity can reach 50mΩ cm 2 The above. The front conductive paste of the N-type TOPCON solar cell needs to be made into silver-aluminum paste, and forms good Ag/Al ohmic contact with the emitter through the combined action of aluminum, silver and glass. Reducing the contact resistance is advantageous for improving the filling, but because of the addition of aluminum powder, the bulk resistance is increased, thereby reducing the conversion efficiency to some extent. Moreover, a large size of silver-aluminum alloy results in enhanced metal recombination, reduced open pressure, and reduced conversion efficiency.
Disclosure of Invention
Technical problem
The purpose of the application is to provide a metallization method of a solar cell and the solar cell aiming at solving the problem that the body resistance is increased and the conversion efficiency is reduced due to the fact that aluminum powder is added into the existing solar cell.
Technical solution
In order to achieve the above object, the technical scheme adopted in the application is as follows:
the first aspect of the application provides a metallization method of a solar cell, which comprises the following steps:
forming a fine grid first layer on the front side of the battery with a first conductive paste, the first conductive paste containing aluminum;
forming a fine grid second layer by using a second conductive paste, wherein the fine grid second layer completely or partially covers the fine grid first layer, and the second conductive paste contains silver and does not contain aluminum;
And sintering the fine grid first layer and the fine grid second layer to obtain the fine grid.
In a second aspect, the present application provides a solar cell comprising a fine grid produced by the metallization process described herein.
Advantageous effects
According to the metallization method of the solar cell, the fine grid first layer is formed on the passivation layer on the front side of the cell through the first conductive paste containing aluminum, the fine grid second layer is formed through the second conductive paste containing silver, and the fine grid second layer completely or partially covers the fine grid first layer, so that the aluminum content in the total conductive paste is reduced. Most of aluminum powder in the first conductive paste can participate in the process of forming ohmic contact by silver-aluminum alloy, aluminum components in the conductive paste can be effectively utilized, and the size and the number of the formed silver-aluminum alloy can be controlled by adjusting the size of a single scattered point and the distance between adjacent scattered points of the first layer of the fine grid, so that the metal composite effect is effectively reduced while the low contact resistance is realized. The second conductive paste which does not contain aluminum powder is matched with the first conductive paste to form a fine grid pattern, and because the paste does not contain aluminum powder, the overall silver content of the paste is high, so that the volume resistance can be reduced. And sintering the first layer of the fine grid and the second layer of the fine grid to realize metallized ohmic contact, so as to obtain the fine grid.
The solar cell in the application comprises the thin grid prepared by the metallization method, so that the conductivity of the solar cell is facilitated. The embodiment research shows that the solar cell has the bulk resistance of 246-344 mΩ, the open voltage of 720.2-723.1 mV, the filling of 82.24-82.87, and the photoelectric conversion efficiency (Eta) of 24.89-25.02 wt%, and compared with the existing cell, the solar cell has the advantages of low bulk resistance, high open voltage, high filling and excellent photoelectric conversion efficiency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the drawings needed in the description of the embodiments, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view (top view) of a scatter pattern provided in an embodiment of the present application;
FIG. 2 is a schematic view (top view) of another scatter plot provided in an embodiment of the present application;
fig. 3 is a schematic view (top view) of a fine gate pattern corresponding to fig. 1 according to an embodiment of the present application;
Fig. 4 is a schematic view (top view) of the fine gate pattern corresponding to fig. 2 according to an embodiment of the present application;
fig. 5 is a schematic view (side view) of a fine gate pattern according to an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b, or c)", or "at least one (a, b, and c)", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the specification of the present 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.
The mass of the related components mentioned in the embodiments of the present application may refer not only to the specific content of each component, but also to the proportional relationship of the mass of each component, so long as the content of the related component is scaled up or down according to the embodiments of the present application, which are within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms first and second are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance or number of features indicated in order to distinguish one object from another. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of the embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
An embodiment of the present application provides a method for metallizing a solar cell, including the following steps:
step S10: forming a fine grid first layer on the front surface of the battery by using a first conductive paste containing aluminum, wherein the first conductive paste contains aluminum;
step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the second conductive paste contains silver and does not contain aluminum;
step S30: and sintering the fine grid first layer and the fine grid second layer to obtain the fine grid.
According to the metallization method of the solar cell, the fine grid first layer is formed on the front surface of the cell through the first conductive paste containing aluminum, and the fine grid second layer is formed by combining the second conductive paste containing silver, so that the content of aluminum in the total conductive paste is reduced, and the volume resistance is reduced. Most of aluminum powder in the first conductive paste can participate in the ohmic contact forming process of the silver-aluminum alloy, and aluminum components in the conductive paste can be effectively utilized to realize low contact resistance. The second conductive paste which does not contain aluminum powder is matched with the first conductive paste to form a fine grid pattern, and because the paste does not contain aluminum powder, the overall silver content of the paste is high, so that the volume resistance can be reduced. And sintering the first layer of the fine grid and the second layer of the fine grid to realize metallized ohmic contact, so as to obtain the fine grid. Further, the first conductive paste containing aluminum forms a fine grid first layer on the passivation layer on the front surface of the battery, and the pattern of the fine grid first layer is scattered. The scattered distribution includes periodic distribution or irregular distribution. The diameter range of the single scattered points is 8-30 microns; the distance between two adjacent scattered points is 10-60 micrometers, and the size and the number of the separated silver-aluminum alloy spines can be controlled by adjusting the size of a single scattered point of the fine grid first layer and the distance between the adjacent scattered points, so that ohmic contact is ensured, the metal composite effect of the solar cell is lightened, and the problems that aluminum powder is added into the existing solar cell, the formed silver-aluminum alloy with larger size leads to metal composite enhancement, opening pressure is reduced, and conversion efficiency is reduced are solved.
Step S10:
in step S10, the pattern of the fine grid first layer is scattered dots. Specifically, as shown in fig. 1 and 2, a scattered dot pattern is formed on the front surface of the battery by using the first conductive paste containing aluminum as a fine grid first layer, and the scattered dot pattern can further reduce the aluminum consumption, reduce the bulk resistance, and improve the conversion efficiency of the battery. By adjusting the size of a single scattered point and the distance between adjacent scattered points, the size and the number of the separated silver-aluminum alloy spines can be controlled, so that ohmic contact is ensured, and the metal composite effect of the solar cell is lightened.
In some embodiments, the first conductive paste comprising aluminum, the scattered pattern distribution comprises a periodic distribution or an irregular distribution. Furthermore, the periodic distribution is beneficial to uniformly distributing the aluminum powder, so that the aluminum component in the first conductive paste can be further effectively utilized, the volume resistance can be reduced, and the conversion efficiency of the battery is improved. For example, as shown in fig. 1, the first layer of the fine grid includes a plurality of repeating units with the same interval distance, the repeating units are distributed along the horizontal direction to form the first layer of the fine grid, each repeating unit includes a first scattered point and a second scattered point, the first scattered point and the second scattered point are diagonally arranged, and the first scattered point and the second scattered point are respectively close to the upper side and the lower side of the fine grid, so that aluminum powder is uniformly distributed.
In some embodiments, the individual dots have diameters of 8-30 microns, such as 8 microns, 15 microns, 30 microns, etc., and the amount of aluminum powder can be controlled by controlling the size of the dots. Specifically, a scattered point pattern is formed on the front surface of the battery by using first conductive paste containing silver and aluminum as a fine grid first layer; the second layer of the fine grid is formed by using the second conductive paste containing silver, and the second layer of the fine grid completely covers the first fine grid pattern, so that the aluminum consumption can be further reduced, the bulk resistance can be reduced, the conversion efficiency of the battery is improved, and the problem of grid breakage of the first layer of the fine grid can be solved by the second layer of the fine grid.
In some embodiments, the distance between two adjacent scattered points is 10-60 microns, such as 10 microns, 30 microns, 60 microns, etc., and the uniformity of the distribution of the aluminum powder can be further improved by controlling the distance between the scattered points. Specifically, a scattered point pattern is formed on the front surface of the battery by using first conductive paste containing silver and aluminum as a fine grid first layer; the second layer of the fine grid is formed by the second conductive paste containing silver, and the second layer of the fine grid completely or partially covers the first fine grid pattern, so that aluminum components in the first conductive paste can be further effectively utilized, the bulk resistance can be reduced, the conversion efficiency of the battery is improved, and the problem of grid breakage of the first layer of the fine grid can be solved by the second layer of the fine grid.
In some embodiments, there are various methods of forming the scattered dot pattern, such as, but not limited to, screen printing, laser transfer printing, inkjet printing.
In some embodiments, the first conductive paste comprises the following components, based on 100wt% mass of the first conductive paste:
in the embodiment of the application, the first glass powder, the first silver powder and the aluminum powder in the first conductive paste act together to separate out silver-aluminum alloy in the silicon substrate, so that ohmic contact is realized. By adjusting the size of a single scattered point and the distance between adjacent scattered points, the size and the number of the separated silver-aluminum alloy spines can be controlled, so that ohmic contact is ensured, and the metal composite effect of the solar cell is lightened. In addition, aluminum powder and first silver powder are dispersed in a first organic carrier, the viscosity of the slurry can be adjusted, printing of materials is facilitated, coating treatment is facilitated on the first conductive slurry, a conductive layer is formed, and in the subsequent sintering process, the first glass powder is beneficial to enhancing the low-temperature silver melting capacity of glass.
In a specific embodiment, the first glass frit comprises the following components in percentage by mass, based on 100% by weight of the first glass frit:
in the embodiment of the application, the first glass powder has a strong corrosion effect, and the glass powder, the aluminum powder and the silver powder act together to separate out silver-aluminum alloy in the silicon substrate, so that ohmic contact is realized.
In a specific embodiment, to further adjust the conductivity of the first conductive paste, some other elements are added to the first glass frit, where the first additive element includes at least one of titanium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, barium, manganese, tungsten, nickel, tin, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium, bismuth, lithium, and zinc.
In a specific embodiment, the first glass frit comprises at least one glass frit. Specifically, the first glass frit may contain one glass frit, and the first glass frit may be formed by mixing at least two glass frits, which may facilitate the raw material source.
In some embodiments, the aluminum powder has a particle size of 0.1-5 microns, such as 0.1 microns, 0.2 microns, 5 microns, etc., which can improve the dispersibility and packing compactness of the conductive paste and reduce the line resistance of the fine grid.
In some embodiments, the particle size of the silver powder is 0.1-5 microns, such as 0.1 micron, 0.2 micron, 5 microns, etc., which can improve the dispersibility and stacking compactness of the conductive paste, is beneficial to improving the sintering compactness of the silver layer and reduces the line resistance of the fine grid.
It is known that the first organic carrier imparts to the paste composition viscosity and rheological characteristics suitable for printing by mechanical mixing with the inorganic components of the composition for solar cell electrodes. The first organic carrier may be any typical organic carrier for the composition of the solar cell electrode, and may contain a binder resin, a solvent, and the like.
In some embodiments, the first organic carrier comprises the following components in mass percent, based on 100 weight percent of the first organic carrier:
in a specific embodiment, the first organic solvent is at least one selected from terpineol, butyl glycol acetate, ethyl glycol acetate, dodecyl ester, cetyl ester, diethylene glycol octyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, butyl carbitol, terpenes. In the above, the mass component of the first organic solvent may be 50wt% to 95wt%.
In a specific embodiment, the first polymer is selected from at least one of cellulose and its derivatives, acrylic resins, alkyd resins, polyester resins. In the above, the mass component of the first polymer may be 1wt% to 40wt%.
In a specific embodiment, the first wetting dispersant is at least one selected from the group consisting of fatty acids, amide derivatives of fatty acids, ester derivatives of fatty acids, polyethylene waxes, polyethylene glycols. In the above, the first wetting dispersant may have a mass component of 0.1wt% to 10wt%.
In a specific embodiment, the first thixotropic agent is selected from at least one of hydrogenated castor oil derivatives, polyamide waxes, polyureas, fumed silica. In the above, the first thixotropic agent may have a mass component of 1wt% to 20wt%.
In a specific embodiment, the first other functional auxiliary is selected from at least one of polymethylphenylsiloxane, polyphenylsiloxane, phthalate, diethyl phthalate, tributyl citrate, dimethyl phthalate, diacetin, diethylene glycol monobutyl ether acetate, dibutyl maleate, dimethyl adipate, dibutyl oxalate, dibutyl phthalate, microcrystalline wax, polydimethylsiloxane, polyvinylbutyral, polyether polyester modified organosiloxane, alkyl modified organosiloxane. In the above, the mass component of the first other functional auxiliary agent may be 0.1wt% to 20wt%.
Step S20:
in step S20, the fine-gate second layer covers the fine-gate first layer in whole or in part. Further, the whole coverage and the second layer of the fine grid can solve the problem of grid breakage of the first layer of the fine grid.
In some embodiments, as shown in fig. 3 to 5, the fine-grid second layer is formed by using the second conductive paste containing silver, and the fine-grid second layer entirely covers the scattered first fine-grid pattern, the scattered dots can further reduce the aluminum consumption, can reduce the bulk resistance, thereby improving the conversion efficiency of the battery, and can solve the problem of broken grid of the fine-grid first layer.
In some embodiments, the second conductive paste comprises the following components, based on 100wt% mass of the second conductive paste:
80 to 98 percent by weight of second silver powder
0.5 to 8 weight percent of second glass powder
3-15 wt% of a second organic carrier.
In the embodiment of the application, after the first conductive paste and the second conductive paste are sintered, metallization of the front surface of the solar cell is jointly achieved. The aluminum powder, the first silver powder and the second silver powder endow the conductive paste with conductive performance under the action of the first glass and the second glass, aluminum components in the conductive paste can be effectively utilized, and the size and the number of separated silver-aluminum alloy spines can be controlled by adjusting the size of a single scattered point and the distance between adjacent scattered points, so that ohmic contact is ensured, and the metal composite effect of the solar cell is lightened. On the other hand, the first layer of the fine grid is formed on the front surface of the battery through the first conductive paste containing aluminum, and the second layer of the fine grid is formed by combining the second conductive paste containing silver, so that the content of aluminum in the total conductive paste is reduced, and the volume resistance is reduced.
The first conductive paste and the second conductive paste in the embodiment of the application are matched for use, so that the volume resistance can be reduced, the lower contact resistance is kept, the metal composite effect is reduced, and the conversion efficiency of the solar cell is improved, and the electricity cost is reduced. In addition, the second silver powder is dispersed in the second organic carrier, the viscosity of the slurry can be adjusted, printing of materials is facilitated, coating treatment is facilitated on the second conductive slurry, a conductive layer is formed, and in the subsequent sintering process, the second glass powder is beneficial to enhancing the low-temperature silver melting capacity of glass.
In some embodiments, the second glass frit comprises the following components in mass percent, based on 100 weight percent of the second glass frit:
in the embodiment of the application, the second glass powder has weak corrosiveness and is mainly used for assisting in silver powder sintering, and after the second conductive paste is sintered, the second glass powder is combined with silver-aluminum alloy formed after the first conductive paste is sintered, so that metallization of the front surface of the solar cell is jointly realized.
In some embodiments, to further adjust the conductivity of the second conductive paste, some other element needs to be added to the second glass frit, where the first additive element includes at least one of tellurium, gallium, barium, and germanium.
In some embodiments, the silver powder has a particle size of 0.1-5 microns, such as 0.2 microns, 5 microns, etc., which can improve the dispersibility and packing compactness of the conductive paste, facilitate the improvement of sintering compactness of the silver layer, and reduce the line resistance of the silver fine grid.
It is known that the second organic carrier imparts to the paste composition viscosity and rheological characteristics suitable for printing by mechanical mixing with the inorganic components of the composition for solar cell electrodes. The second organic carrier may be any typical organic carrier for the composition of the solar cell electrode, and may contain a binder resin, a solvent, and the like.
In some embodiments, the second organic carrier comprises the following components in mass percent, based on 100 weight percent of the second organic carrier:
in a specific embodiment, the second organic solvent is at least one selected from terpineol, butyl glycol acetate, ethyl glycol acetate, dodecyl ester, cetyl ester, diethylene glycol octyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, butyl carbitol, terpenes. In the above, the mass component of the second organic solvent may be 60wt% to 90wt%.
In a specific embodiment, the second polymer is selected from at least one of cellulose and its derivatives, acrylic resins, alkyd resins, polyester resins. In the above, the mass component of the second polymer may be 1wt% to 35wt%.
In a specific embodiment, the second wetting dispersant is at least one selected from the group consisting of fatty acids, amide derivatives of fatty acids, ester derivatives of fatty acids, polyethylene waxes, polyethylene glycols. In the above, the mass component of the second wetting dispersant may be 0.1wt% to 10wt%.
In a specific embodiment, the second thixotropic agent is selected from at least one of hydrogenated castor oil derivatives, polyamide waxes, polyureas, fumed silica. In the above, the second thixotropic agent may have a mass component of 1wt% to 18wt%.
In a specific embodiment, the second other functional auxiliary is selected from at least one of polymethylphenylsiloxane, polyphenylsiloxane, phthalate, diethyl phthalate, tributyl phthalate dimethyl citrate, diacetin, diethylene glycol monobutyl ether acetate, dibutyl maleate, dimethyl adipate, dibutyl oxalate, dibutyl phthalate, microcrystalline wax, polydimethylsiloxane, polyvinylbutyral, polyether polyester modified organosiloxane, alkyl modified organosiloxane. In the above, the mass component of the second other functional auxiliary agent may be 0.1wt% to 18wt%.
In some embodiments, the mass ratio of the first conductive paste to the second conductive paste is 0.1 to 30:99.9 to 70, and the use amount of the aluminum powder can be controlled by controlling the mass ratio of the first conductive paste to the second conductive paste. Further, through adjusting the compound ratio of glass material, organic carrier, aluminium powder and silver powder, can further improve the battery contact resistance that this application embodiment provided lower, and then promote solar cell's conversion efficiency and reduce degree electricity cost.
In some embodiments, the pattern of the fine-grid second layer may be formed by various methods, such as, but not limited to, screen printing, laser transfer, and ink-jet printing.
Step S30:
in step S30, the sintering treatment is performed at a temperature of 700-850 ℃, such as 700 ℃, 750 ℃, 800 ℃, 850 ℃, etc.
In a second aspect, embodiments of the present application provide a battery comprising a fine grid prepared by the metallization method described herein.
The size and the number of the separated silver-aluminum alloy spines can be controlled by adjusting the size of a single scattered point of the fine grid first layer and the distance between adjacent scattered points according to the aluminum powder and silver powder alloying effect in the metallization method, so that ohmic contact is ensured, and the metal composite effect of the solar cell is lightened. In the second aspect, the fine grid first layer is formed on the front surface of the battery through the first conductive paste containing aluminum, the fine grid second layer is formed by combining the second conductive paste containing silver, most of aluminum powder in the first conductive paste can participate in the ohmic contact forming process of the silver-aluminum alloy, aluminum components in the conductive paste can be effectively utilized, the content of aluminum in the total conductive paste is further reduced, and the volume resistance is reduced. Therefore, the battery in the embodiment of the application comprises the thin grid prepared by the metallization method, and the conductivity of the battery can be improved. The embodiment research shows that the solar cell has the bulk resistance of 246-344 mΩ, the open voltage of 720.2-723.1 mV, the filling of 82.24-82.87, and the photoelectric conversion efficiency (Eta) of 24.89-25.02 wt%, and compared with the existing cell, the solar cell has the advantages of lower bulk resistance, high open voltage, high filling and excellent photoelectric conversion efficiency.
In order that the implementation details and operations described above in the present application may be clearly understood by those skilled in the art, and that the metallization method of the solar cell and the advanced performance of the solar cell according to the embodiments of the present application are significantly reflected, the following examples are given to illustrate the above technical solutions by using a plurality of embodiments.
Example 1
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 85wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 3wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 10 microns and the spacing between the scattered points to be 15 microns in periodic arrangement;
specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 Content of2wt%, znO content 5wt%, ga 2 O 3 The content was 2wt%.
The mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows: twelve alcohol esters 15wt%, dimethyl oxalate 20wt%, butyl diglycol acetate 45wt%, oleic acid 1wt%, ethyl cellulose 10wt%, polyethylene glycol 2wt%, tributyl citrate 6wt%, microcrystalline wax 2wt% and hydrogenated castor oil 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the second conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content 11wt%, tiO 2 Content 7wt%, geO 2 Content 6wt%;
the mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Step S30: and sintering the first fine grid layer and the second fine grid layer at 760 ℃ to obtain the fine grid.
Example 2
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
Step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 86wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 2wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 10 microns and the spacing between the scattered points to be 15 microns in periodic arrangement;
specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt% of ZnO, 5wt% of Ga 2 O 3 The content was 2wt%.
The mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows: twelve alcohol esters 15wt%, dimethyl oxalate 20wt%, butyl diglycol acetate 45wt%, oleic acid 1wt%, ethyl cellulose 10wt%, polyethylene glycol 2wt%, tributyl citrate 6wt%, microcrystalline wax 2wt% and hydrogenated castor oil 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the first conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
Specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content 11wt%, tiO 2 Content 7wt%, geO 2 Content 6wt%;
the mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Step S30: and sintering the first fine grid layer and the second fine grid layer at 760 ℃ to obtain the fine grid.
Example 3
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 85wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 3wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 20 microns and the interval between the scattered points to be 40 microns to be periodically arranged;
Specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt%, znO 5wt% and Ga 2 O 3 The content is 2wt%;
the mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows: twelve alcohol esters 15wt%, dimethyl oxalate 20wt%, butyl diglycol acetate 45wt%, oleic acid 1wt%, ethyl cellulose 10wt%, polyethylene glycol 2wt%, tributyl citrate 6wt%, microcrystalline wax 2wt% and hydrogenated castor oil 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the first conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
step S30: sintering the first fine grid layer and the second fine grid layer at 760 ℃ to obtain the fine grid;
specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content of 11wt% TiO 2 Content 7wt%, geO 2 The content was 6wt%.
The mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Example 4
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 86wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 2wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 20 microns and the interval between the scattered points to be 40 microns to be periodically arranged;
specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt%, znO 5wt% and Ga 2 O 3 The content was 2wt%.
The mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows:
alcohol ester twelve content 15wt%, dimethyl oxalate content 20wt%, diethylene glycol butyl ether acetate content 45wt%, oleic acid content 1wt%, ethyl cellulose content 10wt%, polyethylene glycol content 2wt%, tributyl citrate content 6wt%, microcrystalline wax content 2wt%, and hydrogenated castor oil content 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the first conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content 11wt%, tiO 2 Content 7wt%, geO 2 The content was 6wt%.
The mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Step S30: and sintering the first fine grid layer and the second fine grid layer at 760 ℃ to obtain the fine grid.
Example 5
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 85wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 3wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 10 microns and the spacing between the scattered points to be 15 microns in periodic arrangement;
specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt%, znO 5wt% and Ga 2 O 3 The content is 2wt%; the mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows:
alcohol ester twelve content 15wt%, dimethyl oxalate content 20wt%, diethylene glycol butyl ether acetate content 45wt%, oleic acid content 1wt%, ethyl cellulose content 10wt%, polyethylene glycol content 2wt%, tributyl citrate content 6wt%, microcrystalline wax content 2wt%, and hydrogenated castor oil content 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the first conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content 11wt%, tiO 2 Content 7wt%, geO 2 Content 6wt%;
the mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Step S30: and sintering the first fine grid layer and the second fine grid layer at 740 ℃ to obtain the fine grid.
Example 6
The embodiment provides a metallization method of a solar cell, which comprises the following steps:
Step S10: forming a scattered fine grid first layer on the front surface of the battery by using a first conductive paste containing silver and aluminum, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 85wt% of first silver powder; 9wt% of a first organic carrier; 3wt% of a first glass frit; 3wt% of aluminum powder, controlling the diameter of scattered points of the scattered point pattern screen plate to be 10 microns and the spacing between the scattered points to be 15 microns in periodic arrangement;
specifically, the mass content of the first glass powder is 100wt%, and the components are as follows: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt%, znO 5wt% and Ga 2 O 3 The content is 2wt%;
the mass content of the first organic carrier is 100wt%, and the components of the first organic carrier are as follows: alcohol ester twelve content 15wt%, dimethyl oxalate content 20wt%, diethylene glycol butyl ether acetate content 45wt%, oleic acid content 1wt%, ethyl cellulose content 10wt%, polyethylene glycol content 2wt%, tributyl citrate content 6wt%, microcrystalline wax content 2wt%, and hydrogenated castor oil content 2wt%.
Step S20: forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive paste containing silver, wherein the fine grid second layer completely covers the fine grid first layer, and the first conductive paste comprises the following components in percentage by weight based on the mass of the second conductive paste of 100 percent: 89wt% of second silver powder; 9wt% of a second organic carrier; 2wt% of a second glass frit;
Specifically, the mass content of the second glass powder is calculated by taking the mass of the second glass powder as 100 weight percent: pbO content 50wt%, B 2 O 3 Content 5wt%, siO 2 Content of 21wt%, bi 2 O 3 Content 11wt%, tiO 2 Content 7wt%, geO 2 Content 6wt%;
the mass content of the second organic carrier is 100wt%, and the components of the second organic carrier are as follows: 5wt% of dimethyl oxalate, 70wt% of diethylene glycol butyl ether acetate, 1wt% of lauric acid, 10wt% of ethyl cellulose, 2wt% of polyethylene glycol, 10wt% of tributyl citrate and 2wt% of polyamide wax.
Step S30: and sintering the first fine grid layer and the second fine grid layer at 780 ℃ to obtain the fine grid.
Comparative example 1
The comparative example provides a method of metallizing a solar cell comprising the steps of:
step S10: the method comprises the steps of directly printing a first conductive paste containing silver and aluminum on the front surface of a battery to form a fine grid without layering printing, wherein the first conductive paste comprises the following components in percentage by weight based on 100% by weight of the first conductive paste: 85wt% of silver powder; 9wt% of an organic carrier; 5wt% of glass; 2wt% of aluminum powder;
specifically, the glass powder comprises the following components in percentage by mass based on 100% by mass of the glass powder: pbO content 72wt%, B 2 O 3 Content of 12wt%, siO 2 Content of 7wt%, al 2 O 3 2wt% of ZnO, 5wt% of Ga 2 O 3 The content is 2wt%;
the mass content of the organic carrier is calculated as 100 weight percent, and the components of the organic carrier are as follows: twelve alcohol esters 15wt%, dimethyl oxalate 20wt%, butyl diglycol acetate 45wt%, oleic acid 1wt%, ethyl cellulose 10wt%, polyethylene glycol 2wt%, tributyl citrate 6wt%, microcrystalline wax 2wt% and hydrogenated castor oil 2wt%.
Step S30: and sintering the fine grid at 760 ℃ to obtain the fine grid.
Performance testing
The properties of the N-type TOPCON solar cells formed after sintering in examples 1 to 6 are shown in table 1 below:
TABLE 1 Performance test results
Examples 1 to 6 in comparison with comparative example 1, the fine grid first layer was formed on the front surface of the battery by the first conductive paste containing silver and aluminum, and the fine grid second layer was formed in combination with the second conductive paste containing silver, thereby reducing the aluminum content in the total conductive paste. It can be seen from the above table that the body resistance can be effectively reduced, the open pressure and the filling can be improved, and the conversion efficiency can be finally improved by the metallization method and the conductive paste used in combination.
By controlling the diameter and the scattered point distance of the scattered points of the scattered point pattern screen, the using amount of the first conductive paste and the second conductive paste are reasonably matched, the size and the number of the separated silver aluminum alloy spines can be controlled while the volume resistance is reduced, ohmic contact is ensured, the metal composite effect of the solar cell is lightened, and accordingly higher open pressure and higher filling are achieved, and finally higher efficiency is achieved.
The sintering temperature is adjusted, so that a good metallization effect can be obtained in a wider temperature range. Within this temperature range, there is a more suitable sintering temperature, and a higher efficiency can be obtained.
The front-side conductive paste used in the metallization method of the N-type TOPCO solar cell can meet the requirements of silk-screen front-side grid electrodes of the mainstream N-type TOPCO solar cell in the market.
The bulk resistance of the solar cells in examples 1 to 6 can reach 246 to 344mΩ, the open voltage can reach 720.2 to 723.1mV, the filling can reach 82.24 to 82.87, and the photoelectric conversion efficiency (Eta) is 24.89 to 25.02wt%. Therefore, through reasonable collocation, most of aluminum powder in the first conductive paste can participate in the process of forming ohmic contact by silver-aluminum alloy, aluminum components in the conductive paste can be effectively utilized, low contact resistance, low bulk resistance, high open pressure and high filling are realized, and finally high conversion efficiency is realized.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (19)
1. A method of metallizing a solar cell, comprising the steps of:
forming a fine grid first layer on the front side of the cell with a first conductive paste, the first conductive paste comprising aluminum;
forming a fine grid second layer on the surface of the fine grid first layer by using a second conductive slurry, wherein the second conductive slurry contains silver and does not contain aluminum;
and sintering the fine grid first layer and the fine grid second layer to obtain the fine grid.
2. The metallization method of claim 1, wherein the fine-gate second layer covers the fine-gate first layer in whole or in part.
3. The metallization method of claim 1, wherein the pattern of the fine-gate first layer is in the form of discrete dots.
4. A metallization process according to claim 3, wherein the scattered distribution comprises a periodic distribution or an irregular distribution.
5. A metallization process according to claim 3, wherein the individual dots have a diameter in the range of 8 to 30 microns;
Or/and, the distance between two adjacent scattered points is 10-60 microns.
6. The metallization method of claim 1, wherein the mass ratio of the first conductive paste to the second conductive paste is 0.1-30: 99.9 to 70.
7. The metallization method of claim 1, wherein the first conductive paste comprises the following components in percentage by mass, based on 100% by mass of the first conductive paste:
8. the metallization process of claim 7, wherein the aluminum powder has a particle size of 0.1 to 5 microns;
or/and the particle size of the first silver powder is 0.1-5 microns;
or/and, the first glass frit comprises at least one glass frit.
9. The metallization method of claim 7, wherein the first glass frit comprises the following components in mass percent, based on 100 weight percent of the first glass frit:
10. the metallization process of claim 9, wherein the first additive element comprises at least one of titanium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, barium, manganese, tungsten, nickel, tin, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium, bismuth, lithium, zinc.
11. The metallization process of claim 7, wherein the first organic carrier comprises the following components in mass percent, based on 100 weight percent of the first organic carrier:
12. the metallization method of any one of claims 1 to 11, wherein the second conductive paste comprises the following components in mass percent, based on the mass of the second conductive paste being 100 wt%:
80 to 98 percent by weight of second silver powder
0.5 to 8 weight percent of second glass powder
3-15 wt% of a second organic carrier.
13. The metallization process of claim 12, wherein the second silver powder has a particle size of 0.1 to 5 microns.
14. The metallization method of claim 12, wherein the second glass frit comprises the following components in mass percent, based on the mass of the second glass frit as 100 wt%:
15. the metallization method of claim 14, wherein said second additive element comprises at least one of tellurium, gallium, barium, germanium.
16. The metallization process of claim 12, wherein the second organic carrier comprises the following components in mass percent, based on the mass of the second organic carrier being 100 wt%:
17. The metallization process of claim 16, wherein the first and second organic solvents are each independently selected from at least one of terpineol, butyl cellosolve acetate, ethylene glycol diethyl ether acetate, dodecyl ester, cetyl ester, diethylene glycol octyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, butyl carbitol, terpenes;
the first polymer and the second polymer are respectively and independently selected from at least one of cellulose and derivatives thereof, acrylic resin, alkyd resin and polyester resin;
the first wetting dispersant and the second wetting dispersant are respectively and independently selected from at least one of fatty acid, amide derivative of fatty acid, ester derivative of fatty acid, polyethylene wax and polyethylene glycol;
the first thixotropic agent and the second thixotropic agent are respectively and independently selected from at least one of hydrogenated castor oil derivatives, polyamide waxes, polyureas and fumed silica;
the first other functional auxiliary agent and the second other functional auxiliary agent are respectively and independently selected from at least one of polymethylphenylsiloxane, polyphenyl siloxane, phthalate, diethyl phthalate, tributyl citrate dimethyl phthalate, diacetin, diethylene glycol monobutyl ether acetate, dibutyl maleate, dimethyl adipate, dibutyl oxalate, dibutyl phthalate, microcrystalline wax, polydimethylsiloxane, polyvinyl butyral, polyether polyester modified organosiloxane and alkyl modified organosiloxane.
18. The metallization process of claim 1, wherein the sintering process is performed at a temperature of 700 ℃ to 850 ℃.
19. A solar cell comprising a fine grid produced by the metallization method of any one of claims 1-18.
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| CN117116523A (en) * | 2023-08-09 | 2023-11-24 | 江苏日御光伏新材料科技有限公司 | Front side auxiliary grid slurry for TOPCON solar cell secondary printing process and preparation method thereof |
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