CN114267474A - High-performance metallization paste for solar cell and preparation method thereof - Google Patents
High-performance metallization paste for solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 5-10 parts of organic resin, 10-20 parts of organic solvent, 0.2-0.5 part of surfactant, 0.1-0.3 part of coupling agent, 0.2-0.4 part of maleic anhydride grafting compatilizer, 2-5 parts of silver-coated glass powder, 5-12 parts of glass powder, 70-80 parts of silver powder and 1-3 parts of nano alloy powder; the high-performance metallization paste for the solar cell, prepared by the invention, is suitable for a fine line printing process below 25um, and has the characteristics of good fine line printing performance, high conversion efficiency, low composite current, low contact resistance and the like.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to high-performance metallization paste for a solar cell and a preparation method thereof.
Background
The technology of the photovoltaic industry is updated and iterated rapidly, the conversion efficiency of the components determined by the first leaders is the market admission threshold at present, and the foundation of maintaining the competitiveness of the enterprises is only when the enterprises actively develop the research and development and large-scale application of the high-efficiency technology. The N-type crystalline silicon battery is a necessary choice for a high-efficiency battery technology route due to natural advantages of high minority carrier lifetime, no light-induced attenuation and the like, and is also a new generation of battery technology which is entering large-scale production in the photovoltaic industry. The passivation Contact structure of the ultrathin tunneling Oxide layer and the highly doped polysilicon thin layer is introduced into the N-type battery to form a Tunnel Oxide Passivated Contact battery (TOPCon), so that the conversion efficiency of the battery can be greatly improved, and the method is an important development direction of a high-efficiency battery.
When the metallization paste for the P-type photovoltaic cell which is mainstream in the market at present is used for preparing electrodes of a TOPCon cell and a perovskite laminated cell thereof, due to the difference of the cell surface structure, a passivation layer structure can be burnt through, so that the loss of the cell in a Filling Factor (FF) and an open-circuit voltage (Voc) is brought, and the conversion efficiency of the cell is seriously influenced. Therefore, a novel metallization slurry is developed, damage to a passivation layer of a high-efficiency battery including a TOPCon and a perovskite laminated battery thereof is reduced in a battery sintering process, high conversion efficiency is achieved, and the development of the high-efficiency battery in the future is very critical.
Patent 201911377189.5 provides a high-efficiency nano-silver coated glass powder and doped nano-oxide conductive paste and a preparation method thereof, the nano-silver coated glass powder and the nano-oxide are selected to prepare the conductive paste, compared with the conductive paste prepared without coating and nano-oxide, the UOC is improved by 0.33%, the FF is improved by 0.2%, the conversion efficiency Ncell is improved to 22.76%, and the requirement of high conversion efficiency cannot be met.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a preparation method of high-performance metallization paste for a solar cell, the high-performance metallization paste for the solar cell prepared by the method is suitable for an ultra-thin line printing process below 25um, and has the characteristics of good thin line printing performance, high conversion efficiency, low composite current, low contact resistance rate and the like.
The technical scheme of the invention is as follows:
the invention provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 5-10 parts of organic resin, 10-20 parts of organic solvent, 0.2-0.5 part of surfactant, 0.1-0.3 part of coupling agent, 0.2-0.4 part of maleic anhydride grafting compatilizer, 2-5 parts of silver-coated glass powder, 5-12 parts of glass powder, 70-80 parts of silver powder and 1-3 parts of nano alloy powder.
As a further limitation of the present invention, the organic resin is a thermoplastic resin, and the thermoplastic resin is at least one of polyethylene, polypropylene, polystyrene, and polyvinyl butyral.
As a further limitation of the present invention, the organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is at least one of methanol, ethanol, acetone, formic acid and acetic acid; the lipophilic organic solvent is at least one of dimethyl adipate, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, terpineol and dioctyl phthalate.
As a further limitation of the present invention, the maleic anhydride grafted compatibilizer is at least one of maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted polypropylene, and maleic anhydride grafted polyethylene.
As a further limitation of the present invention, the silver powder is a mixture of one or more of a spherical silver powder, a flake silver powder, an irregular silver powder, and a linear silver powder; the D50 of the silver powder is 400-600 nm.
As a further limitation of the present invention, the nano alloy powder is at least one of tin-based, lead-based, aluminum-based, and copper-based alloy powders; the particle size of the nano alloy powder is 100-300 nm.
As a further limitation of the present invention, the silver-coated glass frit is prepared by the following method:
a. slowly dropwise adding ammonia water with the concentration of 0.01-0.05 mol/L into a silver nitrate solution with the concentration of 0.01-0.05 mol/L, and stirring for 1-2 h to obtain a silver ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution;
c. adding glass powder into the mixed liquid obtained in the step b, ultrasonically dispersing for 10-30 min by using a cell ultrasonic crusher, and then heating for 2-4 h in a water bath at the temperature of 60-80 ℃ to obtain mixed liquid containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.01-0.1 mlo/L into the mixed solution obtained in the step c, reacting for 20-60 min under the conditions of water bath heating and magnetic stirring after dripping is finished for 2-3 min; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in an oven with the temperature of 80-90 ℃, and drying for 6-8 h to obtain the silver-coated glass powder.
The mass ratio of the silver nitrate solution to the ammonia water in the step a is 1: 1-10.
In a further limitation of the present invention, in the step b, the absolute ethyl alcohol accounts for 5-15% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1-3% of the mass of the silver-ammonia solution.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell, which comprises the following steps:
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and an organic resin into a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 120-140 ℃ for 1-2 h, adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at the rotating speed of 2000-3000 RPM (revolutions per minute) at the activation temperature of 60-80 ℃, and reacting for 1-2 h to obtain an organic carrier with the viscosity of 30-45 Pa.S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 4-6 hours at the temperature of 40-60 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 150-350 Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
The beneficial technical effects of the invention are as follows:
(1) the organic solvent adopts a hydrophilic organic solvent and lipophilic organic solvent composite technology, has different surface tensions, contains more active functional groups, and can enhance the bonding effect between organic resin and silver powder, silver paste slurry and a battery sheet base material in an organic carrier; on one hand, the lipophilic organic solvent can lubricate the silver powder, reduce the friction among the powder, increase the arrangement compactness and the stacking compactness of the sintered and solidified silver powder in the silver grid line, and weaken the friction between the slurry and the screen printing plate during printing, so as to improve and enhance the fine grid and high-speed printing performance of the slurry; on the other hand, the hydrophilic organic solvent can improve the compatibility and wettability of the silver powder and the resin in the organic carrier, and endow the slurry with lower viscosity and better fluidity, so that the slurry has excellent printing superfine linearity.
(2) The organic carrier is prepared by two-stage heat treatment activation, organic resin and an organic solvent in the organic carrier are heated and dissolved, then the surfactant, the coupling agent and the maleic anhydride grafted compatilizer are mixed with the organic resin and the organic solvent, and the organic carrier obtained by heating activation treatment has the characteristics of proper viscosity and high viscosity stability, can effectively reduce the generation probability of silver sheets during silver paste production, and is suitable for the speed of quick printing.
(3) The maleic anhydride grafted compatilizer is added, so that the compatibility of the organic resin with silver powder, glass powder and nano alloy powder can be improved, the organic carrier can better cover the conductive particles, and agglomeration, coagulation and precipitation among the particles are prevented, so that the conductive particles can form a good conductive chain when the conductive paste is sintered, and a continuous and compact conductive silver film is finally obtained.
Detailed Description
The present invention will be described in detail with reference to examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 5 parts of organic resin, 20 parts of organic solvent, 0.2 part of surfactant, 0.3 part of coupling agent, 0.2 part of maleic anhydride grafting compatilizer, 2 parts of silver-coated glass powder, 12 parts of glass powder, 70 parts of silver powder and 1 part of nano alloy powder.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is methanol, and the lipophilic organic solvent is dimethyl adipate.
The organic resin is thermoplastic resin, and the thermoplastic resin is polyethylene.
The maleic anhydride grafted compatilizer is maleic anhydride grafted ethylene-vinyl acetate copolymer.
The silver powder is spherical silver powder, and the D50 of the silver powder is 400 nm.
The nano alloy powder is tin-based alloy powder, and the particle size of the nano alloy powder is 100 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.01mol/L ammonia water (mass ratio is 1:1) into 0.01mol/L silver nitrate solution, and stirring for 1h to obtain silver-ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 5% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver-ammonia solution.
c. Adding glass powder into the mixed solution, ultrasonically dispersing for 10min by using a cell ultrasonic crusher, and then heating for 2h in water bath at 80 ℃ to obtain mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.01mlo/L into the mixed solution obtained in the step c, reacting for 20min under the conditions of water bath heating and magnetic stirring after 3min dripping is finished; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in a drying oven at the temperature of 90 ℃ and drying for 6 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 120 ℃ for 2 hours, then adding a surfactant, a coupling agent and a maleic anhydride graft compatilizer, stirring at the rotating speed of 3000RPM (revolutions per minute), and reacting for 2 hours at the activation temperature of 60 ℃ to obtain an organic carrier with the viscosity of 45Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 4 hours at 60 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 350Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
Example 2
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 10 parts of organic resin, 10 parts of organic solvent, 0.5 part of surfactant, 0.3 part of coupling agent, 0.4 part of maleic anhydride grafting compatilizer, 5 parts of silver-coated glass powder, 5 parts of glass powder, 80 parts of silver powder and 3 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is polypropylene ethylene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is ethanol, and the lipophilic organic solvent is diethylene glycol dimethyl ether.
The maleic anhydride grafted compatilizer is maleic anhydride grafted polypropylene.
The silver powder is flake silver powder, and the D50 of the silver powder is 400 nm.
The nano alloy powder is lead-based alloy powder, and the particle size of the nano alloy powder is 300 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.05mol/L ammonia water (mass ratio is 1:10) into 0.05mol/L silver nitrate solution, and stirring for 2h to obtain silver-ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 15% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 3% of the mass of the silver-ammonia solution.
c. Adding glass powder into the mixed solution, ultrasonically dispersing for 30min by using a cell ultrasonic crusher, and then heating for 4h in a water bath at 60 ℃ to obtain a mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.1mlo/L into the mixed solution obtained in the step c, reacting for 60min under the conditions of water bath heating and magnetic stirring after 3min dripping is finished; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in a drying oven with the temperature of 80 ℃, and drying for 6-8 h to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 140 ℃ for 1h, then adding a surfactant, a coupling agent and a maleic anhydride graft compatilizer, stirring at the rotating speed of 2000RPM (revolution per minute), and reacting for 1h at the activation temperature of 80 ℃ to obtain an organic carrier with the viscosity of 30Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 6 hours at 40 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 150Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
Example 3
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 15 parts of organic solvent, 0.3 part of surfactant, 0.2 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 4 parts of silver-coated glass powder, 10 parts of glass powder, 75 parts of silver powder and 2 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is polystyrene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, the hydrophilic organic solvent is acetone, and the lipophilic organic solvent is diethylene glycol butyl ether acetate.
The maleic anhydride grafted compatilizer is maleic anhydride grafted polyethylene.
The silver powder is linear silver powder, and the D50 of the silver powder is 600 nm.
The nano alloy powder is aluminum-based alloy powder, and the particle size of the nano alloy powder is 200 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.02mol/L ammonia water (mass ratio is 1:5) into 0.03mol/L silver nitrate solution, and stirring for 2h to obtain silver-ammonia solution;
adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 10% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 2% of the mass of the silver-ammonia solution.
b. Adding glass powder into the mixed solution, ultrasonically dispersing for 20min by using a cell ultrasonic crusher, and then heating for 3h in water bath at 70 ℃ to obtain mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.05mlo/L into the mixed solution obtained in the step c, reacting for 40min under the conditions of water bath heating and magnetic stirring after 3min dripping is finished; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in a drying oven with the temperature of 85 ℃, and drying for 7 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 130 ℃ for 1h, then adding a surfactant, a coupling agent and a maleic anhydride graft compatilizer, stirring at the rotating speed of 2500RPM (revolutions per minute), and reacting for 1h at the activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 200Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
Example 4
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 12 parts of organic solvent, 0.4 part of surfactant, 0.1 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 3 parts of silver-coated glass powder, 8 parts of glass powder, 72 parts of silver powder and 2.5 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is polyvinyl butyral.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is formic acid, and the lipophilic organic solvent is diethylene glycol dibutyl ether.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polypropylene.
The silver powder is irregular silver powder, and the D50 of the silver powder is 500 nm.
The nano alloy powder is copper-based alloy powder, and the particle size of the nano alloy powder is 100 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.03mol/L ammonia water (mass ratio is 1:6) into 0.02mol/L silver nitrate solution, and stirring for 2h to obtain silver-ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 8% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver-ammonia solution.
c. Adding glass powder into the mixed solution, ultrasonically dispersing for 10min by using a cell ultrasonic crusher, and then heating for 4h in a water bath at 60 ℃ to obtain a mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.02mlo/L into the mixed solution obtained in the step c, reacting for 50min under the conditions of water bath heating and magnetic stirring after 3min of dripping is finished; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in an oven with the temperature of 88 ℃ and drying for 7h to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 120 ℃ for 2 hours, adding a surfactant, a coupling agent and a maleic anhydride graft compatilizer, stirring at the rotating speed of 2500RPM (revolutions per minute), reacting for 1 hour at the activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 180 Pa.S, so as to obtain the high-performance metalized slurry for the solar cell.
Example 5
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 8 parts of organic resin, 12 parts of organic solvent, 0.4 part of surfactant, 0.1 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 3 parts of silver-coated glass powder, 8 parts of glass powder, 72 parts of silver powder and 2.5 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is a mixture of polyethylene and polystyrene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is formic acid, and the lipophilic organic solvent is diethylene glycol dibutyl ether.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polypropylene.
The silver powder is irregular silver powder, and the D50 of the silver powder is 500 nm.
The nano alloy powder is copper-based alloy powder, and the particle size of the nano alloy powder is 100 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.03mol/L ammonia water (mass ratio is 1:6) into 0.02mol/L silver nitrate solution, and stirring for 2h to obtain silver-ammonia solution;
adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 8% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver-ammonia solution.
b. Adding glass powder into the mixed solution, ultrasonically dispersing for 10min by using a cell ultrasonic crusher, and then heating for 4h in a water bath at 60 ℃ to obtain a mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.02mlo/L into the mixed solution obtained in the step c, reacting for 50min under the conditions of water bath heating and magnetic stirring after 3min of dripping is finished; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in an oven with the temperature of 88 ℃ and drying for 7h to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 120 ℃ for 2 hours, adding a surfactant, a coupling agent and a maleic anhydride graft compatilizer, stirring at the rotating speed of 2500RPM (revolutions per minute), reacting for 1 hour at the activation temperature of 70 ℃ to obtain an organic carrier with the viscosity of 40Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5 hours at 50 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 180 Pa.S, so as to obtain the high-performance metalized slurry for the solar cell.
Example 6
The embodiment provides a high-performance metallization paste for a solar cell, which comprises the following raw materials in parts by weight: 6 parts of organic resin, 16 parts of organic solvent, 0.3 part of surfactant, 0.2 part of coupling agent, 0.3 part of maleic anhydride grafting compatilizer, 4 parts of silver-coated glass powder, 9 parts of glass powder, 75 parts of silver powder and 2 parts of nano alloy powder.
The organic resin is thermoplastic resin, and the thermoplastic resin is a mixture of polyethylene and polypropylene.
The organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, wherein the hydrophilic organic solvent is acetic acid, and the lipophilic organic solvent is dioctyl phthalate.
The maleic anhydride grafted compatilizer is a mixture of maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
The silver powder is spherical silver powder and flaky silver powder, and the D50 of the silver powder is 400 nm.
The nano alloy powder is tin-copper alloy powder, and the particle size of the nano alloy powder is 200 nm.
The silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding 0.04mol/L ammonia water (mass ratio is 1:8) into 0.03mol/L silver nitrate solution, and stirring for 1.5h to obtain silver ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution; the absolute ethyl alcohol accounts for 8% of the mass of the silver-ammonia solution, and the polyvinylpyrrolidone accounts for 1% of the mass of the silver-ammonia solution.
c. Adding glass powder into the mixed solution, ultrasonically dispersing for 15min by using a cell ultrasonic crusher, and then heating for 3h in water bath at 70 ℃ to obtain mixed solution containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.08mlo/L into the mixed solution obtained in the step c, reacting for 30min under the conditions of water bath heating and magnetic stirring after dripping for 2.5 min; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in an oven with the temperature of 82 ℃ and drying for 6.5 hours to obtain the silver-coated glass powder.
The invention also provides a preparation method of the high-performance metallization paste for the solar cell,
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and organic resin in a reaction kettle according to a certain proportion, heating and stirring to dissolve the resin at the temperature of 110 ℃ for 1.5h, then adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at the rotating speed of 2800RPM, reacting for 1.5h at the activation temperature of 65 ℃ to obtain an organic carrier with the viscosity of 40Pa & S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 5.5 hours at 45 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 300Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
Comparative example 1
This comparative example is essentially the same as example 1, except that a conventional organic solvent was used.
Comparative example 2
The comparative example is substantially the same as example 1, except that the organic vehicle is prepared by using a traditional activation method of stress stirring and rolling machine grinding.
Comparative example 3
The high-performance metallization paste for the solar cell of this comparative example was prepared according to the method of patent 201911377189.5.
Test example
The high-performance metallization paste for the solar cell prepared in the embodiment 1-6 and the comparative examples 1-3 are subjected to performance test, and the test method comprises the following steps: the contact resistivity is tested according to the TLM rule; the composite current was tested using a SunsVoc tester.
The test results are shown in the following table:
through comparison of performances of examples 1-6 and comparative examples 1-3, the conversion efficiency of the high-performance metallization paste for the solar cell prepared by the invention is 25.8% at most, which is 13% higher than comparative example 3, and the contact resistivity is improved by the same time<1mΩ.cm2Composite current<50fA/cm2The high-performance metallization paste for the solar cell, which is prepared by the invention, has the advantages of high conversion efficiency, low recombination current and low contact resistance.
While the embodiments of the present invention have been disclosed above, it is not limited to the applications listed in the description and embodiments, but is fully applicable to various fields suitable for the present invention, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principle and spirit of the present invention, and therefore the present invention is not limited to the specific details without departing from the general concept defined in the claims and the scope of equivalents thereof.
Claims (10)
1. The high-performance metallization paste for the solar cell is characterized by comprising the following raw materials in parts by weight: 5-10 parts of organic resin, 10-20 parts of organic solvent, 0.2-0.5 part of surfactant, 0.1-0.3 part of coupling agent, 0.2-0.4 part of maleic anhydride grafting compatilizer, 2-5 parts of silver-coated glass powder, 5-12 parts of glass powder, 70-80 parts of silver powder and 1-3 parts of nano alloy powder.
2. The high-performance metallization paste for solar cells according to claim 1, wherein said organic resin is a thermoplastic resin, and said thermoplastic resin is at least one of polyethylene, polypropylene, polystyrene, and polyvinyl butyral.
3. The high-performance metallization paste for a solar cell according to claim 1, wherein the organic solvent comprises a hydrophilic organic solvent and a lipophilic organic solvent, and the hydrophilic organic solvent is at least one of methanol, ethanol, acetone, formic acid, and acetic acid; the lipophilic organic solvent is at least one of dimethyl adipate, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, terpineol and dioctyl phthalate.
4. The high-performance metallization paste for solar cells according to claim 1, wherein the maleic anhydride grafted compatibilizer is at least one of maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted polypropylene, and maleic anhydride grafted polyethylene.
5. The high-performance metallization paste for solar cells according to claim 1, wherein the silver powder is a mixture of one or more of spherical silver powder, flake silver powder, irregular silver powder, and linear silver powder; the D50 of the silver powder is 400-600 nm.
6. The high-performance metallization paste for the solar cell according to claim 1, wherein the nano alloy powder is at least one of tin-based, lead-based, aluminum-based, and copper-based alloy powders; the particle size of the nano alloy powder is 100-300 nm.
7. The high-performance metallization paste for solar cells according to claim 1, wherein the silver-coated glass powder is prepared by the following method:
a. slowly dropwise adding ammonia water with the concentration of 0.01-0.05 mol/L into a silver nitrate solution with the concentration of 0.01-0.05 mol/L, and stirring for 1-2 h to obtain a silver ammonia solution;
b. adding absolute ethyl alcohol and polyvinylpyrrolidone into the silver-ammonia solution, and magnetically stirring until the absolute ethyl alcohol and the polyvinylpyrrolidone are fully dissolved to obtain a mixed solution;
c. adding glass powder into the mixed liquid obtained in the step b, ultrasonically dispersing for 10-30 min by using a cell ultrasonic crusher, and then heating for 2-4 h in a water bath at the temperature of 60-80 ℃ to obtain mixed liquid containing activated glass powder;
d. slowly dripping a glucose solution with the concentration of 0.01-0.1 mlo/L into the mixed solution obtained in the step c, reacting for 20-60 min under the conditions of water bath heating and magnetic stirring after dripping is finished for 2-3 min; after the reaction is finished, alternately washing and centrifuging by deionized water and absolute ethyl alcohol for 3 times respectively; and finally, placing the glass powder in an oven with the temperature of 80-90 ℃, and drying for 6-8 h to obtain the silver-coated glass powder.
8. The high-performance metallization paste for the solar cell according to claim 7, wherein the mass ratio of the silver nitrate solution to the ammonia water in the step a is 1: 1-10.
9. The high-performance metallization paste for the solar cell according to claim 7, wherein the absolute ethanol accounts for 5-15% of the mass of the silver-ammonia solution in the step b, and the polyvinylpyrrolidone accounts for 1-3% of the mass of the silver-ammonia solution.
10. A method of preparing a high performance metallization paste for solar cells according to claims 1-9, characterized in that:
(1) putting the silver-coated glass powder, the silver powder and the nano-alloy powder into a ball mill, and grinding while stirring until the mixture is uniformly mixed to obtain mixed powder;
(2) putting an organic solvent and an organic resin into a reaction kettle in proportion, heating and stirring to dissolve the resin at the temperature of 120-140 ℃ for 1-2 h, adding a surfactant, a coupling agent and a maleic anhydride grafting compatilizer, stirring at the rotating speed of 2000-3000 RPM (revolutions per minute) at the activation temperature of 60-80 ℃, and reacting for 1-2 h to obtain an organic carrier with the viscosity of 30-45 Pa.S;
(3) adding the mixed powder in the step (1) into the organic carrier in the step (2), and stirring for 4-6 hours at the temperature of 40-60 ℃ to obtain uniformly mixed slurry;
(4) and (4) grinding the slurry obtained in the step (3) in a three-roll mill, and finely adjusting the organic solvent to enable the fineness of the silver paste to be below 25um and the viscosity to be 150-350 Pa & S, so as to obtain the high-performance metalized slurry for the solar cell.
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| CN115073011A (en) * | 2022-04-27 | 2022-09-20 | 中南大学 | Low-lead glass powder, preparation method and application thereof, back silver paste and application thereof |
| CN115101236A (en) * | 2022-07-12 | 2022-09-23 | 浙江奕成科技有限公司 | Silver paste containing coated glass powder and crystalline silicon solar cell manufactured by silver paste |
| CN116314369A (en) * | 2023-02-14 | 2023-06-23 | 英利能源发展(保定)有限公司 | Silver paste for improving printing effect of back surface of N-type TOPCon crystalline silicon battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115073011A (en) * | 2022-04-27 | 2022-09-20 | 中南大学 | Low-lead glass powder, preparation method and application thereof, back silver paste and application thereof |
| CN115073011B (en) * | 2022-04-27 | 2023-07-07 | 中南大学 | Low-lead glass powder, preparation method and application thereof, back silver paste and application thereof |
| CN115101236A (en) * | 2022-07-12 | 2022-09-23 | 浙江奕成科技有限公司 | Silver paste containing coated glass powder and crystalline silicon solar cell manufactured by silver paste |
| CN116314369A (en) * | 2023-02-14 | 2023-06-23 | 英利能源发展(保定)有限公司 | Silver paste for improving printing effect of back surface of N-type TOPCon crystalline silicon battery and preparation method thereof |
| CN116959778A (en) * | 2023-07-03 | 2023-10-27 | 隆基绿能科技股份有限公司 | Use of accelerator and conductive additive in preparing low-temperature conductive copper paste and low-temperature conductive copper paste |
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