CN115938640A - Acetic acid resistant solar cell silver paste and preparation method thereof - Google Patents
Acetic acid resistant solar cell silver paste and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an acetic acid resistant solar cell silver paste and a preparation method thereof. And alkaline organic auxiliary agents are introduced, so that alkaline oxides independently existing in the sintered grid lines are embedded in the silver grid lines, and even if a small amount of acetic acid steam enters the grid lines, the alkaline substances further react with the acetic acid steam to form acetate, so that the acetate is difficult to enter a silver-silicon interface, the damage of the acetic acid to the electrical property is further reduced, and the higher power generation efficiency of the solar cell is kept.
Description
Technical Field
The invention relates to a front silver paste of a solar cell, in particular to an acetic acid resistant silver paste of the solar cell and a preparation method thereof, and belongs to the technical field of front silver paste of the solar cell.
Background
In recent years, the development of new energy industry is vigorously promoted by the nation, and the fossil energy industry is influenced by different degrees due to the development and change of the world pattern, and even a local fossil energy crisis is caused in serious cases. Meanwhile, the solar energy industry develops rapidly, and the installed capacity is continuously new and high. The national development reform Commission and the national energy agency have issued the "fourteen five" modern energy system plans, which indicate: rapidly developing non-fossil energy; the development of wind power and solar power generation is accelerated; the large-scale development and high-quality development of wind power and solar power generation are comprehensively promoted, local and near development and utilization are preferentially carried out, the distributed wind power and distributed photovoltaic construction of a load center and peripheral areas is accelerated, and the low-wind-speed wind power technology is popularized and applied. This series of actions accelerates the development of solar energy, and therefore it is predicted that a 250GW photovoltaic system will be installed in the recent years around the world, and the global cumulative total installed capacity approaches 1TW, which is a milestone of global energy transformation. The newly added photovoltaic installed capacity in 2022 of china is about 108GW, which is almost twice as much as about 55GW in 2021.
Most of the current solar cell modules are packaged by EVA, and the modules cause serious power loss in long-term damp and hot environments. The EVA packaging material can be decomposed to generate acetic acid when exposed in the atmosphere and under the illumination condition, and the acetic acid can accelerate the corrosion of the silver electrode on the surface of the cell, so that the silver electrode is blackened, the efficiency of the cell is reduced, and the power generation power of the assembly is reduced. Therefore, there is a need to develop a novel solar front silver paste which can effectively suppress or significantly reduce the influence of acetic acid generated by EVA, maintain the power generation of the module at a high level, and increase the power generation amount. With the continuous improvement of the requirements of customers on solar modules, some mainstream factories in China begin to provide strict requirements on the acetic acid resistance of the solar front silver paste, but the efficiency attenuation of the solar cell prepared by the solar front silver paste on the market at present basically reaches more than 20% after an acetic acid experiment, and the solar cell does not reach the requirements of solar cell enterprises or module enterprises, and the prior art of the solar front silver paste with excellent acetic acid resistance reported by related documents is not available until now.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an acetic acid resistant solar cell silver paste and a preparation method thereof. The porosity of silver slurry sintering is reduced by adding the alkaline boride, so that acetic acid steam is difficult to enter the silver grid line, and the influence of the acetic acid steam on the electrical property is reduced; meanwhile, an alkaline organic auxiliary agent is introduced, so that an alkaline oxide independently existing in the sintered grid line is embedded in the silver grid line, the damage of acetic acid to the electrical property is further reduced, and the purpose of keeping higher power generation efficiency of the solar cell is realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the invention, an acetic acid resistant solar cell silver paste is provided:
an acetic acid resistant solar cell silver paste, the solar cell silver paste comprising: 82 to 92wt% (preferably 85 to 90 wt%) of silver powder, 5 to 15wt% (preferably 8 to 12 wt%) of organic vehicle, 0.5 to 5wt% (preferably 0.8 to 4 wt%) of glass frit, 0.1 to 5wt% (preferably 0.5 to 4 wt%) of alkali boride and 0.1 to 5wt% (preferably 0.5 to 4 wt%) of organic assistant.
Preferably, the organic vehicle comprises: 70-92wt% (preferably 75-88 wt%) of organic solvent, 5-20wt% (preferably 8-18 wt%) of high molecular polymer and 0.1-10wt% (preferably 2-8 wt%) of additive.
Preferably, the organic solvent is one or more of dodecyl glycol ester, diethylene glycol monobutyl ether, oleic acid, diethylene glycol monobutyl ether acetate and terpineol.
Preferably, the high molecular polymer is one or more of acrylic resin, ethyl cellulose and rosin resin.
Preferably, the additive is a polybasic amide polycarboxylate and/or a bovine ester diamine dioleate.
Preferably, the silver powder is spherical silver powder, and the particle diameter of the spherical silver powder is 0.5-5 μm, preferably 0.8-4 μm, and more preferably 1-3 μm.
Preferably, the glass powder is a Pb-Te system glass powder (e.g., a commercially available solar-grade silver glass powder, approximately 20% PbO, 40% TeO) 2 、25％Bi 2 0 3 、7％SiO 2 、3％ZnO、2％W0 3 、2％B 2 O 3 、1％LiO 2 ) The particle size of the glass frit is 0.2 to 4 μm, preferably 0.5 to 3.5 μm, and more preferably 0.8 to 3 μm.
Preferably, the boride is vanadium boride and/or yttrium boride, preferably yttrium tetraboride and/or yttrium hexaboride, more preferably yttrium hexaboride. The boride has a particle size range of D50=0.1-2 μm, preferably D50=0.2-1.5 μm, more preferably D50=0.3-1 μm.
Preferably, the organic auxiliary agent is a potassium-based polymer, and the methyl polymer is selected from one or more of potassium tert-butoxide, potassium sorbate, potassium monoethylmalonate, potassium monomethyl malonate, potassium trihydrooxalate, potassium hydrogen phthalate and potassium methylsulfonate.
According to a second embodiment of the invention, a method for preparing an acetic acid resistant silver paste for a solar cell is provided.
A method of making an acetic acid resistant solar cell silver paste or a method of making an acetic acid resistant solar cell silver paste according to the first embodiment, the method comprising the steps of:
1) The organic carrier, the glass powder, the alkaline boride and the organic auxiliary agent are mixed and dispersed uniformly according to the proportion, and then the silver powder is added to be continuously mixed and dispersed uniformly to obtain the mixed slurry.
2) And grinding the mixed slurry, then adding a solvent, and uniformly mixing and dispersing to obtain the solar cell silver paste.
Preferably, in the step 1), the mass ratio of the silver powder, the organic vehicle, the glass powder, the alkali boride and the organic auxiliary agent is 82-92.
Preferably, in the step 1), the organic carrier is obtained by uniformly mixing and dispersing an organic solvent, a high molecular polymer and an additive in a mass ratio of 70-92. Wherein: the organic solvent is one or more of dodecyl glycol ester, diethylene glycol monobutyl ether, oleic acid, diethylene glycol monobutyl ether acetate and terpineol. The high molecular polymer is one or more of acrylic resin, ethyl cellulose and rosin resin. The additive is polybasic amide polycarboxylate and/or tallow diamine dioleate.
Preferably, the silver powder is a spherical silver powder, and the spherical silver powder has a particle diameter of 0.5 to 5 μm, preferably 0.8 to 4 μm, and more preferably 1 to 3 μm.
Preferably, the glass frit is a Pb-Te system glass frit, and the particle size of the glass frit is 0.2 to 4 μm, preferably 0.5 to 3.5 μm, and more preferably 0.8 to 3 μm.
Preferably, the boride is vanadium boride and/or yttrium boride, preferably yttrium tetraboride and/or yttrium hexaboride, more preferably yttrium hexaboride. The boride has a particle size range of D50=0.1-2 μm, preferably D50=0.2-1.5 μm, more preferably D50=0.3-1 μm.
Preferably, the organic auxiliary agent is a potassium-based polymer, and is preferably one or more of potassium tert-butoxide, potassium sorbate, potassium monoethylmalonate, potassium monomethyl malonate, potassium trihydrooxalate, potassium hydrogenphthalate and potassium methylsulfonate.
Preferably, in step 1), the first mixing and dispersing is performed at 200-1000rpm (300-800 rpm) for 1-40min (5-30 min is preferred). The second mixing and dispersing process is to disperse for 10-60min (20-40 min is preferable) at 800-2000rpm (1000-1800 rpm is preferable).
Preferably, in step 2), the grinding is carried out 2 to 10 times (preferably 3 to 8 times) on a three-roll grinder. The mixing and dispersing are carried out for 1-10min (preferably 2-8 min) at the rotating speed of 1000-3000rpm (preferably 1200-2500 rpm).
Preferably, in step 2), the solvent is diethylene glycol monobutyl ether. The adding amount of the solvent is 0.1-3%, preferably 0.3-2% of the total mass of the mixed slurry.
In the prior art, solar cell modules are mostly encapsulated with EVA, which leads to a severe loss of power in a long-term hot and humid environment. The EVA packaging material can be decomposed to generate acetic acid under the conditions of exposure to the atmosphere and illumination, and the acetic acid can accelerate corrosion of the silver electrode on the surface of the cell, so that the silver electrode is blackened, the efficiency of the cell is reduced, and the power generation power of the assembly is reduced. The efficiency attenuation of the solar front silver paste and the solar cell prepared by the solar front silver paste in the current market through an acetic acid experiment basically reaches more than 20 percent, and the solar front silver paste and the solar cell prepared by the solar front silver paste do not meet the requirements of solar cell enterprises or component enterprises.
In the invention, alkaline boride such as vanadium boride and/or yttrium boride is introduced into the battery slurry as a filler, the filler is used for reducing the clearance rate so as to improve the compactness of the silver grid line, and meanwhile, the superior resistance of filler elements is also used for improving the acid resistance of a grid line system in a bidirectional manner, so that the aim of reducing the acid resistance of the solar front silver slurry is fulfilled, and the influence of acetic acid on the conductivity of the grid line is reduced.
In the invention, the boride is vanadium boride and/or yttrium boride, and compared with other borides (such as zinc boride, titanium boride, lanthanum boride, magnesium boride and the like), the vanadium boride has better electric and heat conducting properties, does not influence the absorption of silver powder glass powder to heat, has the characteristic of resisting molten metal erosion, does not act with the internal glass powder, and thus does not influence the function of the glass powder and the efficiency of a battery. The boride is an alkaline material, and also has the effects of obviously hindering the diffusion of acetic acid and reducing the attenuation of efficiency; titanium boride, lanthanum boride and the like are basically cathode materials, are easily compounded with a battery after being used for a front electrode, lead to efficiency loss, and particularly, zinc element has potential energy close to that of silicon, is impurity ions in the introduction process, plays a role in compounding a center, reacts with the silicon surface, increases the difficulty of electronic transition, has higher contact resistance, and is not beneficial to improving the efficiency of the battery.
In the invention, the alkaline material of methyl polymer is introduced into the battery slurry as an auxiliary agent, the alkaline organic auxiliary agent is added and effectively dispersed into the slurry, and exists in the silver body after the silver grid line is prepared by sintering, and simultaneously, the alkaline organic auxiliary agent has smaller particle state, so that the acetic acid steam can be ensured to continuously react and neutralize after the action of the first layer of alkaline boride is broken through, the stability in a grid line system is further ensured, and the damage to the battery efficiency is reduced to the minimum.
In the invention, the glass powder is Pb-Te system glass powder, and compared with other system glass powder, the Pb-Te system glass powder has higher fluidity and stronger silver dissolving capacity, silver particles are separated out in the cooling process, so that the slurry can be suitable for higher sheet resistance silicon wafers, and has better contact resistance and process window. And the glass powder of the conventional system is difficult to meet the requirement of the solar cell on the continuously improved sheet resistance, so that the Pb-Te system glass plays an important role in silver paste.
In the invention, the organic auxiliary agent mainly contains alkaline organic auxiliary agent, which has the function of reducing the corrosion of acetic acid to silver wires, and because the content is less and the organic auxiliary agent is more favorable for dispersing into each part of the slurry, the organic auxiliary agent is selected and dispersed into the slurry system, thereby effectively blocking the entry of acetic acid steam after sintering. And alkaline organic auxiliary agents are not basically added in the conventional organic carriers, so that the requirement of an acetic acid experiment cannot be met, and the efficiency of the battery plate is reduced by more than 20%.
Compared with the prior art, the invention has the following beneficial technical effects:
1: the invention obviously improves the acid resistance of the slurry in the formula by using the basic boride as the filler. The method is characterized in that the alkaline boride is introduced to reduce the gap rate and further improve the compactness of the silver grid line, and meanwhile, the superior resistance of the elements is utilized to improve the acid resistance of a grid line system in a two-way mode, so that acetic acid steam is difficult to enter the silver grid line, and the influence of the acetic acid steam on the electrical property is reduced.
2: the invention also introduces the organic auxiliary agent containing alkalinity, so that the alkaline oxide independently existing in the grid line after sintering is embedded in the silver grid line, even if a small amount of acetic acid steam enters the grid line, the alkaline substance further reacts with the grid line to form acetate, so that the acetate is difficult to enter the silver-silicon interface, the damage of the acetic acid to the electrical property is further reduced, and the higher generating efficiency of the solar cell is kept.
3: the acetic acid resistant solar cell front silver paste disclosed by the invention is simple in component composition, cheap and easily available in raw materials, short in preparation flow, excellent in acetic acid resistance, and wide in market prospect and economic benefit.
Drawings
Fig. 1 is a plot of post-cell acetic EL for the slurry prepared in example 1.
Fig. 2 is a plot of the post-cell acetic EL of the paste prepared in comparative example 1.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
A method for preparing acetic acid resistant solar cell silver paste comprises the following steps:
1) The organic carrier, the glass powder, the alkaline boride and the organic auxiliary agent are mixed and dispersed uniformly according to the proportion, and then the silver powder is added to be continuously mixed and dispersed uniformly to obtain the mixed slurry.
2) And grinding the mixed slurry, then adding a solvent, and uniformly mixing and dispersing to obtain the solar cell silver paste.
Preferably, in the step 1), the mass ratio of the silver powder, the organic vehicle, the glass powder, the alkali boride and the organic auxiliary agent is 82-92.
Preferably, in the step 1), the organic carrier is obtained by uniformly mixing and dispersing an organic solvent, a high molecular polymer and an additive in a mass ratio of 70-92. Wherein: the organic solvent is one or more of dodecyl glycol ester, diethylene glycol monobutyl ether, oleic acid, diethylene glycol monobutyl ether acetate and terpineol. The high molecular polymer is one or more of acrylic resin, ethyl cellulose and rosin resin. The additive is polybasic amide polycarboxylate and/or tallow diamine dioleate.
Preferably, the silver powder is a spherical silver powder, and the spherical silver powder has a particle diameter of 0.5 to 5 μm, preferably 0.8 to 4 μm, and more preferably 1 to 3 μm.
Preferably, the glass frit is a Pb-Te system glass frit, and the particle size of the glass frit is 0.2 to 4 μm, preferably 0.5 to 3.5 μm, and more preferably 0.8 to 3 μm.
Preferably, the boride is vanadium boride and/or yttrium boride, preferably yttrium tetraboride and/or yttrium hexaboride, more preferably yttrium hexaboride. The particle size range of the boride is D50=0.1-2 μm, preferably D50=0.2-1.5 μm, more preferably D50=0.3-1 μm.
Preferably, the organic auxiliary agent is a potassium-based polymer, and is preferably one or more of potassium tert-butoxide, potassium sorbate, potassium monoethyl malonate, potassium monomethyl malonate, potassium trihydrooxalate, potassium hydrogenphthalate and potassium methylsulfonate.
Preferably, in step 1), the first mixing and dispersing is performed at 200-1000rpm (300-800 rpm) for 1-40min (5-30 min is preferred). The second mixing and dispersing process is to disperse for 10-60min (20-40 min is preferable) at 800-2000rpm (1000-1800 rpm is preferable).
Preferably, in step 2), the grinding is carried out 2 to 10 times (preferably 3 to 8 times) on a three-roll grinder. The mixing and dispersing are carried out for 1-10min (preferably 2-8 min) at the rotating speed of 1000-3000rpm (preferably 1200-2500 rpm).
Preferably, in step 2), the solvent is diethylene glycol monobutyl ether. The adding amount of the solvent is 0.1-3%, preferably 0.3-2% of the total mass of the mixed slurry.
Example 1
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3: 1; cooling to 25 deg.C after completely dispersing and dissolving, then adding 1 part of additive (tallow diamine dioleate), stirring and mixing for 20min to obtain uniform organic carrier.
Preparing battery silver paste: weighing 2 parts of Pb-Te system glass powder (commercially available solar energy positive silver glass powder, approximate composition: 20% by weight of PbO, 40% by weight of TeO 2 、25％Bi 2 0 3 、7％SiO 2 、3％ZnO、2％W0 3 、2％B 2 O 3 、1％LiO 2 The same applies below), 8 parts of an organic vehicle, 2 parts of vanadium boride (D50 =0.5 μm), and 2 parts of potassium sorbate, which are then dispersed in a disperser at 300rpm for 10min, followed by addition of 86 parts of spherical silver powder (average particle size of about 1.2 μm) and dispersion in a disperser at 1100rpm for 40min to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 0.8 part of organic solvent (diethylene glycol monobutyl ether), and dispersing for 5min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
By adopting the prepared sample, electrode grid lines are formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm by screen printing with 520 meshes, the width of a main grid is 0.4 micron, the width of a fine grid is 25 microns, and the electrode grid lines are sintered in a Despatch sintering furnace, wherein the peak actual temperature is 760.5 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.31A, open-circuit voltage is 685.2mv, and photoelectric conversion efficiency is 23.22%. And then, carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency attenuation rate data as follows: short-circuit current is 13.21A, open-circuit voltage is 684.3mv, photoelectric conversion efficiency is 22.92%, and efficiency attenuation rate is 1.29%.
Example 2
Preparation of organic vehicle: mixing 93 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 deg.C after completely dispersing and dissolving, adding 1 part of additive (tallow diamine dioleate), stirring and mixing for 20min to obtain uniform organic carrier.
Preparing the battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 8 parts of organic vehicle, 2.5 parts of vanadium boride (D50 =0.4 μm) and 1.5 parts of potassium methanesulfonate, dispersing them in a dispersion machine at the rotation speed of 350rpm for 12min, then adding 86 parts of spherical silver powder (average particle size of about 1.0 μm) and dispersing them in a dispersion machine at the rotation speed of 1200rpm for 40min to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 1 part of organic solvent (diethylene glycol monobutyl ether), and dispersing for 5min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
By adopting the prepared sample, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm by screen printing with 520 meshes, the width of a main grid is 0.4 micron, the width of a fine grid is 25 microns, and the electrode grid line is sintered in a Despatch sintering furnace, wherein the peak actual temperature is 744.9 ℃.
The electrical data after sintering are tested as follows: short-circuit current is 13.27A, open-circuit voltage is 686.1mv, and photoelectric conversion efficiency is 23.14%. And then carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency decay rate data as follows: short-circuit current is 13.11A, open-circuit voltage is 684.5mv, photoelectric conversion efficiency is 22.78%, and efficiency attenuation rate is 1.56%.
Example 3
Preparation of organic vehicle: mixing 87 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; after complete dispersion and dissolution, the mixture is cooled to 25 ℃, and then 1.2 parts of additive (polybasic amide polycarboxylate) is added, stirred and mixed for 20min to obtain the uniform organic carrier.
Preparing the battery silver paste: weighing 2.2 parts of Pb-Te system glass powder (same as example 1), 6.8 parts of organic vehicle, 1.5 parts of yttrium tetraboride (D50 =0.4 μm) and 1.5 parts of potassium monomethyl malonate, dispersing them in a dispersion machine at the rotation speed of 400rpm for 10min, then adding 88 parts of spherical silver powder (the average particle size is about 1.4 μm) and dispersing in a dispersion machine at the rotation speed of 1200rpm for 30min to obtain mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 5 times (the fineness is lower than 6 mu m), then adding 1.1 parts of organic solvent (diethylene glycol monobutyl ether), and dispersing for 8min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is adopted, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 micron, the mixture is sintered in a Despatch sintering furnace, and the actual peak temperature is 752.4 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.28A, open-circuit voltage is 684.3mv, and photoelectric conversion efficiency is 23.08%. And then, carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency attenuation rate data as follows: short-circuit current is 13.16A, open-circuit voltage is 683.2mv, photoelectric conversion efficiency is 22.06%, and efficiency attenuation rate is 4.42%.
Example 4
Preparation of organic vehicle: mixing 88.7 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 ℃ after complete dispersion and dissolution, then adding 1.3 parts of additive (polybasic amide polycarboxylate), stirring and mixing for 20min to obtain the uniform organic carrier.
Preparing battery silver paste: weighing 1.8 parts of Pb-Te system glass powder (same as example 1), 7.2 parts of an organic vehicle, 2 parts of yttrium tetraboride (D50 =0.5 μm) and 3 parts of potassium hydrogen phthalate, dispersing them in a dispersion machine at the rotation speed of 400rpm for 10min, then adding 86 parts of spherical silver powder (the average particle size is about 2.5 μm) and dispersing for 30min in a dispersion machine at the rotation speed of 1200rpm to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 5 times (the fineness is lower than 6 mu m), then adding 1.1 parts of organic solvent (diethylene glycol monobutyl ether), and dispersing for 8min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is adopted, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 micron, sintering is carried out in a Despatch sintering furnace, and the peak actual temperature is 770.3 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.31A, open-circuit voltage is 686.7mv, and photoelectric conversion efficiency is 23.18%. And then carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency decay rate data as follows: short-circuit current is 13.13A, open-circuit voltage is 683.0mv, photoelectric conversion efficiency is 21.49%, and efficiency attenuation rate is 7.29%.
Example 5
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 ℃ after complete dispersion and dissolution, then adding 1 part of additive (polybasic amide polybasic carboxylate) and stirring and mixing for 20min to obtain the uniform organic carrier.
Preparing the battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 6 parts of organic vehicle, 2.3 parts of yttrium hexaboride (D50 =0.5 μm) and 1.7 parts of potassium trihydrooxalate, dispersing them in a dispersion machine at the rotation speed of 400rpm for 10min, then adding 88 parts of spherical silver powder (average particle size about 0.8 μm) and dispersing in a dispersion machine at the rotation speed of 1200rpm for 30min to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 1.1 parts of organic solvent (diethylene glycol monobutyl ether), and dispersing for 8min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
By adopting the prepared sample, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm by screen printing with 520 meshes, the width of a main grid is 0.4 micron, the width of a fine grid is 25 microns, and the electrode grid line is sintered in a Despatch sintering furnace, wherein the peak actual temperature is 749.0 ℃.
The electrical data after sintering are tested as follows: short-circuit current is 13.32A, open-circuit voltage is 686.8mv, and photoelectric conversion efficiency is 23.24%. And then, carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency attenuation rate data as follows: short-circuit current is 13.09A, open-circuit voltage is 684.1mv, photoelectric conversion efficiency is 22.98%, and efficiency attenuation rate is 1.12%.
Comparative example 1
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 deg.C after completely dispersing and dissolving, then adding 1 part of additive (tallow diamine dioleate), stirring and mixing for 20min to obtain uniform organic carrier.
Preparing the battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 8 parts of organic carrier and 2 parts of potassium sorbate, dispersing the materials in a dispersion machine at the rotating speed of 300rpm for 10min, then adding 88 parts of spherical silver powder (the average particle size is about 2 μm) and dispersing the mixture in a dispersion machine at the rotating speed of 1100rpm for 40min to obtain mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 0.8 part of organic solvent (diethylene glycol monobutyl ether), and dispersing for 5min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is used for forming an electrode grid line on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 micron, the mixture is sintered in a Despatch sintering furnace, and the peak actual temperature is 758.1 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.18A, open-circuit voltage is 682.5mv, and photoelectric conversion efficiency is 20.12%. And then carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency decay rate data as follows: short-circuit current is 13.00A, open-circuit voltage 678.7mv, photoelectric conversion efficiency is 14.71%, and efficiency attenuation rate is 26.88%.
Comparative example 2
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 deg.C after completely dispersing and dissolving, adding 1 part of additive (tallow diamine dioleate), stirring and mixing for 20min to obtain uniform organic carrier.
Preparing the battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 8 parts of organic vehicle, and 2 parts of vanadium boride (D50 =0.5 μm), dispersing them in a disperser rotating at 300rpm for 10min, then adding 88 parts of spherical silver powder (average particle size about 2 μm), and dispersing in a disperser rotating at 1100rpm for 40min to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 0.8 part of organic solvent (diethylene glycol monobutyl ether), and dispersing for 5min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is adopted, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 micron, the mixture is sintered in a Despatch sintering furnace, and the actual peak temperature is 752.0 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.16A, open-circuit voltage is 681.1mv, and photoelectric conversion efficiency is 21.04%. And then, carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency attenuation rate data as follows: short-circuit current is 12.97A, open-circuit voltage is 679.9mv, photoelectric conversion efficiency is 15.80%, and efficiency attenuation rate is 24.91%.
Comparative example 3
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; cooling to 25 ℃ after complete dispersion and dissolution, then adding 1 part of additive (polybasic amide polycarboxylate), stirring and mixing for 20min to obtain the uniform organic carrier.
Preparing battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 6 parts of organic vehicle, 2.3 parts of zinc boride (D50 =0.5 μm) and 1.7 parts of potassium trihydrooxalate, dispersing them in a dispersion machine at the rotation speed of 400rpm for 10min, then adding 88 parts of spherical silver powder (average particle size of about 0.8 μm) and dispersing in a dispersion machine at the rotation speed of 1200rpm for 30min to obtain a mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 1.1 parts of organic solvent (diethylene glycol monobutyl ether), and dispersing for 8min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is adopted, an electrode grid line is formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 microns, the mixture is sintered in a Despatch sintering furnace, and the peak actual temperature is 750.8 ℃.
The electrical data after sintering is as follows: short-circuit current is 13.10A, open-circuit voltage is 681.3mv, and photoelectric conversion efficiency is 22.18%. And then carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency decay rate data as follows: short-circuit current is 12.99A, open-circuit voltage is 680.6mv, photoelectric conversion efficiency is 17.52%, and efficiency attenuation rate is 21.0%.
Comparative example 4
Preparation of organic vehicle: mixing 85 parts of an organic solvent (dodecanol ester: diethylene glycol monobutyl ether: oleic acid: diethylene glycol monobutyl ether acetate =3, mass ratio: 1; after complete dispersion and dissolution, cooling to 25 ℃, then adding 1 part of additive (polybasic amide polycarboxylate), stirring and mixing for 20min to obtain the uniform organic carrier.
Preparing battery silver paste: weighing 2 parts of Pb-Te system glass powder (same as example 1), 6 parts of organic carrier, 2.3 parts of lanthanum hexaboride (D50 =0.5 μm) and 1.7 parts of potassium trihydrooxalate, dispersing the materials in a dispersion machine at the rotating speed of 400rpm for 10min, adding 88 parts of spherical silver powder (the average particle size is about 0.8 μm), and dispersing the mixture in a dispersion machine at the rotating speed of 1200rpm for 30min to obtain mixed slurry; and finally, grinding the mixed slurry on a three-roll grinder for 6 times (the fineness is lower than 5 mu m), then adding 1.1 parts of organic solvent (diethylene glycol monobutyl ether), and dispersing for 8min at the rotating speed of 1500rpm by using a high-speed dispersion machine, thus obtaining the acetic acid resistant solar cell silver paste after the dispersion is finished.
The prepared sample is adopted, electrode grid lines are formed on a P-type silicon wafer with the specification of 182mm multiplied by 182mm through 520-mesh screen printing, the width of a main grid is 0.4 micron, the width of a fine grid is 25 microns, the mixture is sintered in a Despatch sintering furnace, and the actual peak temperature is 752.6 ℃.
The electrical data after sintering are tested as follows: short-circuit current is 13.12A, open-circuit voltage is 680.0mv, and photoelectric conversion efficiency is 21.00%. And then, carrying out an acetic acid experiment on the cell, and testing the efficiency and calculating the efficiency attenuation rate data as follows: short-circuit current is 13.00A, open-circuit voltage is 679.3mv, photoelectric conversion efficiency is 16.18%, and efficiency attenuation rate is 22.95%.
After an acetic acid experiment is carried out on a common battery, grid lines of the battery turn yellow and black, and meanwhile, the grid lines are easy to fall off, so that the EL image is obviously dark, and the situation that one grid is broken due to the fact that partial grid lines fall off is similar. Fig. 1 is a plot of the post-cell acetic EL of the slurry prepared in example 1. Fig. 2 is a plot of the post-cell acetic EL of the paste prepared in comparative example 1. As can be seen from the two figures: the boride-containing solar cell silver paste prepared in example 1 of the present application has better acetic acid resistance than the boride-free solar cell silver paste prepared in comparative example 1.
Claims (10)
1. The acetic acid resistant solar cell silver paste is characterized in that: the solar cell silver paste comprises: 82 to 92wt% (preferably 85 to 90 wt%) of silver powder, 5 to 15wt% (preferably 8 to 12 wt%) of organic vehicle, 0.5 to 5wt% (preferably 0.8 to 4 wt%) of glass frit, 0.1 to 5wt% (preferably 0.5 to 4 wt%) of alkali boride and 0.1 to 5wt% (preferably 0.5 to 4 wt%) of organic assistant.
2. The solar cell silver paste of claim 1, wherein: the organic vehicle includes: 70-92wt% (preferably 75-88 wt%) of an organic solvent, 5-20wt% (preferably 8-18 wt%) of a high molecular polymer, and 0.1-10wt% (preferably 2-8 wt%) of an additive.
3. The solar cell silver paste of claim 2, wherein: the organic solvent is one or more of dodecyl glycol ester, diethylene glycol monobutyl ether, oleic acid, diethylene glycol monobutyl ether acetate and terpineol; and/or
The high molecular polymer is one or more of acrylic resin, ethyl cellulose and rosin resin; and/or
The additive is a polybasic amide polycarboxylate and/or a tallow diamine dioleate.
4. The solar cell silver paste according to any one of claims 1 to 3, wherein: the silver powder is spherical silver powder, and the particle size of the spherical silver powder is 0.5-5 μm, preferably 0.8-4 μm, and more preferably 1-3 μm; and/or
The glass powder is Pb-Te system glass powder, and the particle size of the glass powder is 0.2-4 μm, preferably 0.5-3.5 μm, and more preferably 0.8-3 μm.
5. The solar cell silver paste of any one of claims 1-4, wherein: the boride is vanadium boride and/or yttrium boride, preferably yttrium tetraboride and/or yttrium hexaboride, and more preferably yttrium hexaboride; the boride has a particle size range of D50=0.1-2 μm, preferably D50=0.2-1.5 μm, more preferably D50=0.3-1 μm.
6. The solar cell silver paste according to any one of claims 1 to 5, wherein: the organic auxiliary agent is a potassium-based polymer, and preferably, the methyl polymer is one or more selected from potassium tert-butoxide, potassium sorbate, potassium monoethylmalonate, potassium monomethyl malonate, potassium trihydrooxalate, potassium hydrogenphthalate and potassium methylsulfonate.
7. A method for preparing an acetic acid resistant solar cell silver paste or a method for preparing an acetic acid resistant solar cell silver paste according to any one of claims 1-6, wherein the method comprises the following steps: the method comprises the following steps:
1) Mixing and dispersing the organic carrier, the glass powder, the alkaline boride and the organic auxiliary agent uniformly according to the proportion, then adding the silver powder, and continuously mixing and dispersing uniformly to obtain mixed slurry;
2) And grinding the mixed slurry, then adding a solvent, and uniformly mixing and dispersing to obtain the solar cell silver paste.
8. The method of claim 7, wherein: in the step 1), the mass ratio of the silver powder, the organic carrier, the glass powder, the alkaline boride and the organic auxiliary agent is (wt ratio) 82-92;
preferably, the organic carrier is obtained by uniformly mixing and dispersing an organic solvent, a high molecular polymer and an additive in a mass ratio of 70-92; wherein: the organic solvent is one or more of dodecyl glycol ester, diethylene glycol monobutyl ether, oleic acid, diethylene glycol monobutyl ether acetate and terpineol.
9. The method according to claim 7 or 8, characterized in that: the silver powder is spherical silver powder, and the particle size of the spherical silver powder is 0.5-5 μm, preferably 0.8-4 μm, and more preferably 1-3 μm; and/or
The glass powder is Pb-Te system glass powder, and the particle size of the glass powder is 0.2-4 μm, preferably 0.5-3.5 μm, and more preferably 0.8-3 μm; and/or
The boride is vanadium boride and/or yttrium boride, preferably yttrium tetraboride and/or yttrium hexaboride, and more preferably yttrium hexaboride; the particle size range of the boride is D50=0.1-2 μm, preferably D50=0.2-1.5 μm, more preferably D50=0.3-1 μm; and/or
The organic auxiliary agent is a potassium-based polymer, preferably one or more of potassium tert-butoxide, potassium sorbate, monoethyl malonate potassium salt, monomethyl malonate potassium salt, potassium trihydrooxalate, potassium hydrogen phthalate and potassium methylsulfonate.
10. The method according to any one of claims 7-9, wherein: in the step 1), the first mixing and dispersing is to disperse for 1-40min (preferably 5-30 min) at the rotating speed of 200-1000rpm (preferably 300-800 rpm); the second mixing and dispersing is to disperse for 10-60min (preferably 20-40 min) at the rotating speed of 800-2000rpm (preferably 1000-1800 rpm); and/or
In step 2), the grinding is carried out for 2 to 10 times (preferably 3 to 8 times) on a three-roll grinding machine; the mixing and dispersing are carried out for 1-10min (preferably 2-8 min) at the rotating speed of 1000-3000rpm (preferably 1200-2500 rpm);
preferably, in step 2), the solvent is diethylene glycol monobutyl ether; the adding amount of the solvent is 0.1-3%, preferably 0.3-2% of the total mass of the mixed slurry.
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