CN110603606B - Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell - Google Patents
Crystalline silicon solar cell front conductive paste and preparation method thereof and solar cell Download PDFInfo
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Abstract
The invention provides a crystalline silicon solar cell front conductive paste which is calculated according to parts by weightThe conductive slurry for the front surface of the crystalline silicon solar cell comprises the following raw material components: 80.0-93.0 parts of metal powder; 6.0-15.0 parts of an organic carrier; 1.0-5.0 parts of oxide etching agent; wherein the oxide etchant at least contains PbO and B2O3MgO and WO3And said MgO and WO3The weight ratio is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3And the weight ratio of PbO is 1: 50-15: 25. The front conductive slurry can enable metal powder and silicon to form good ohmic contact in the sintering process, greatly reduce resistance, and finally obtain a front electrode with low contact resistance, good conductivity and strong adhesive force.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to crystalline silicon solar cell front conductive paste, a preparation method thereof and a solar cell.
Background
Solar energy is an inexhaustible clean energy. With the increasing exhaustion of non-renewable energy sources such as coal and petroleum, the development and utilization of solar energy become a big hot spot. The solar cell developed based on the idea is an important means for utilizing solar energy. At present, a crystalline silicon solar cell for realizing industrialization is a model of solar cell application.
The cell is used as a core component of the crystalline silicon solar cell, and in order to collect and guide out the current generated under illumination, an electrode needs to be respectively manufactured on the front surface and the back surface of the cell. The method for manufacturing the electrode is various, and screen printing and co-firing are the most common production processes at present. For example, in the manufacture of the front electrode, the conductive paste is coated on the silicon wafer by screen printing, and the front electrode is formed on the front surface of the silicon wafer by sintering. The sintered positive electrode of the crystalline silicon solar cell needs to be firmly attached to a silicon wafer, the grid line is narrow and high, the shading area is small, welding is easy, and the conductive slurry for the positive electrode of the crystalline silicon solar cell needs to have the capability of penetrating through a silicon nitride antireflection film in the sintering process and form good ohmic contact with the silicon wafer.
The common conductive paste for the front of the crystalline silicon solar cell contains silver powder, glass powder and an organic carrier, and the conductive paste is sintered to form a front electrode. In the sintering process, the oxide etchant in the conductive paste etches and penetrates through an antireflection insulating layer such as silicon nitride, titanium oxide, aluminum oxide, silicon oxide or silicon oxide/titanium oxide on the front surface or the light irradiation surface of the crystalline silicon solar cell, so that the silver powder is in contact with a crystalline silicon solar cell substrate to form a front electrode. Along with the improvement of the sheet resistance of the solar cell, the traditional front conductive slurry and the used glass powder cannot etch the antireflection insulating layer on the surface of the cell piece well, and the contact resistance between the front electrode formed by the front conductive slurry and the surface of the silicon wafer is high, so that the photoelectric conversion efficiency of the cell piece is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the crystalline silicon solar cell front conductive paste and the preparation method thereof are provided to solve the problems that an antireflection insulating layer on the surface of a cell cannot be effectively etched in the existing front conductive paste, so that the resistance value of a front electrode in contact with the surface of a silicon wafer is increased, and the photoelectric conversion efficiency of the cell is reduced.
Furthermore, the invention also provides a manufacturing method of the crystalline silicon solar cell front electrode and a solar cell.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the crystalline silicon solar cell front conductive paste comprises the following raw material components in parts by weight of 100:
80.0-93.0 parts of metal powder;
6.0-15.0 parts of an organic carrier;
1.0-5.0 parts of oxide etching agent;
wherein the oxide etchant at least contains PbO and B2O3MgO and WO3And said MgO and WO3The weight ratio is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3And the weight ratio of PbO is 1: 50-15: 25.
Correspondingly, the preparation method of the crystalline silicon solar cell front conductive paste at least comprises the following steps:
s01, melting raw material components of an oxide etchant to obtain an oxide etchant solution, carrying out quenching treatment on the solution to obtain oxide etchant particles, and crushing the oxide etchant particles to obtain oxide etchant powder with the particle size of 0.1-5.0 mu m;
s02, placing the organic carrier raw materials in an environment of 40-100 ℃ for mixing treatment to obtain an organic carrier;
and S03, mixing the metal powder, the oxide etching agent powder obtained in the step S01 and the organic carrier obtained in the step S02 to obtain the front conductive paste of the crystalline silicon solar cell.
Correspondingly, the manufacturing method of the front electrode of the crystalline silicon solar cell at least comprises the following steps:
providing a crystalline silicon semiconductor element with an insulating film laminated on the surface;
the crystalline silicon solar cell front conductive paste is printed on the surface of the insulating film in a printing mode, and then drying, sintering and cooling treatment are sequentially carried out to obtain the crystalline silicon solar cell front electrode.
And the crystalline silicon solar cell adopts the crystalline silicon solar cell front electrode.
The invention has the beneficial effects that: compared with the prior art, the crystalline silicon solar cell front conductive paste provided by the invention contains PbO and B in the oxide etching agent2O3MgO and WO3The components exist in specific proportions, the components in the specific proportions can show excellent etching performance, so that the oxide etchant can dissolve enough silver in the sintering process, one part of the oxide etchant liquid in which the silver is dissolved is used for wetting metal powder and promoting the metal powder to be sintered, the other part of the oxide etchant liquid flows to the surface of the solar cell to react with the antireflection layer, the antireflection layer can be effectively etched, in the cooling process, the silver dissolved in the oxide etchant liquid is precipitated to form micro nano silver particles, the metal powder and silicon form good ohmic contact, the resistance of the front electrode is greatly reduced, and the front electrode with low contact resistance, good conductivity and strong adhesion is finally obtained.
The preparation method of the crystalline silicon solar cell front conductive paste provided by the invention has the advantages that the process conditions are simple, the obtained front conductive paste has uniform components and good performance, and the preparation method is suitable for industrial large-scale production.
According to the manufacturing method of the crystalline silicon solar cell front electrode, due to the adoption of the crystalline silicon solar cell front conductive slurry, the oxide etchant can dissolve enough silver in the sintering process, one part of the oxide etchant liquid in which the silver is dissolved is used for wetting metal powder and promoting the metal powder to be sintered, the other part of the oxide etchant liquid flows to the surface of the solar cell to react with the antireflection layer, the antireflection layer can be effectively etched, and in the cooling process, the silver dissolved in the oxide etchant liquid is separated out to form tiny nano silver particles, so that the metal powder and the silicon form good ohmic contact, the resistance of the front electrode is greatly reduced, and the front electrode with low contact resistance, good conductivity and strong adhesion is finally obtained.
According to the crystalline silicon solar cell provided by the invention, due to the adoption of the crystalline silicon solar cell front electrode structure, the solar cell structure shows good adhesive force, and meanwhile, the silver electrode and the silicon wafer have good ohmic contact, so that the conversion efficiency of the solar cell is improved.
Drawings
To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a process flow diagram of a preparation method of a crystalline silicon solar cell front conductive paste provided by the invention;
fig. 2 is a process flow diagram of a manufacturing method of a front electrode of a crystalline silicon solar cell provided by the invention;
FIG. 3 is a schematic view of a crystalline silicon semiconductor element provided by the present invention and having an insulating film on the surface thereof, printed with a front-side conductive paste according to the present invention;
FIG. 4 is a schematic representation of the crystalline silicon semiconductor element of FIG. 3 after sintering with front and back side pastes printed thereon in accordance with the present invention;
fig. 5 is a schematic diagram of a 180 degree tensile test.
Wherein, the 100-crystalline silicon cell piece; a 200-P/N junction; 300-an insulating film; 400-printed front side conductive paste, 401-metal powder, 402-organic vehicle, 403-oxide etchant; 500-printed back silver paste; 600-printed back side aluminum paste; 700-front electrode; 800-welding a strip; 900-a stretcher; 901-stretcher sample first fixing bolt; 902-stretcher sample second fixing bolt; f-the direction of the pulling force.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides crystalline silicon solar cell front side conductive paste which comprises the following raw material components in parts by weight of 100 parts:
80.0-93.0 parts of metal powder;
6.0-15.0 parts of an organic carrier;
1.0-5.0 parts of oxide etching agent;
wherein the oxide etchant at least contains PbO and B2O3MgO and WO3And said MgO and WO3The weight ratio is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3And the weight ratio of PbO is 1: 50-15: 25.
More specifically, the oxide etchant comprises the following components by weight of 100 percent of the oxide etchant:
in the formula components of the invention, the oxide etching agent contains PbO and B2O3MgO and WO3And the components are present in specific proportions which can exhibit excellent etching properties, when the oxide etchant is melted into a liquid during sintering so that silver is dissolved therein in sufficient quantities, a portion of the oxide etchant liquid in which silver is dissolved is used to wet the metal powder and cause the metal powder to sinter; and the other part of the oxide etching agent liquid with the silver dissolved therein flows to the surface of the solar cell to react with the antireflection layer, so that the antireflection layer can be effectively etched, and in the cooling process after sintering, the silver dissolved in the oxide etching agent liquid is separated out to form micro nano silver particles, so that metal powder and silicon form good ohmic contact, the resistance is reduced, and a front electrode with low contact resistance, good conductivity and strong adhesion is formed.
Preferably, the additive element in the oxide of the additive element is one or two or more of titanium, aluminum, 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, and the like.
The oxide of the present invention includes not only chemically prepared oxide and oxide obtained after high temperature treatment, but also carbonate, phosphate, fluoride, etc. containing cations, for example, the oxide of lithium includes Li2O and Li2CO3The copper oxide comprises CuO and Cu2(OH)2CO3CuO, the zinc oxide including ZnO and Zn3(PO4)2The calcium oxide comprises CaO and CaCO3。
Preferably, the oxide etchant may be crystalline, amorphous, or a mixture of amorphous and crystalline.
Preferably, the metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium and rhodium.
Further preferably, the metal powder is at least one of silver-coated copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum and manganese, wherein the thickness of the silver-coated layer is 10-50 nm.
Preferably, the metal powder is a mixture of non-silver-coated metal powder and silver-coated metal powder, wherein the weight ratio of the non-silver-coated metal powder to the silver-coated metal powder is 5/95-95/5, and the non-silver-coated metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium and rhodium; the silver-coated metal powder is at least one of copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum and manganese, and the thickness of the silver-coated layer is 10-50 nm.
The organic carrier comprises an organic solvent, a polymer, a wetting dispersant, a thixotropic agent, other functional auxiliaries and the like.
The organic carrier comprises the following components in parts by weight of 100: 50-95 parts of an organic solvent; 1-40 parts of a polymer; 0.1-10 parts of wetting dispersant; 1-20 parts of a thixotropic agent; 0.1-20 parts of other functional additives.
Wherein the organic solvent is at least one of high boiling point solvents such as terpineol, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, glycol decamethylene, diethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, terpenes and the like.
The polymer is at least one selected from ethyl cellulose, methyl cellulose, cellulose and derivatives thereof, acrylic resin, alkyd resin and polyester resin.
The wetting dispersant is selected from one or more of fatty acid (oleic acid, stearic acid and the like), amide derivative of fatty acid (oleamide, stearamide and the like), ester derivative of fatty acid, polyethylene wax and polyethylene glycol, and is mainly used for assisting the dispersion of inorganic powder in an organic carrier.
The thixotropic agent is selected from one or more than two of hydrogenated castor oil derivatives, polyamide wax, polyurea and fumed silica, and is mainly used for improving the thixotropy of the paste in the printing process, so that the consistency of the paste is reduced when the paste is sheared in the printing process, the paste is easy to screen print, and the consistency is increased when the shearing is stopped, so that the electrode has an excellent height-width ratio.
Further, the organic carrier may further include other functional additives, wherein the other functional additives are 0.1 to 20 parts by weight and are selected from one or more of polymethylphenylsiloxane, polyphenylsiloxane, phthalate esters (such as diethyl phthalate, dibutyl phthalate, and the like), microcrystalline wax, polydimethylsiloxane, polyvinyl butyral (PVB), polyether polyester modified organosiloxane, and alkyl modified organosiloxane. The other functional additives can be optionally added according to needs, such as microcrystalline wax and the like to reduce surface tension, dibutyl phthalate (DBP) and the like to improve the flexibility of the slurry, polyvinyl butyral (PVB) and the like to improve adhesion.
As shown in fig. 1, the preparation method of the crystalline silicon solar cell front surface conductive paste comprises the following steps:
s01, preparing an oxide etching agent as follows: weighing the raw materials of the oxide etchant according to the raw material proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 900-1100 ℃, and preserving heat at 900-1100 ℃ for 60-180min to obtain a molten liquid oxide etchant; quenching the molten liquid oxide etchant to obtain oxide etchant particles; drying the oxide etchant particles at the temperature of 60-80 ℃; and crushing the dried oxide etchant particles to obtain oxide etchant powder with the particle size of 0.5-5.0 mu m, and drying at 80-100 ℃ to obtain the dried oxide etchant powder.
Preferably, the quenching is carried out by pouring the molten liquid oxide etchant into water at 5-25 deg.C for cooling or in flowing room temperature air at 25 deg.C or below.
The crushing of the oxide etching particles can be carried out by ball milling by adopting a ball mill, and the particle size of the oxide etching agent particles can be reduced by adopting other modes.
S02, preparing an organic carrier as follows: and sequentially weighing the raw materials of the organic carrier according to the weight proportion of the raw materials of the organic carrier, putting the weighed raw materials of the organic carrier into a container, and stirring and mixing at the temperature of 40-100 ℃ for 100-160 min to obtain the organic carrier.
S03, preparing front side slurry, namely mixing and grinding metal powder, the prepared oxide etching agent and the organic carrier to obtain the front side conductive silver slurry.
The preparation method of the crystalline silicon solar cell front conductive paste also comprises the following replacement method:
in one embodiment, the oxide etchant and the metal powder are mixed to obtain a first mixture, the first mixture is mixed with the organic carrier, and then grinding treatment is carried out to obtain the conductive paste of the front electrode of the crystalline silicon solar cell.
In another embodiment, the oxide etchant and the organic carrier are mixed to obtain a first mixture, then metal powder is added into the first mixture, and then grinding treatment is carried out to obtain the conductive slurry of the front electrode of the crystalline silicon solar cell.
In another embodiment, the metal powder and the organic carrier are mixed to obtain a first mixture, an oxide etching agent is added into the first mixture, and then grinding treatment is carried out to obtain the conductive paste of the front electrode of the crystalline silicon solar cell.
In another embodiment, the metal powder, the organic carrier and the oxide etchant are mixed in an amount of 20-60 parts by weight and the organic carrier in an amount of 20-60 parts by weight, respectively, based on 100 parts by weight of each of the metal powder, the organic carrier and the oxide etchant, to obtain a first mixture; and mixing 40-80 parts by weight of oxide etchant and part of organic carrier to obtain a second mixture, mixing the first mixture and the second mixture, and grinding to obtain the conductive paste for the front electrode of the crystalline silicon solar cell.
Referring to fig. 2, fig. 3 and fig. 4, the invention further provides a method for manufacturing a front electrode of a crystalline silicon solar cell.
The manufacturing method relates to a crystalline silicon semiconductor element with an insulating film laminated on the surface, the crystalline silicon semiconductor element is structurally shown in fig. 3, 100 is a crystalline silicon cell piece with a first surface and a second surface which are opposite, a P/N junction 200 and the insulating film 300 are sequentially laminated on the first surface outwards, a back silver paste 500 and a back aluminum paste 600 are printed on the first surface, and the insulating film 300 can be at least one of a silicon nitride film, a titanium oxide film, an aluminum oxide film and a silicon oxide film.
Specifically, the method for manufacturing the front electrode of the crystalline silicon solar cell at least comprises the following steps:
step S04, providing a crystalline silicon semiconductor element with the surface being overlapped with the insulating film 300;
step S05, printing the conductive paste 400 (wherein 401 is metal powder, 402 is an organic carrier, and 403 is an oxide etchant) on the front surface of the crystalline silicon solar cell according to any one of the above schemes on the surface of the insulating film 300 in a printing manner;
and S06, drying, sintering and cooling the crystalline silicon semiconductor element processed in the step S05 in sequence to obtain the crystalline silicon solar cell front electrode 700.
Specifically, the drying temperature is 80-400 ℃, the sintering temperature is 700-820 ℃, and the cooling condition is natural cooling.
The invention further provides a crystalline silicon solar cell, which adopts the crystalline silicon solar cell front electrode.
In order to better illustrate the crystalline silicon solar cell front conductive paste and the preparation method thereof provided by the embodiment of the invention, the following further explains the crystalline silicon solar cell front conductive paste by a plurality of embodiments.
Example 1
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components in percentage by weight based on 100 percent of the total weight of the oxide etching agent:
PbO 25％、TeO2 35％、Li2O 0.5％、SiO2 6％、B2O3 6％、Bi2O3 14.4％、ZnO 6％、WO31％、MgO 6％、Al2O3 0.1％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.0 parts of silver powder, 9.0 parts of organic carrier and 3.0 parts of oxide etchant powder according to the weight ratio of the formula, uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 1 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are printed on the back of the crystalline silicon solar cell in a silk-screen printing mode, and then sintering is carried out at 770 ℃, so that the front electrode of the crystalline silicon solar cell is obtained.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 2
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 50％、TeO2 10％、Li2O 10％、SiO2 1％、B2O3 0.1％、Bi2O3 13.2％、ZnO 0.1％、WO3 15％、MgO 0.1％、TiO2 0.5％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 2 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are printed on the back of the crystalline silicon solar cell in a silk-screen printing mode, and then sintering is carried out at 800 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 3
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 40％、TeO2 11％、Li2O 1.2％、SiO2 0.5％、B2O3 2.2％、Bi2O3 26.3％、ZnO 4.5％、WO3 11％、MgO 3％、Cr2O3 0.3％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 3 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are printed on the back of the crystalline silicon solar cell in a silk-screen printing mode, and then sintering is carried out at 780 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 4
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 42％、TeO2 15％、Li2O 1.3％、SiO2 0.8％、B2O3 5％、Bi2O3 12.7％、ZnO 5％、WO3 13％、MgO 5％、MoO3 0.2％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 4 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are silk-screen printed on the back of the solar cell, and then sintering is carried out at 780 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 5
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 15％、TeO2 47.5％、Li2O 1％、SiO2 10％、B2O3 7％、Bi2O3 11.9％、ZnO 0.1％、WO3 0.5％、MgO 7％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 5 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are printed on the back of the crystalline silicon solar cell in a silk-screen printing mode, and then sintering is carried out at 790 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 6
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 51％、TeO2 5％、Li2O 1.5％、SiO2 0.1％、B2O3 9％、Bi2O3 5.6％、ZnO 2.8％、WO3 17％、MgO 8％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 6 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are silk-screen printed on the back of the solar cell, and then sintering is carried out at 800 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 7
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 17.6％、TeO2 27.1％、Li2O 0.2％、SiO2 0.5％、B2O3 11％、Bi2O3 9.9％、ZnO 3.7％、WO3 20％、MgO 10％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 7 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are silk-screen printed on the back of the solar cell, and then sintering is carried out at 800 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Example 8
The crystalline silicon solar cell front conductive paste comprises the following components in proportion by weight based on 100 parts of total weight: 88.5 parts of silver powder; 9.0 parts of an organic carrier; 2.5 parts of oxide etching agent.
Wherein the oxide etching agent comprises the following components by weight percent of 100 percent:
PbO 53％、TeO2 10％、Li2O 2％、SiO2 2％、B2O3 13％、Bi2O3 3.9％、ZnO 5％、WO30.1％、MgO 11％。
the preparation method of the oxide etching agent comprises the following steps: weighing the raw materials of the oxide etchant according to the proportion and uniformly mixing; heating the uniformly mixed oxide etchant raw materials in a heating furnace to 1000 ℃, and preserving heat at 1000 ℃ for 120min to obtain a molten liquid oxide etchant; pouring the molten liquid oxide etchant into water at normal temperature (25 ℃) for cooling to obtain oxide etchant particles; placing the oxide etchant particles in a drying oven to be dried at 80 ℃; and (3) grinding the dried oxide etchant particles in a ball mill to obtain oxide etchant powder with the particle size of 0.5-7.0 mu m, and then drying the oxide etchant powder in a drying oven at 100 ℃ to obtain the dried oxide etchant powder.
The organic carrier comprises the following components by weight of 100 percent of the organic carrier: 70% of a mixture of terpineol, dodecanol ester and terpene; 10% of ethyl cellulose, 15% of rosin resin and 5% of polyamide wax.
The preparation method of the crystalline silicon solar cell front side conductive paste comprises the following steps:
and weighing 88.5 parts of silver powder, 9.0 parts of organic carrier and 2.5 parts of oxide etchant powder according to the weight ratio of the formula, and uniformly mixing and grinding to obtain the conductive paste for the front surface of the crystalline silicon solar cell.
A method for manufacturing a front electrode of a crystalline silicon solar cell comprises the following steps:
the front conductive paste of the crystalline silicon solar cell in the embodiment 8 is printed on the front of the crystalline silicon solar cell with the insulating film in a silk-screen printing mode, the back silver and the back aluminum are silk-screen printed on the back of the solar cell, and then sintering is carried out at 800 ℃ to obtain the front electrode of the crystalline silicon solar cell.
The efficiency of the cell obtained from the test is summarized in table 1, I-V test results.
Comparative example
The front conductive paste PVM1B of the crystalline silicon solar cell widely used in the market is screen-printed on the front surface of the crystalline silicon solar cell with the same insulating film as the embodiment, the back surface of the solar cell is screen-printed with back silver and back aluminum, then the crystalline silicon solar cell is heated to 800 ℃ for sintering to obtain the front electrode of the crystalline silicon solar cell, and then the efficiency of the cell piece is tested, and the I-V test results are summarized in Table 1.
And (3) performance testing:
(1) I-V test
The battery pieces of examples 1 to 8 and the battery piece of comparative example were subjected to an I-V test on a HALM IV tester, and the test results are shown in table 1.
(2) Tension test
Welding a solder strip on the main grid by a tensile test tensile force of 180 degrees, wherein the width of the main grid is 0.7mm, welding the solder strip with the width of 0.9mm on the main grid, the width of the solder strip is 0.9mm, the thickness of the solder strip is 0.23mm, and the solder strip is made of 96.5 percent of Sn3.5 percent of Ag. Fig. 5 is a schematic diagram of a 180-degree tensile test, specifically, a solder strip 800 is welded on the surface of a main grid, and then the crystalline silicon cell 100 is fixed on a stretcher 900 by a first fixing bolt 901 and a second fixing bolt 902, and a tensile test is performed according to the direction of a tensile force F. The tensile test results are shown in table 1.
TABLE 1 statistics of crystalline silicon solar cell performance test data obtained in examples 1-8 and comparative examples
| Scheme(s) | Pulling force (N) | Number of | Uoc | Isc | FF | Eta | Rs | Rsh | IRev1 |
| Example 1 | 3.06 | 20pcs | 0.6321 | 1.9132 | 76.17 | 18.28 | 0.0197 | 53.8 | 0.56 |
| Example 2 | 2.76 | 20pcs | 0.6326 | 1.9145 | 76.58 | 18.40 | 0.0187 | 89.6 | 0.38 |
| Example 3 | 2.87 | 20pcs | 0.6312 | 1.9097 | 76.55 | 18.30 | 0.0187 | 70.8 | 0.49 |
| Example 4 | 2.75 | 20pcs | 0.6324 | 1.9212 | 76.25 | 18.38 | 0.0189 | 94.0 | 0.39 |
| Example 5 | 2.42 | 20pcs | 0.6060 | 1.8541 | 75.86 | 16.91 | 0.0212 | 682 | 0.05 |
| Example 6 | 2.86 | 20pcs | 0.6069 | 1.8564 | 75.86 | 16.95 | 0.0213 | 375 | 0.08 |
| Example 7 | 2.71 | 20pcs | 0.6048 | 1.8502 | 75.78 | 16.82 | 0.0216 | 646 | 0.05 |
| Example 8 | 2.93 | 20pcs | 0.6069 | 1.8592 | 75.63 | 16.93 | 0.0217 | 375 | 0.08 |
| Comparative example | 2.26 | 20pcs | 0.6321 | 1.9044 | 76.16 | 18.26 | 0.0199 | 102 | 0.16 |
As can be seen from Table 1, the solar cells of examples 1 to 4 had high conversion rates, R, as compared with the comparative examplesThe advantages of low tensile force and high tensile force show that the oxide etchant used in examples 1-4 has excellent etching performance, not only effectively wets and sinters silver powder, but also effectively etches the insulating film on the surface of the solar cell piece, so that the silver electrode and the surface of the solar cell piece form good ohmic contact, thereby the solar cell piece has high conversion efficiency and contact resistance RsLow tension and high tensile force. MgO and WO in the etchant for oxide etching used in examples 1 to 43The weight ratio of (A) to (B) is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3And PbO in a weight ratio of 1:50 to 15:25, and WO3And Li2The weight ratio of O is 1: 10-15: in the range of 0.5, the unique oxide component proportion ensures that the oxide etchant can dissolve enough silver in the sintering process, can fully etch through the insulating layer on the surface of the cell but does not excessively corrode the silicon cell, so that the silver electrode and the silicon wafer not only form good ohmic contact, but also have good adhesive force. The solar cells of examples 5-8 had lower conversion rates than the comparative examples and also lower conversion rates than the cells of examples 1-4, and had series resistances (R)S) This is significantly higher than examples 1-4 because of the different ratios of the oxide etchant components used. Example 5 cell conversion was low due to the low PbO content in the oxide etchant used, B2O3High content of (A), high content of MgO, WO3Since these oxide contents deviate from the optimum content range described in the present invention, it is shown that these oxide contents greatly affect the performance of the oxide etchant described in the present invention, and it is necessary to maintain an appropriate ratio. Example 6 the low conversion rate of the cell was due to the oxide etching usedHigh content of PbO in etching agent, B2O3High content of (A), high content of MgO, WO3Since these oxide contents deviate from the optimum content range described in the present invention, it is shown that these oxide contents have a great influence on the performance of the oxide etchant described in the present invention, and it is necessary to maintain an appropriate ratio. Example 7 cell conversion was low due to the low PbO content in the oxide etchant used, B2O3High content of (A), high content of MgO, WO3Since these oxide contents deviate from the optimum content range described in the present invention, it is shown that these oxide contents have a great influence on the performance of the oxide etchant described in the present invention, and it is necessary to maintain an appropriate ratio. Example 8 cell conversion was low due to the high PbO content in the oxide etchant used, B2O3High content of (A), high content of MgO, WO3Since these oxide contents deviate from the optimum content range described in the present invention, it is shown that these oxide contents greatly affect the performance of the oxide etchant described in the present invention, and it is necessary to maintain an appropriate ratio. The optimal proportion range of the oxide etchant is as follows: MgO and WO3The weight ratio of (A) to (B) is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3And the weight ratio of PbO is 1: 50-15: 25. The data of examples 1-4 show high battery conversion and low contact resistance, indicating that if PbO, B are present2O3MgO and WO3The weight ratio of the oxide etchant is in the range, the oxide etchant can effectively corrode the insulating layer on the surface of the cell piece, and the front electrode and the surface of the silicon chip form good ohmic contact. The data of examples 5-8 show low battery conversion and high contact resistance, indicating if PbO, B are present2O3MgO and WO3The weight ratio of the oxide etching agent is not in the above range, and the oxide etching agent cannot effectively etch the antireflection insulating layer on the surface of the cell, so that the contact resistance between the formed front electrode and the surface of a silicon wafer is high, and the photoelectric conversion efficiency of the cell is influenced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (16)
1. The crystalline silicon solar cell front conductive paste is characterized by comprising the following raw material components in parts by weight of 100:
80.0-93.0 parts of metal powder;
6.0-15.0 parts of an organic carrier;
1.0-5.0 parts of oxide etching agent;
wherein the oxide etchant at least contains PbO and B2O3MgO and WO3(ii) a And said MgO and WO3The weight ratio is 0.1: 15-6: 1; b is2O3And WO3In a weight ratio of 0.1:15 to 6: 1; WO3The weight ratio of PbO to PbO is 1: 50-15: 25; the oxide etchant comprises the following components by taking the weight of the oxide etchant as 100 percent:
0 to 5.0% of an oxide of the additive element.
2. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein WO is contained in the oxide etchant3And Li2The weight ratio of O is 1: 10-15: 0.5.
3. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein B in the oxide etchant2O3The weight ratio of MgO to MgO is 0.1: 6-6: 0.1.
4. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein the additive element in the oxide of the additive element is one or two or more of titanium, aluminum, 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, and germanium.
5. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein the oxide etchant is at least one of crystalline and amorphous.
6. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein the metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium and rhodium.
7. The crystalline silicon solar cell front surface conductive paste according to claim 1, wherein the metal powder is at least one of silver-coated copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum and manganese, and the thickness of the silver-coated layer is 10-50 nm.
8. The crystalline silicon solar cell front conductive paste as claimed in claim 1, wherein the metal powder is a mixture of non-silver-coated metal powder and silver-coated metal powder, wherein the weight ratio of the non-silver-coated metal powder to the silver-coated metal powder is 5/95-95/5, and the non-silver-coated metal powder is at least one of silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum, manganese, palladium and rhodium; the silver-coated metal powder is at least one of copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminum and manganese, and the thickness of the silver-coated layer is 10-200 nm.
9. The crystalline silicon solar cell front side conductive paste according to claim 1, wherein the organic vehicle comprises an organic solvent, a polymer, a wetting dispersant, a thixotropic agent, other functional auxiliaries;
50-95 parts of organic solvent by weight of 100 parts of organic carrier; 1-40 parts of a polymer; 0.1-10 parts of wetting dispersant; 1-20 parts of a thixotropic agent; 0.1-20 parts of other functional additives.
10. The crystalline silicon solar cell front conductive paste as claimed in claim 9, wherein the organic solvent is at least one of terpineol, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, decaglycol ester, diethylene glycol butyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, terpenes, and the like;
the polymer is selected from at least one of cellulose and derivatives thereof, acrylic resin, alkyd resin and polyester resin;
the wetting dispersant is selected from one or a mixture of more than two of fatty acid, amide derivative of fatty acid, ester derivative of fatty acid, polyethylene wax and polyethylene glycol;
the thixotropic agent is selected from at least one of hydrogenated castor oil derivatives, polyamide wax, polyurea and fumed silica; the functional assistant is at least one selected from polymethylphenylsiloxane, polyphenylsiloxane, phthalate ester, diethyl phthalate, dibutyl phthalate, microcrystalline wax, polydimethylsiloxane, polyvinyl butyral, polyether polyester modified organic siloxane and alkyl modified organic siloxane.
11. The preparation method of the crystalline silicon solar cell front surface conductive paste according to any one of claims 1 to 10, characterized by at least comprising the following steps:
s01, melting raw material components of an oxide etchant to obtain an oxide etchant solution, carrying out quenching treatment on the solution to obtain oxide etchant particles, and crushing to obtain oxide etchant powder with the particle size of 0.1-5.0 microns;
s02, placing the organic carrier raw materials in an environment of 40-100 ℃ for mixing treatment to obtain an organic carrier;
and S03, mixing the metal powder, the oxide etching agent powder obtained in the step S01 and the organic carrier obtained in the step S02 to obtain the front conductive paste of the crystalline silicon solar cell.
12. The method for preparing the crystalline silicon solar cell front conductive paste according to claim 11, wherein the quenching treatment is a water cooling treatment or a cold air treatment.
13. A method for manufacturing a front electrode of a crystalline silicon solar cell is characterized by at least comprising the following steps:
providing a crystalline silicon semiconductor element with an insulating film laminated on the surface;
printing the crystalline silicon solar cell front conductive paste as defined in any one of claims 1 to 10 on the surface of the insulating film in a printing manner, and sequentially performing drying, sintering and cooling treatment to obtain the crystalline silicon solar cell front electrode.
14. The method for manufacturing the front electrode of the crystalline silicon solar cell according to claim 13, wherein the sintering temperature is 700-820 ℃; and/or the drying temperature is 80-400 ℃.
15. The method for manufacturing the front electrode of the crystalline silicon solar cell according to claim 13, wherein the insulating film is at least one of a silicon nitride film, a titanium oxide film, an aluminum oxide film and a silicon oxide film.
16. The crystalline silicon solar cell is characterized in that the crystalline silicon solar cell is manufactured by the manufacturing method of the crystalline silicon solar cell front electrode according to any one of claims 13 to 15.
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| CN103545016A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN104008789A (en) * | 2013-10-28 | 2014-08-27 | 苏州晶银新材料股份有限公司 | Front conductive silver paste for crystal silicon solar cells |
| CN107004457A (en) * | 2014-11-27 | 2017-08-01 | 株式会社则武 | Conductive composition |
| JP2017162636A (en) * | 2016-03-09 | 2017-09-14 | ナミックス株式会社 | Conductive paste and solar cell |
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| CN103545016A (en) * | 2013-10-21 | 2014-01-29 | 深圳首创光伏有限公司 | Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof |
| CN104008789A (en) * | 2013-10-28 | 2014-08-27 | 苏州晶银新材料股份有限公司 | Front conductive silver paste for crystal silicon solar cells |
| CN107004457A (en) * | 2014-11-27 | 2017-08-01 | 株式会社则武 | Conductive composition |
| JP2017162636A (en) * | 2016-03-09 | 2017-09-14 | ナミックス株式会社 | Conductive paste and solar cell |
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