CN115925267A - Preparation method of PERC solar cell back silver glass powder and high-reliability silver paste - Google Patents
Preparation method of PERC solar cell back silver glass powder and high-reliability silver paste Download PDFInfo
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- CN115925267A CN115925267A CN202211620430.4A CN202211620430A CN115925267A CN 115925267 A CN115925267 A CN 115925267A CN 202211620430 A CN202211620430 A CN 202211620430A CN 115925267 A CN115925267 A CN 115925267A
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Abstract
The invention discloses a preparation method of PERC solar cell back silver glass powder and high-reliability silver paste, wherein the prepared glass powder system is a Bi-Si-Al-Cu system, the glass powder is prepared by mixing, calcining, water quenching, ball milling and freeze drying, a plurality of oxides in the components interact to form a stable metal coordination structure and can adapt to the sintering process of back silver, the glass powder is uniformly mixed with silver powder, an organic carrier and an additive and then ground by a three-roll grinder to obtain the silver paste, gaps can be filled with one another in the sintering process to generate a synergistic effect, the surface is smoother after sintering, the surface cracking is reduced, and the overall stability of the silver paste is enhanced.
Description
Technical Field
The invention belongs to the field of preparation of solar PERC (cathode-ray tube) battery slurry, and particularly relates to a preparation method of a rear silver glass powder and a high-reliability silver paste of a PERC solar battery.
Background
The silver paste for the solar cell plays an important role in the solar cell and plays an important role in the solar cell. Researches find that the problems of bubbling after printing, poor reliability and the like exist in the silver paste on the back of the PERC solar cell, and the reason is mainly that the formula of the glass powder needs to be optimized, the softening range of some glass powder does not meet the sintering requirement, so that the sintering film forming of the paste is influenced, and in addition, the glass powder needs to be reasonably matched with the silver powder and an organic carrier when being applied to the silver paste.
According to investigation, most of the existing industrialized glass powder continues to use the traditional glass powder and the silver-backed front silver glass powder. Meanwhile, the silver paste components are not properly matched, because the concept of the action among the silver powder, the glass powder and the organic carrier is not clear enough. These problems all result in a large area of bubbling on the surface of the PERC back silver print and poor water boiling tear, aging tension, etc.
Aiming at the problems faced by the silver paste, the invention provides a preparation method of a silver-back glass powder of a PERC solar cell and the silver paste with high reliability.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of PERC solar cell back silver glass powder and high-reliability silver paste, the prepared glass powder system is a Bi-Si-Al-Cu system, the glass powder is prepared by mixing, calcining, water quenching, ball milling and freeze drying, a plurality of oxides in the glass powder interact to form a stable metal coordination structure and can adapt to the sintering process of back silver, the glass powder is uniformly mixed with silver powder, an organic carrier and an additive and then ground by a three-roll grinder to obtain the silver paste, gaps can be mutually filled in the sintering process to generate a synergistic effect, the surface is smoother after sintering, the surface cracking is reduced, and the overall stability of the silver paste is enhanced.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a PERC solar cell back silver glass powder and a preparation method thereof, the glass powder system is a Bi-Si-Al-Cu system, comprising Bi 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 Is prepared from a plurality of the above raw materials;
the preparation method of the PERC solar cell back silver glass powder comprises the following steps:
s1, weighing Bi according to a certain proportion 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 At least 6 of the raw materials are uniformly mixed;
s2, placing the mixed material obtained in the step S1 into a ceramic crucible, and placing the ceramic crucible into a muffle furnace to be fired at a certain temperature;
s3, after the step S2 is finished, placing the molten glass liquid into cold water for water crushing treatment;
s4, placing the solid sample subjected to water quenching in the S3 into a ball mill for ball milling treatment;
and S5, grinding the ball-milled sample of S4 by using a sand mill, and finally performing freeze drying to obtain the finished glass powder.
As an improvement of the invention, the mass fraction of each component in the S1 is Bi 2 O 3 （10~40 wt%）、SiO 2 （10~30 wt%）、Al 2 O 3 （0~10 wt%）、ZnO（0~10 wt%）、V 2 O 5 （5~10 wt%）、CuO（10~20 wt%）、PbO（10~20 wt%）、Fe 2 O 3 (0 to 10 wt.%), and other oxides (0 to 20 wt.%).
As an improvement of the invention, in S2, the capacity of the crucible is 100 to 200 mL, the mixed materials are placed in a ceramic crucible without covering, the muffle furnace calcination temperature is 1000 to 1300 ℃, the heating rate is 5 to 15 ℃/min, and the calcination time is 30 to 50 min.
As an improvement of the invention, in the S4, the ball milling processing time is 8 to 10 hours, and the rotating speed is 300 to 500 r/min.
As an improvement of the invention, the grain diameter of the finished glass powder in S5 is 0.5-3 μm.
The invention also provides a high-reliability PERC back silver paste which comprises 50-75% of silver powder, 1-3% of glass powder, 30-50% of organic carrier and 1-3% of additive in mass ratio, wherein the organic carrier comprises resin and solvent, and the glass powder is the glass powder in claim 1.
As an improvement of the invention, the silver powder is a mixed spherical silver powder with at least two particle sizes, the particle size D50 is 0.3-1.0 μm, and the specific surface area is 1-2 m 2 /g。
As an improvement of the invention, the resin is at least one of CAB, ethyl cellulose and PVB, and the solvent is at least one of abietyl alcohol, toluol, butyl carbitol, butyl triethylene glycol ether and alcohol ester dodeca.
As a modification of the invention, the additive is at least one of hydrogenated castor oil, span and BYK-110.
The invention also provides a preparation method of the high-reliability PERC back silver paste, which is characterized by comprising the following steps:
(1) Preparing PERC back silver glass powder: adding Bi 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 At least 6 of the raw materials are fully mixed, calcined at 1000 to 1300 ℃, water-quenched, fully ball-milled for 8 to 10 hours, and then freeze-dried to obtain glass powder;
(2) Preparation of organic vehicle: selecting resin and an organic solvent, and placing the resin and the organic solvent in a stirrer to be stirred for 4 hours at 70 ℃ in a 400r/min stirrer to obtain an organic carrier;
(3) Preparing high-reliability silver paste of PERC back silver: uniformly mixing silver powder, the glass powder prepared in the step (1), the organic carrier prepared in the step (2) and an additive according to the mass ratio of 50-75%: 1-3%: 20-40%: 1-3%, and then grinding by using a three-roll grinder to obtain the silver paste.
The invention has the beneficial effects that:
(1) The invention adopts an independent preparation process to successfully prepare the Bi-Si-Al-Cu glass powder. Wherein the glass powder is constructed by using Bi-Si-Al-Cu as main glass powder as glass powder, and adopting a clarifier-like oxide Sb 2 O 3 、CeO 2 The method can effectively remove redundant bubbles in the process of silver paste sintering film forming so as to avoid the bubbling phenomenon after film forming, and adopts the oxide ZrO with strong electron withdrawing ability 2 、Fe 2 O 3 The phenomenon that the junction is permeated and irregular after the alloy at the silver-aluminum lap joint is formed can be effectively avoided.
(2) According to the invention, the glass powder is matched with at least two spherical silver powders with different sizes and particle sizes D50 of 0.3-1.0 μm, and a specific organic carrier and an additive are selected and matched, so that gaps can be filled with the silver powders in the sintering process, a synergistic effect is generated, the surface is smoother after sintering, surface cracking is reduced, and the overall stability of the silver paste is enhanced.
Drawings
FIG. 1 is a comparison of bubbling on the surface of silver paste under a microscope between an example of the present invention and a comparative example.
FIG. 2 is a comparison of silver-aluminum contact under a microscope between an example of the present invention and a comparative example.
FIG. 3 is a graph comparing the peeling of the inventive example and the comparative example under a microscope.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
(1) Preparing PERC back silver glass powder: taking Bi 2 O 3 、SiO 2 、Al 2 O 3 、CuO、CeO 2 、Fe 2 O 3 、Sb 2 O 3 、ZrO 2 And (2) uniformly mixing, wherein the mass fraction ratio of the raw materials is 34. Wherein the softening point of the glass powder is 550 ℃.
(2) Preparation of organic vehicle: and (2) selecting the ethyl cellulose, the butyl triethylene glycol ether and the alcohol ester with the mass fraction ratio of 13.
(3) Preparing high-reliability silver paste of PERC back silver: uniformly mixing spherical silver powder with the particle size D50 of 0.68 μm, spherical silver powder with the particle size D50 of 0.4 μm, finished glass powder prepared in the step (1), the organic carrier prepared in the step (2), span and hydrogenated castor oil, wherein the mass fraction ratio of the raw materials is (50).
Example 2
(1) Preparing PERC back silver glass powder: taking Bi 2 O 3 、SiO 2 、Al 2 O 3 、CuO、CeO 2 、Fe 2 O 3 、Sb 2 O 3 、ZrO 2 And (2) uniformly mixing, wherein the mass fraction ratio of the raw materials is 34. Wherein the glass powder has a softening point of550℃。
(2) Preparation of organic vehicle: and (2) selecting the ethyl cellulose, the butyl triethylene glycol ether and the alcohol ester with the mass fraction ratio of 13.
(3) Preparing high-reliability silver paste of PERC back silver: uniformly mixing spherical silver powder with the particle size D50 of 0.73 μm, spherical silver powder with the particle size D50 of 0.38 μm, finished glass powder prepared in the step (1), the organic carrier prepared in the step (2), span and hydrogenated castor oil, and grinding the uniformly mixed raw materials by a three-roll grinder for 9 times to obtain the prepared silver paste, wherein the fineness of the silver paste is less than 4 μm.
Example 3
(1) Preparing PERC back silver glass powder: taking Bi 2 O 3 、SiO 2 、Al 2 O 3 、CuO、CeO 2 、Fe 2 O 3 、Sb 2 O 3 、ZrO 2 And (2) mixing uniformly, wherein the mass fraction ratio of the raw materials is 34. Wherein the softening point of the glass powder is 550 ℃.
(2) Preparation of organic vehicle: and (2) selecting the ethyl cellulose, the butyl triethylene glycol ether and the alcohol ester with the mass fraction ratio of 13.
(3) Preparing silver paste with high reliability of PERC back silver: uniformly mixing spherical silver powder with the particle size D50 of 0.73 μm, spherical silver powder with the particle size D50 of 0.42 μm, finished glass powder prepared in the step (1), the organic carrier prepared in the step (2), span and hydrogenated castor oil, and grinding the uniformly mixed raw materials by a three-roll grinder for 9 times to obtain the prepared silver paste, wherein the fineness of the silver paste is less than 4 μm.
Comparative example
The industrial PERC silver paste with back silver is used as a comparative example.
The silver pastes of the examples 1 to 3 and the comparative example are printed on the back of the PERC electrode by a PERC back silver screen printer, and then sintered by a Despatch sintering furnace at 700 ℃ to 900 ℃. And (3) boiling the sintered PERC battery electrode with the back face upward for 20min at the water temperature of 85 ℃, and tearing and pulling the battery electrode by using a 3M adhesive tape at a reverse direction of 180 degrees to test the boiling powder falling condition. And adhering the tested 3M adhesive tape on white paper to observe a test result. Welding the welding strip on the silver paste on the back silver surface of the PERC by using a welding pen with the temperature of 400 ℃, putting the welded PERC battery electrode with the back face upward into a 160 ℃ oven, keeping the temperature for 30min, taking out, and testing the oven tension by using a tension meter. The sintered PERC cell was placed under a microscope to observe and test the silver-aluminum lap and the bubbling, and the test results are shown in table 1:
as shown in table 1 and fig. 1 to 3, the glass powder used in the present invention and the silver paste components are reasonably matched, so that the generation of silver-aluminum alloy is avoided, the lap joint position of the silver paste and the aluminum paste is smoother, and the bubbling phenomenon caused in the sintering process is solved by the oxide contained in the specific clarifier in the glass powder. Simultaneously also make the silver thick liquid possess higher oven pulling force. Three experiments in examples 1 to 3 show that compared with the silver paste of a comparison sample, the silver paste prepared by the glass powder and the silver paste components reasonably matched has high performance and high stability.
It should be noted that the above-mentioned embodiments illustrate only preferred embodiments of the invention, and are not intended to limit the scope of the invention, and that those skilled in the art will be able to make modifications and alterations to the above-mentioned embodiments without departing from the spirit of the invention, and such modifications and alterations are intended to be within the scope of the appended claims.
Claims (10)
1. The PERC solar cell back silver glass powder and the preparation method thereof are characterized in that: the glass powder system is a Bi-Si-Al-Cu system including Bi 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 The preparation method comprises the following steps:
s1, weighing Bi according to a certain proportion 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 At least 6 of the raw materials are uniformly mixed;
s2, placing the mixed material obtained in the step S1 into a ceramic crucible, and placing the ceramic crucible into a muffle furnace to be fired at a certain temperature;
s3, after the step S2 is finished, placing the molten glass liquid into cold water for water crushing treatment;
s4, placing the solid sample subjected to water quenching in the S3 into a ball mill for ball milling treatment;
and S5, grinding the ball-milled sample of S4 by using a sand mill, and finally performing freeze drying to obtain the finished glass powder.
2. The PERC solar cell back silver glass powder and the preparation method thereof according to claim 1, wherein the glass powder comprises the following components in parts by weight: the mass fraction of each component in S1 is Bi 2 O 3 （10~40 wt%）、SiO 2 （10~30 wt%）、Al 2 O 3 （0~10 wt%）、ZnO（0~10 wt%）、V 2 O 5 （5~10 wt%）、CuO（10~20 wt%）、PbO（10~20 wt%）、Fe 2 O 3 (0 to 10 wt.%), and other oxides (0 to 20 wt.%).
3. The PERC solar cell back silver glass powder and the preparation method thereof according to claim 1, wherein the glass powder comprises the following components in parts by weight: the capacity of the crucible in the S2 is 100 to 200 mL, the mixed materials are placed in a ceramic crucible without being covered, the muffle furnace calcination temperature is 1000 to 1300 ℃, the heating rate is 5 to 15 ℃/min, and the calcination time is 30 to 50 min.
4. The PERC solar cell back silver glass powder and the preparation method thereof according to claim 1, wherein the glass powder comprises the following components in parts by weight: and in the S4, the ball milling processing time is 8 to 10 hours, and the rotating speed is 300 to 500 r/min.
5. The PERC solar cell back silver glass powder and the preparation method thereof according to claim 1, wherein the glass powder comprises the following components in parts by weight: the particle size of the finished product glass powder in S5 is 0.5-3 mu m.
6. The high-reliability PERC back silver paste is characterized in that: the high-reliability PERC back silver paste comprises 50-75% of silver powder, 1-3% of glass powder, 30-50% of organic carrier and 1-3% of additive in mass ratio, the organic carrier comprises resin and solvent, and the glass powder is the glass powder in claim 1.
7. The high reliability PERC back silver paste of claim 6, wherein: the silver powder is mixed spherical silver powder with at least two particle diameters, the particle diameter D50 is 0.3-1.0 mu m, and the specific surface area is 1-2 m 2 /g。
8. The highly reliable PERC back silver paste of claim 6, wherein: the resin is at least one of CAB, ethyl cellulose and PVB, and the solvent is at least one of abienol, toluol, butyl carbitol, butyl triethylene glycol butyl ether and alcohol ester twelve.
9. The high reliability PERC back silver paste of claim 6, wherein: the additive is at least one of hydrogenated castor oil, span and BYK-110.
10. A preparation method of high-reliability PERC back silver paste is characterized by comprising the following steps:
(1) Preparing PERC back silver glass powder: adding Bi 2 O 3 、SiO 2 、Al 2 O 3 、ZnO、V 2 O 5 、CuO、MgCO 3 、Na 2 O、PbO、Fe 2 O 3 、CaCO 3 、Sb 2 O 3 、ZrO 2 、CeO 2 At least 6 of the raw materials are fully mixed, calcined at 1000 to 1300 ℃, water-quenched, fully ball-milled for 8 to 10 hours, and then freeze-dried to obtain glass powder;
(2) Preparation of organic vehicle: selecting resin and an organic solvent, and placing the resin and the organic solvent in a stirrer to be stirred for 4 hours at 70 ℃ in a 400r/min stirrer to obtain an organic carrier;
(3) Preparing silver paste with high reliability of PERC back silver: uniformly mixing silver powder, the glass powder prepared in the step (1), the organic carrier prepared in the step (2) and an additive according to the mass ratio of 50-75%: 1-3%: 20-40%: 1-3%, and then grinding by using a three-roll grinder to obtain the silver paste.
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