CN113284644B - Silver paste for heterojunction battery and preparation method and application thereof - Google Patents

Silver paste for heterojunction battery and preparation method and application thereof Download PDF

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CN113284644B
CN113284644B CN202110397851.4A CN202110397851A CN113284644B CN 113284644 B CN113284644 B CN 113284644B CN 202110397851 A CN202110397851 A CN 202110397851A CN 113284644 B CN113284644 B CN 113284644B
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silver
parts
powder
resin
coated copper
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CN113284644A (en
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丁冰冰
黄淑枚
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WUXI RUXING TECHNOLOGY DEVELOPMENT CO LTD
Guangzhou Ruxing Technology Development Co ltd
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WUXI RUXING TECHNOLOGY DEVELOPMENT CO LTD
Guangzhou Ruxing Technology Development Co ltd
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Priority to PCT/CN2021/118930 priority patent/WO2022217832A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The invention discloses a special templateSilver paste for a mass junction battery and a preparation method and application thereof relate to the technical field of solar batteries. The silver paste for the heterojunction battery comprises the following components in parts by weight: 16 to 95 portions of silver powder, 15 to 85 portions of silver-coated copper powder, 1 to 5 portions of resin A, 0.1 to 2 portions of curing agent, 0.05 to 0.5 portion of accelerant, 0.5 to 1.5 portions of dispersant and 0.5 to 1.5 portions of resin B; the resin A comprises at least one of polyester resin and epoxy resin; and the resin B is white carbon black modified phenolic resin. According to the invention, the components and the content of the silver paste are selected, so that the open-circuit voltage Voc of a battery piece using the paste is more than or equal to 745mV, the photoelectric conversion efficiency of the battery is more than or equal to 23.7%, and the series resistance Rs is less than or equal to 2.4m omega; the volume resistivity of the slurry is less than or equal to 8 multiplied by 10 ‑6 Omega.cm; the silver paste has good cohesiveness and wear resistance, and the production cost of the silver paste is greatly reduced by replacing part of silver powder with the silver-coated copper powder under the condition of not losing electrical property.

Description

Silver paste for heterojunction battery and preparation method and application thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to silver paste for a heterojunction cell and a preparation method and application thereof.
Background
The main grid and the fine grid of the traditional heterojunction solar cell are made of the same slurry, the main grid needs to have good welding tension, the fine grid needs to have lower contact resistance, and the main grid and the fine grid are difficult to balance. In addition, the silver paste adopted in the prior art is full-silver powder silver paste, the silver consumption is large, the cost is high, and the cost of the silver paste accounts for more than 30% of the total cost of the battery, so that the heterojunction battery does not have the cost advantage, and has a certain distance from large-scale popularization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the silver paste for the heterojunction battery, which has good electrical property, low cost and good cohesiveness, and the preparation method and the application thereof. According to the invention, the fine grid is independently researched, so that the contact resistance and the volume resistivity of the fine grid are improved, and the electrical property of the heterojunction cell is improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the silver paste for the heterojunction battery comprises the following components in parts by weight: 16 to 95 portions of silver powder, 15 to 85 portions of silver-coated copper powder, 1 to 5 portions of resin A, 0.1 to 2 portions of curing agent, 0.05 to 0.5 portion of accelerant, 0.5 to 1.5 portions of dispersant and 0.5 to 1.5 portions of resin B; the resin A comprises at least one of polyester resin and epoxy resin; and the resin B is white carbon black modified phenolic resin.
According to the invention, silver-coated copper powder is used for replacing part of silver powder, so that the cost of silver paste is greatly reduced. The copper powder has good conductivity and low cost, but the oxidation resistance of the copper powder is poor, the silver powder is coated on the copper powder, so that the copper powder can be prevented from being oxidized, and meanwhile, the silver-coated copper powder can be ensured to have good conductivity. The white carbon black modified phenolic resin can enhance the adhesive capacity of the cured silver paste and the battery substrate, reduce contact resistance and improve electrical performance. Si-OH groups on the surface of the white carbon black have strong activity, and the surface layer of the particles has high activity and is easy to bond with peripheral ions; the active hydroxyl on the surface of the white carbon black particle can react with a small amount of hydroxyl on the organic macromolecular chain to form a chemical bond or form a hydrogen bond with hydrogen on the organic macromolecular chain; in addition, the interaction between the white carbon black particles and the bridge chain between the white carbon black-polymer-white carbon black and the white carbon black aggregate form a space network structure, and the white carbon black is used as a chain extender and a cross-linking agent.
Preferably, the silver powder comprises the following components in parts by weight: 5-35 parts of flake silver powder, 1-10 parts of nano silver powder and 10-50 parts of spherical silver powder; the silver-coated copper powder comprises the following components in parts by weight: 10-50 parts of spherical silver-coated copper powder and 5-35 parts of flaky silver-coated copper powder.
According to the invention, the flake silver powder, the nano silver powder and the spherical silver powder are mixed for use, so that the whole system has a relatively low volume resistivity. The flaky silver powder is arranged in a flaky structure, and the flowability among particles is good; the filling rate of the flake silver powder is high, the total shrinkage is small, and the compactness of the silver paste after sintering is improved. However, the flaky silver powder has a large particle size, and is difficult to screen in the screen printing process, and meanwhile, because the contact resistance between the flaky silver powder and the silicon substrate is poor, the spherical silver powder needs to be added for compensation, has high reaction activity, and can form good close physical contact with the silicon substrate to reduce the contact resistance between the slurry and the silicon substrate. The gaps between the flake silver powder can be filled with the spherical silver powder and the nanometer silver powder, so that the original non-contact adjacent silver flakes are contacted with each other, the conductive paths are increased, or more parallel conductive paths are formed in the silver paste.
Preferably, the silver powder comprises the following components in parts by weight: 15-30 parts of flake silver powder, 5-8 parts of nano silver powder and 20-35 parts of spherical silver powder; the silver-coated copper powder comprises the following components in parts by weight: 15-35 parts of spherical silver-coated copper powder and 5-20 parts of flaky silver-coated copper powder.
The applicant selects the contents of different silver powder and silver-coated copper powder, so that the silver paste compounded according to the proportion has optimal electrical property.
Preferably, the ratio of the diameter to the thickness of the flake silver powder is 5 to 20; the particle size of the nano silver powder is 30-100 nm; the D50 particle size of the spherical silver powder is 1-5 mu m; the content of silver in the silver-coated copper powder is 15-25 wt.%; the D50 particle size of the spherical silver-coated copper powder is 0.5-3.5 mu m; the tap density of the flake silver-coated copper powder is 2-2.2 g/cm 3 And the D50 particle size is 1-8 μm. The silver content in the silver-coated copper powder is too high, the cost is reduced very little, and the silver content is too low, so that the coated silver layer is too thin, and the coated copper powder is easy to oxidize. The applicant of the invention has verified through a plurality of tests that the silver-coated copper powder has the optimal comprehensive performance when the silver content is 15-25 wt.%.
Preferably, the curing agent comprises at least one of isocyanate curing agent and amino resin curing agent; the accelerant comprises at least one of cobalt naphthenate and lead naphthenate.
In addition, the invention also discloses a preparation method of the silver paste for the heterojunction battery, which comprises the following steps: adding silver powder and silver-coated copper powder into a mixer, adding resin A, a curing agent, an accelerator, a dispersant and resin B, uniformly mixing by using the mixer, grinding by using a three-roll grinder, loosely rolling for 1 time, tightly rolling for 3 times, and loosely rolling for 2 times to obtain the silver paste for the heterojunction battery.
Meanwhile, the invention also discloses an application method of the silver paste for the heterojunction battery in the heterojunction battery, and the silver paste is coated on the heterojunction battery through screen printing, dried and cured.
Preferably, the drying temperature is 180-220 ℃, and the drying time is 5-10 min; the curing temperature is 180-200 ℃, and the curing time is 10-20 min.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the types and contents of silver powder and silver-coated copper powder are selected, and the phenolic resin modified by white carbon black is used, so that the prepared silver paste has good electrical property, the silver paste is printed on a battery piece, the generated open-circuit voltage Voc is not less than 745mV, the photoelectric conversion efficiency of the battery is not less than 23.7%, and the series resistance Rs is not more than 2.4m omega; the volume resistivity of the slurry is less than or equal to 8 multiplied by 10 -6 Omega cm; the slurry has good cohesiveness and wear resistance, the 3M glue does not fall off after being torn and pulled, and the scraping-resistant times are more than or equal to 40 times; by replacing part of silver powder with the silver-coated copper powder, the production cost of the silver paste is greatly reduced under the condition of not losing electrical property.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In an embodiment of the silver paste for the heterojunction battery, a preparation method of the silver paste of this embodiment includes: adding 25 parts of flaky silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 micrometers, 7 parts of nano silver powder with the average particle diameter of 65nm, 32 parts of spherical silver powder with the D50 particle diameter of 2.5 micrometers, 20 parts of spherical silver-coated copper powder with the silver content of 20wt.%, 20 parts of spherical silver-coated copper powder with the D50 particle diameter of 2 micrometers, and 10 parts of flaky silver-coated copper powder with the silver content of 20wt.% and the D50 particle diameter of 5 micrometers into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin, uniformly mixing by using a mixer, feeding into a grinding machine, and carrying out loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times to obtain the three-roller silver paste for the heterojunction battery.
Example 2
In an embodiment of the silver paste for the heterojunction battery, a preparation method of the silver paste of this embodiment includes: adding 15 parts of flaky silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 micrometers, 8 parts of nano silver powder with the average particle diameter of 65nm, 35 parts of spherical silver powder with the D50 particle diameter of 2.5 micrometers, 35 parts of spherical silver-coated copper powder with the silver content of 20wt.%, 35 parts of spherical silver-coated copper powder with the D50 particle diameter of 2 micrometers, and 5 parts of flaky silver-coated copper powder with the silver content of 20wt.% and the D50 particle diameter of 5 micrometers into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin, uniformly mixing by using a mixer, feeding into a grinding machine, and carrying out loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times to obtain the three-roller silver paste for the heterojunction battery.
Example 3
In an embodiment of the silver paste for the heterojunction battery of the present invention, the preparation method of the silver paste of this embodiment is: 30 parts of flake silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 mu m, 5 parts of nano silver powder with the average particle diameter of 65nm, 20 parts of spherical silver powder with the D50 particle diameter of 2.5 mu m, 15 parts of spherical silver-coated copper powder with the silver content of 20 wt%, and 20 parts of flake silver-coated copper powder with the D50 particle diameter of 5 mu m are added into a mixer kettle, and then 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin are added into the mixer kettle, and the mixture is uniformly mixed by a mixer and then enters a three-roll grinder to be subjected to loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times to obtain the silver paste for the heterojunction battery.
Example 4
In an embodiment of the silver paste for the heterojunction battery, a preparation method of the silver paste of this embodiment includes: 5 parts of flake silver powder with the diameter-thickness ratio of 5D 50 particle size of 5 microns, 1 part of nano silver powder with the average particle size of 65nm, 50 parts of spherical silver powder with the D50 particle size of 2.5 microns, 10 parts of spherical silver-coated copper powder with the silver content of 20 wt%, and 10 parts of flake silver-coated copper powder with the D50 particle size of 2 microns, and 35 parts of flake silver-coated copper powder with the silver content of 20 wt% and the D50 particle size of 5 microns are added into a mixer kettle, and then 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin are added into the mixer kettle and uniformly mixed, and then the mixture enters a three-roll grinder to be subjected to loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times, so that the silver paste for the heterojunction battery is obtained.
Example 5
In an embodiment of the silver paste for the heterojunction battery, a preparation method of the silver paste of this embodiment includes: adding 35 parts of flaky silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 micrometers, 10 parts of nano silver powder with the average particle diameter of 65nm, 10 parts of spherical silver powder with the D50 particle diameter of 2.5 micrometers, 50 parts of spherical silver-coated copper powder with the silver content of 20 wt%, and 5 parts of flaky silver-coated copper powder with the D50 particle diameter of 5 micrometers into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin, uniformly mixing the materials by using a mixer, feeding the mixture into a three-roll grinder, and carrying out loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times to obtain the silver paste for the heterojunction battery.
Example 6
In an embodiment of the silver paste for the heterojunction battery of the present invention, the preparation method of the silver paste of this embodiment is: adding 60 parts of flake silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 microns, 7 parts of nano silver powder with the average particle diameter of 65nm, 20 wt% of silver, 20 parts of spherical silver-coated copper powder with the D50 particle diameter of 2 microns, 20 wt% of silver and 10 parts of flake silver-coated copper powder with the D50 particle diameter of 5 microns into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin, uniformly mixing the materials by using a mixer, feeding the mixture into a three-roll grinder, carrying out loose rolling for 1 time and tight rolling for 3 times, and carrying out loose rolling for 2 times to obtain the silver paste for the heterojunction battery.
Example 7
In an embodiment of the silver paste for the heterojunction battery of the present invention, the preparation method of the silver paste of this embodiment is: adding 7 parts of nano silver powder with the average particle size of 65nm, 57 parts of spherical silver powder with the D50 particle size of 2.5 microns, 20 parts of spherical silver-coated copper powder with the silver content of 20wt.%, 20 parts of spherical silver-coated copper powder with the D50 particle size of 2 microns, 10 parts of flake silver-coated copper powder with the silver content of 20wt.% and the D50 particle size of 5 microns into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of white carbon black modified phenolic resin, uniformly mixing by using a mixer, feeding into a three-roll grinder, loosely rolling for 1 time, tightly rolling for 3 times, and loosely rolling for 2 times to obtain the heterogeneous battery silver paste.
Comparative example 1
The preparation method of the silver paste comprises the following steps: adding 25 parts of flaky silver powder with the diameter-thickness ratio of 5 and the D50 particle diameter of 5 micrometers, 7 parts of nano silver powder with the average particle diameter of 65nm, 32 parts of spherical silver powder with the D50 particle diameter of 2.5 micrometers, 20 parts of spherical silver-coated copper powder with the silver content of 20 wt%, 20 parts of flaky silver-coated copper powder with the D50 particle diameter of 2 micrometers, and 10 parts of flaky silver-coated copper powder with the silver content of 20 wt% and the D50 particle diameter of 5 micrometers into a mixer kettle, adding 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, 1 part of dispersing agent and 1 part of phenolic resin, uniformly mixing the materials by using a mixer, feeding the mixture into a grinding machine, and carrying out loose rolling for 1 time, tight rolling for 3 times and loose rolling for 2 times to obtain the silver paste for the heterojunction battery.
Performance testing
1) The volume resistivity of the silver pastes prepared in examples 1 to 7 and comparative example 1 were measured, respectively, and the test results are shown in table 1.
2) The silver pastes for the heterojunction cells prepared in the embodiments 1 to 7 and the comparative example 1 are respectively coated on the crystalline silicon heterojunction cell by screen printing, then dried at 200 ℃ for 8min and cured at 200 ℃ for 20min, then the photoelectric conversion efficiency, the open-circuit voltage and the series resistance of the cell are measured, the 3M glue is used for tearing the paste, whether powder falling occurs or not is observed, and the abrasion resistance (scraping times) of the paste is evaluated, wherein the abrasion resistance test method comprises the following steps: uniformly coating the slurry on a substrate, wherein the thickness of an electrode is less than or equal to 25 micrometers, curing according to process conditions, selecting a friction rod with a smooth and round bottom (the diameter is 1 mm), performing a reciprocating friction test on the surface of the electrode, observing the change of the surface of the electrode until the electrode falls off, recording the friction times, and indicating that the wear resistance is better when the times are more. The test results are shown in table 1.
Table 1 results of performance testing
Figure BDA0003017640080000061
Figure BDA0003017640080000071
As can be seen from table 1, the silver pastes described in examples 1 to 5 have the best overall properties, and have good electrical properties, and good adhesion and abrasion resistance, while examples 6 to 7, which all contain only two of the spherical silver powder, the flake silver powder and the nano silver powder, have poorer electrical conductivity than examples 1 to 5, but still have good adhesion and abrasion resistance. Comparative example 1 used an unmodified phenol resin, which had better electrical properties, but had significantly poorer abrasion resistance than examples 1 to 7, and could not be used for a long period of time.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (7)

1. The silver paste for the heterojunction battery is characterized by comprising the following components in parts by weight: 16 to 95 portions of silver powder, 15 to 85 portions of silver-coated copper powder, 1 to 5 portions of resin A, 0.1 to 2 portions of curing agent, 0.05 to 0.5 portion of accelerant, 0.5 to 1.5 portions of dispersant and 0.5 to 1.5 portions of resin B; the resin A comprises at least one of polyester resin and epoxy resin; the resin B is white carbon black modified phenolic resin;
the silver powder comprises the following components in parts by weight: 15-35 parts of flake silver powder, 5-10 parts of nano silver powder and 10-35 parts of spherical silver powder; the silver-coated copper powder comprises the following components in parts by weight: 15-50 parts of spherical silver-coated copper powder and 5-20 parts of flaky silver-coated copper powder.
2. The silver paste for the heterojunction battery according to claim 1, wherein the silver powder comprises the following components in parts by weight: 15-30 parts of flake silver powder, 5-8 parts of nano silver powder and 20-35 parts of spherical silver powder; the silver-coated copper powder comprises the following components in parts by weight: 15-35 parts of spherical silver-coated copper powder and 5-20 parts of flaky silver-coated copper powder.
3. The silver paste for a heterojunction battery according to claim 1, wherein the flake silver powder has a aspect ratio of 5 to 20; the particle size of the nano silver powder is 30-100 nm; the D50 particle size of the spherical silver powder is 1-5 mu m; the content of silver in the silver-coated copper powder is 15-25 wt.%; the D50 particle size of the spherical silver-coated copper powder is 0.5-3.5 mu m; the tap density of the flake silver-coated copper powder is 2-2.2 g/cm 3 And the D50 particle size is 1-8 μm.
4. The silver paste for a heterojunction cell according to claim 1, wherein the curing agent comprises at least one of an isocyanate-based curing agent and an amino resin-based curing agent; the accelerant comprises at least one of cobalt naphthenate and lead naphthenate.
5. The preparation method of the silver paste for the heterojunction battery as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: adding silver powder and silver-coated copper powder into a mixer, adding resin A, a curing agent, an accelerator, a dispersant and resin B, uniformly mixing by using the mixer, grinding by using a three-roll grinder, and rolling to obtain the silver paste for the heterojunction battery.
6. The application method of the silver paste for the heterojunction cell as claimed in any one of claims 1 to 4 in the heterojunction cell is characterized in that the silver paste is coated on the heterojunction cell by screen printing, dried and cured.
7. The application method of the silver paste for the heterojunction battery in the heterojunction battery as claimed in claim 6, wherein the drying temperature is 180-220 ℃, and the drying time is 5-10 min; the curing temperature is 180-200 ℃, and the curing time is 10-20 min.
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CN114999707A (en) * 2022-07-07 2022-09-02 江苏日御光伏新材料科技有限公司 HJT silver paste and application thereof
CN116060610B (en) * 2023-03-07 2023-10-20 东方电气集团科学技术研究院有限公司 Silver-coated copper powder and preparation method and application thereof
CN116709667B (en) * 2023-06-30 2024-01-19 常州海弘电子有限公司 Silver paste hole filling process method for circuit board
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