WO2022217832A1 - Silver paste for heterojunction cell, preparation method therefor, and application thereof - Google Patents
Silver paste for heterojunction cell, preparation method therefor, and application thereof Download PDFInfo
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- WO2022217832A1 WO2022217832A1 PCT/CN2021/118930 CN2021118930W WO2022217832A1 WO 2022217832 A1 WO2022217832 A1 WO 2022217832A1 CN 2021118930 W CN2021118930 W CN 2021118930W WO 2022217832 A1 WO2022217832 A1 WO 2022217832A1
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- silver
- parts
- powder
- resin
- paste
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 130
- 239000004332 silver Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 229920001225 polyester resin Polymers 0.000 claims abstract description 11
- 239000004645 polyester resin Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 3
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- -1 silica modified phenolic resin Chemical group 0.000 claims description 11
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 10
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000006229 carbon black Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention relates to the technical field of solar cells. Disclosed in the present invention are a silver paste for a heterojunction solar cell, a method for preparing the silver paste, and the application thereof. The silver paste for a heterojunction cell of the present invention contains the following ingredients in parts by weight: 16-95 parts of silver powder, 15- 85 parts of silver-coated copper powder, 1-5 parts of resin A, 0.1-2 parts of a curing agent, 0.05-0.5 parts of a promoter, 0.5-1.5 parts of a dispersing agent, and 0.5-1.5 parts of resin B. The resin A contains at least one of a polyester resin and an epoxy resin. The resin B is a white carbon black modified phenolic resin. By means of the present invention, the ingredients of a silver paste and the quantities of the ingredients are selected, such that an open-circuit voltage Voc of a cell sheet using the paste is greater than or equal to 745 mV, the photoelectric conversion efficiency of a cell is greater than or equal to 23.7%, and the series resistance Rs is less than or equal to 2.4 mΩ. The volume resistivity of the paste is less than or equal to 8x10-6Ω·cm. In addition, the paste has good cohesiveness and abrasion resistance, such that by means of replacing some silver powder with silver-coated copper powder, the production cost of the silver paste is greatly reduced without a loss in electrical performance.
Description
本发明涉及太阳能电池技术领域，尤其涉及一种异质结电池用银浆及其制备方法与应用。The invention relates to the technical field of solar cells, in particular to a silver paste for heterojunction cells and a preparation method and application thereof.
传统异质结太阳能电池的主栅和细栅为同种浆料，主栅需要具有良好的焊接拉力，而细栅需要具有较低的接触电阻，两者较难达到平衡，因此，现有异质结太阳能电池的电性能相对来说较为普通。此外，现有技术采用的银浆为全银粉银浆，银耗量大，成本高，银浆的成本占电池总成本的30％以上，这使得异质结电池尚不具备成本优势，距离规模化推广还有一定距离。The busbar and fine grid of traditional heterojunction solar cells are of the same paste, the busbar needs to have good welding tension, while the fine grid needs to have low contact resistance, and it is difficult to achieve a balance between the two. The electrical properties of mass junction solar cells are relatively common. In addition, the silver paste used in the prior art is an all-silver powder silver paste, which consumes a large amount of silver and has a high cost. The cost of the silver paste accounts for more than 30% of the total cost of the battery, which makes the heterojunction battery still do not have the cost advantage, and the distance scale There is still a certain distance to promote.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服上述现有技术的不足之处而提供一种具有良好电性能、成本低、粘结性好的异质结电池用银浆及其制备方法与应用。本发明单独对细栅进行研究，专注于改善细栅的接触电阻和体积电阻率，提升异质结电池的电性能。The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a silver paste for heterojunction batteries with good electrical properties, low cost and good cohesiveness, and a preparation method and application thereof. The present invention conducts research on the fine grid alone, focusing on improving the contact resistance and volume resistivity of the fine grid, and improving the electrical performance of the heterojunction battery.
为实现上述目的，本发明所采取的技术方案为：一种异质结电池用银浆，包含如下重量份的成分：银粉16～95份、银包铜粉15～85份、树脂A 1～5份、固化剂0.1～2份、促进剂0.05～0.5份、分散剂0.5～1.5份和树脂B 0.5～1.5份；所述树脂A包含聚酯树脂、环氧树脂中的至少一种；所述树脂B为白炭黑改性酚醛树脂。In order to achieve the above purpose, the technical scheme adopted in the present invention is: a kind of silver paste for heterojunction battery, comprising the following components by weight: 16-95 parts of silver powder, 15-85 parts of silver-coated copper powder, 1- 5 parts, 0.1-2 parts of curing agent, 0.05-0.5 part of accelerator, 0.5-1.5 part of dispersant, and 0.5-1.5 part of resin B; the resin A comprises at least one of polyester resin and epoxy resin; The resin B is a silica modified phenolic resin.
本发明以银包铜粉替代部分银粉，极大地降低了银浆的成本。铜粉具有良好的导电性，成本较低，但其抗氧化性较差，以银粉包覆铜粉可避免铜粉的氧化，同时能保证银包铜粉具有良好的导电性。采用白炭黑改性酚醛树脂可以增强固化后银浆和电池基底的附着能力，减少接触电阻，提升电性能。白炭黑的 表面的Si-OH基团具有很强的活性，微粒表层活性大，易于与周围离子键合；而白炭黑粒子表面的活性羟基可与有机大分子链上的少量羟基发生化学反应形成化学键，或与有机大分子链上的氢形成氢键；此外，白炭黑粒子间的相互作用、白炭黑-聚合物-白炭黑与白炭黑聚集体间的“桥”链构成了空间网络结构，白炭黑充当了扩链剂和交联剂。The invention replaces part of the silver powder with silver-coated copper powder, which greatly reduces the cost of silver paste. Copper powder has good electrical conductivity and low cost, but its oxidation resistance is poor. Coating copper powder with silver powder can avoid oxidation of copper powder, and at the same time can ensure that silver-coated copper powder has good conductivity. The use of silica modified phenolic resin can enhance the adhesion between the cured silver paste and the battery substrate, reduce contact resistance, and improve electrical performance. The Si-OH groups on the surface of silica particles have strong activity, and the surface layer of the particles is highly active and easy to bond with surrounding ions; while the active hydroxyl groups on the surface of silica particles can chemically react with a small amount of hydroxyl groups on the organic macromolecular chain. Reaction to form chemical bonds, or hydrogen bonds with hydrogen on organic macromolecular chains; in addition, the interaction between silica particles, the "bridge" chain between silica-polymer-silica and silica aggregates Constituting a spatial network structure, silica acts as a chain extender and a crosslinking agent.
优选地，所述银粉包含如下重量份的成分：片状银粉5～35份、纳米银粉1～10份和球形银粉10～50份；所述银包铜粉包含如下重量份的成分：球形银包铜粉10～50份和片状银包铜粉5～35份。Preferably, the silver powder comprises the following components 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 by weight: spherical silver powder 10-50 parts of copper-coated powder and 5-35 parts of flake silver-coated copper powder.
本发明通过将片状银粉、纳米银粉和球形银粉混合使用，使得整个体系具有较小的体积电阻率率。片状银粉呈片式结构排列，颗粒间流动性较好；片状银粉填充率较大，总收缩量小，利于提升银浆烧结后的致密性。但片状银粉的粒径较大，丝网印刷过程中很难过网，同时由于片状银粉与硅基之间的接触电阻较差，所以还需要球形银粉的加入来弥补，球形银粉反应活性高，可以与硅基形成良好的紧密的物理接触减少浆料和硅基之间的接触电阻。球形银粉和纳米银粉可以填充片状银粉之间的空隙，使原来的不接触的相邻银片相互接触，增加了导电通路，或者使银浆中形成更多的并联导电通路。In the present invention, the flake silver powder, the nanometer silver powder and the spherical silver powder are mixed and used, so that the whole system has a smaller volume resistivity. The flaky silver powder is arranged in a flaky structure, and the fluidity between particles is good; the filling rate of the flaky silver powder is large, and the total shrinkage is small, which is beneficial to improve the compactness of the silver paste after sintering. However, the particle size of the flake silver powder is large, and it is difficult to pass through the screen during the screen printing process. At the same time, due to the poor contact resistance between the flake silver powder and the silicon base, the spherical silver powder needs to be added to make up for it, and the spherical silver powder has high reactivity. , which can form a good close physical contact with the silicon substrate to reduce the contact resistance between the paste and the silicon substrate. The spherical silver powder and nano-silver powder can fill the gaps between the flake silver powders, making the original non-contact adjacent silver flakes contact each other, increasing the conductive path, or forming more parallel conductive paths in the silver paste.
优选地，所述银粉包含如下重量份的成分：片状银粉15～30份、纳米银粉5～8份和球形银粉20～35份；所述银包铜粉包含如下重量份的成分：球形银包铜粉15～35份和片状银包铜粉5～20份。Preferably, the silver powder contains the following components 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 contains the following components by weight: spherical silver powder 15-35 parts of copper-coated powder and 5-20 parts of flake silver-coated copper powder.
本发明申请人对不同银粉和银包铜粉的含量进行选择，使得按上述配比复配后的银浆具有最优的电性能。The applicant of the present invention selects the contents of different silver powders and silver-coated copper powders, so that the silver paste compounded according to the above-mentioned proportions has optimal electrical properties.
优选地，所述片状银粉的径厚比为5～20；所述纳米银粉的粒度为30～100nm；所述球形银粉的D50粒径为1～5μm；所述银包铜粉中银含量为15～25wt.％；所述球形银包铜粉的D50粒径为0.5～3.5μm；所述片状银包铜粉的振实密度为2～2.2g/cm
3，D50粒径为1～8μm。银包铜粉中银的含量太高，成本下降则微乎其微，银的含量过低，则包覆的银层太薄，被包覆的铜粉易被氧化。本发明申请人经多次试验证实，当银包铜粉中银含量为15～25wt.％时，具有最优的综合性能。
Preferably, the diameter-to-thickness ratio of the flake silver powder is 5-20; the particle size of the nano-silver powder is 30-100 nm; the D50 particle size of the spherical silver powder is 1-5 μm; the silver content in the silver-coated copper powder is 15-25wt.%; the D50 particle size of the spherical silver-coated copper powder is 0.5-3.5 μm; the tap density of the flake silver-coated copper powder is 2-2.2g/cm 3 , and the D50 particle size is 1- 8μm. If the content of silver in the silver-coated copper powder is too high, the cost reduction will be minimal. If the content of silver is too low, the coated silver layer will be too thin, and the coated copper powder will be easily oxidized. The applicant of the present invention has confirmed by many tests that when the silver content in the silver-coated copper powder is 15-25 wt.%, it has the best comprehensive performance.
优选地，所述固化剂包含异氰酸酯类固化剂、氨基树脂类固化剂中的至少一种；所述促进剂包含环烷酸钴、环烷酸铅中的至少一种。Preferably, the curing agent includes at least one of isocyanate curing agent and amino resin curing agent; and the accelerator includes at least one of cobalt naphthenate and lead naphthenate.
此外，本发明还公开了一种异质结电池用银浆的制备方法，所述方法为：将银粉、银包铜粉加入混料机中，再加入树脂A、固化剂、促进剂、分散剂、树脂B，以混料机混合均匀，再经三辊研磨机进行研磨，松轧1次，紧轧3次，再松轧2次，得到所述异质结电池用银浆。In addition, the present invention also discloses a preparation method of silver paste for heterojunction battery, the method is as follows: adding silver powder and silver-coated copper powder into a mixer, then adding resin A, curing agent, accelerator, dispersion The agent and resin B were mixed uniformly with a mixer, then ground by a three-roll mill, loosened once, squeezed 3 times, and loosened twice to obtain the silver paste for the heterojunction battery.
同时，本发明还公开了所述异质结电池用银浆在异质结电池中的应用方法，将所述银浆通过丝网印刷涂覆于异质结电池上，烘干、固化。At the same time, the invention also discloses an application method of the silver paste for the heterojunction battery in the heterojunction battery. The silver paste is coated on the heterojunction battery by screen printing, dried and cured.
优选地，所述烘干温度为180～220℃，烘干时间为5～10min；所述固化温度为180～200℃，固化时间为10～20min。Preferably, the drying temperature is 180-220°C, and the drying time is 5-10 minutes; the curing temperature is 180-200°C, and the curing time is 10-20 minutes.
相比于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明通过对银粉及银包铜粉的种类和含量进行选择，使用白炭黑改性的酚醛树脂，使得制备出的银浆具有良好的电性能，将银浆印刷到电池片上，所产生的开路电压Voc≥745mV，电池的光电转换效率≥23.7％，串联电阻Rs≤2.4mΩ；所述浆料的体积电阻率≤8×10
-6Ω·cm；并且所述浆料具有良好的粘结性和耐磨性，3M胶撕拉不掉粉，耐刮擦次数≥40次；通过以银包铜粉代替部分银粉，在不损失电性能的情况下，极大地降低了银浆的生产成本。
The present invention selects the type and content of silver powder and silver-coated copper powder, and uses phenolic resin modified by white carbon black, so that the prepared silver paste has good electrical properties, and the silver paste is printed on the battery sheet. The open circuit voltage Voc≥745mV, the photoelectric conversion efficiency of the battery is ≥23.7%, the series resistance Rs≤2.4mΩ; the volume resistivity of the paste is less than or equal to 8×10 -6 Ω·cm; and the paste has good adhesion 3M glue can not tear off the powder, and the number of scratches is more than 40 times; by replacing part of the silver powder with silver-coated copper powder, the production cost of silver paste is greatly reduced without losing electrical properties. .
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments.
实施例1Example 1
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉25份、平均粒径为65nm的纳米银粉7份、D50粒径为2.5μm的球形银粉32份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉20份、银含量为20wt.％、D50粒径为5μm的片状 银包铜粉10份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 25 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size of 7 parts of nano silver powder with diameter of 65nm, 32 parts of spherical silver powder with D50 particle size of 2.5μm, silver content of 20wt.%, D50 particle size of 2μm spherical silver-coated copper powder 20 parts, silver content of 20wt.%, D50 Add 10 parts of flake silver-coated copper powder with a particle size of 5 μm into the mixer kettle, then add 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, and 1 dispersant 1 part of silica modified phenolic resin, mixed evenly with a mixer, then entered into a three-roll mill, loosened once, rolled 3 times, and loosened twice to obtain the heterostructure Silver paste for batteries.
实施例2Example 2
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉15份、平均粒径为65nm的纳米银粉8份、D50粒径为2.5μm的球形银粉35份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉35份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉5份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 15 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size 8 parts of nano silver powder with diameter of 65nm, 35 parts of spherical silver powder with D50 particle size of 2.5μm, silver content of 20wt.%, 35 parts of spherical silver-coated copper powder with D50 particle diameter of 2μm, silver content of 20wt.%, D50 Add 5 parts of flake silver-coated copper powder with a particle size of 5 μm into the mixer kettle, then add 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, and 1 part of dispersant 1 part of silica modified phenolic resin, mixed evenly with a mixer, then entered into a three-roll mill, loosened once, rolled 3 times, and loosened twice to obtain the heterostructure Silver paste for batteries.
实施例3Example 3
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉30份、平均粒径为65nm的纳米银粉5份、D50粒径为2.5μm的球形银粉20份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉15份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉20份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 30 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size of 5 parts of nano silver powder with diameter of 65nm, 20 parts of spherical silver powder with D50 particle size of 2.5μm, silver content of 20wt.%, D50 particle size of 2μm spherical silver-coated copper powder 15 parts, silver content of 20wt.%, D50 20 parts of flake silver-coated copper powder with a particle size of 5μm was added to the 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, and 1 dispersant were added. 1 part of silica modified phenolic resin, mixed evenly with a mixer, then entered into a three-roll mill, loosened once, rolled 3 times, and loosened twice to obtain the heterostructure Silver paste for batteries.
实施例4Example 4
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉5份、平均粒径为65nm的纳米银粉1份、D50粒径为2.5μm的球形银粉50份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉10份、银含量为20wt.％、D50粒径为5μm的片状 银包铜粉35份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 5 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size of 1 part of nano silver powder with diameter of 65nm, 50 parts of spherical silver powder with D50 particle size of 2.5μm, silver content of 20wt.%, 10 parts of spherical silver-coated copper powder with D50 particle size of 2μm, silver content of 20wt.%, D50 35 parts of flake silver-coated copper powder with a particle size of 5 μm was added to the 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, and 1 dispersant were added. 1 part of silica modified phenolic resin, mixed evenly with a mixer, then entered into a three-roll mill, loosened once, rolled 3 times, and loosened twice to obtain the heterostructure Silver paste for batteries.
实施例5Example 5
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉35份、平均粒径为65nm的纳米银粉10份、D50粒径为2.5μm的球形银粉10份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉50份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉5份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 35 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size of 10 parts of nano silver powder with diameter of 65nm, 10 parts of spherical silver powder with D50 particle size of 2.5μm, silver content of 20wt.%, 50 parts of spherical silver-coated copper powder with D50 particle size of 2μm, silver content of 20wt.%, D50 Add 5 parts of flake silver-coated copper powder with a particle size of 5 μm into the mixer kettle, then add 3 parts of polyester resin, 1 part of curing agent, 0.05 part of cobalt naphthenate, 0.3 part of lead naphthenate, and 1 part of dispersant 1 part of silica modified phenolic resin, mixed evenly with a mixer, then entered into a three-roll mill, loosened once, rolled 3 times, and loosened twice to obtain the heterostructure Silver paste for batteries.
实施例6Example 6
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将D50粒径为5μm的径厚比为5的片状银粉60份、平均粒径为65nm的纳米银粉7份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉20份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉10份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 60 parts of flake silver powder with a D50 particle size of 5 μm and a diameter-to-thickness ratio of 5, an average particle size of 7 parts of nano silver powder with diameter of 65nm, silver content of 20wt.%, D50 particle size of 2μm spherical silver-coated copper powder 20 parts, silver content of 20wt.%, D50 particle size of 5μm flake silver-coated copper powder 10 Add 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 dispersant, and 1 part of silica modified phenolic resin, The mixture is uniformly mixed with a mixer, and then entered into a three-roll mill, loosely rolled once, tightly rolled for 3 times, and loosely rolled for 2 times to obtain the silver paste for the heterojunction battery.
实施例7Example 7
本发明所述异质结电池用银浆的一种实施例，本实施例所述银浆的制备方法为：将平均粒径为65nm的纳米银粉7份、D50粒径为2.5μm的球形银粉57份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉20份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉10份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、白炭黑改性酚 醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。An embodiment of the silver paste for heterojunction batteries of the present invention, the preparation method of the silver paste in this embodiment is as follows: 7 parts of nano silver powder with an average particle size of 65nm and spherical silver powder with a D50 particle size of 2.5μm 57 parts, silver content of 20wt.%, D50 particle size of 2μm spherical silver-coated copper powder 20 parts, silver content of 20wt.%, D50 particle size of 5μm flake silver-coated copper powder 10 parts into the mixer kettle Inside, add 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 dispersant, and 1 part of silica modified phenolic resin, and mix it with a mixer. Mix evenly, then enter into a three-roll mill, loosen-roll once, tighten-roll 3 times, and loosen-roll 2 times to obtain the silver paste for a heterojunction battery.
对比例1Comparative Example 1
一种银浆，其制备方法为：将D50粒径为5μm的径厚比为5的片状银粉25份、平均粒径为65nm的纳米银粉7份、D50粒径为2.5μm的球形银粉32份、银含量为20wt.％、D50粒径为2μm的球形银包铜粉20份、银含量为20wt.％、D50粒径为5μm的片状银包铜粉10份加入混料机釜内，再加入聚酯树脂3份、固化剂1份、环烷酸钴0.05份、环烷酸铅0.3份、分散剂1份、酚醛树脂1份，以混料机将其混合均匀，再进入三辊研磨机，松轧1次、紧轧3次，再松轧2次，得到所述异质结电池用银浆。A silver paste, the preparation method of which is as follows: 25 parts of flake silver powder with a diameter-to-thickness ratio of 5 with a D50 particle size of 5 μm, 7 parts of nano-silver powder with an average particle size of 65 nm, and 32 parts of spherical silver powder with a D50 particle size of 2.5 μm 20 parts of spherical silver-coated copper powder with a silver content of 20wt.% and a D50 particle size of 2μm, 10 parts of flake silver-coated copper powder with a silver content of 20wt.% and a D50 particle size of 5μm into the mixer kettle , and then add 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 dispersant, and 1 part of phenolic resin, mix them evenly with a mixer, and then enter the three parts. Roll mill, loose rolling 1 time, tight rolling 3 times, and loose rolling 2 times to obtain the silver paste for the heterojunction battery.
性能测试Performance Testing
1)分别测量实施例1～7和对比例1制备的银浆的体积电阻率，测试结果如表1所示。1) Measure the volume resistivity of the silver pastes prepared in Examples 1 to 7 and Comparative Example 1 respectively, and the test results are shown in Table 1.
2)将实施例1～7和对比例1制备的异质结电池用银浆分别通过丝网印刷涂覆于晶体硅异质结电池上，再于200℃干燥8min、200℃固化20min，随后测量电池的光电转换效率、开路电压、串联电阻，并用3M胶撕拉浆料，观察是否掉粉，并对浆料的耐磨性(刮擦次数)进行评估，耐磨性测试方法为：将浆料均匀涂布在基片上，电极厚度≤25μm，按照工艺条件固化后，选用底部是光滑圆形(直径为1mm)的摩擦棒，在电极表面，来回往复摩擦测试，观察电极表面的变化直至出现脱落，记录摩擦次数，次数越多，说明耐磨性能越好。测试结果如表1所示。2) The silver pastes for heterojunction cells prepared in Examples 1 to 7 and Comparative Example 1 were respectively coated on the crystalline silicon heterojunction cells by screen printing, dried at 200 °C for 8 min, cured at 200 °C for 20 min, and then Measure the photoelectric conversion efficiency, open circuit voltage, series resistance of the battery, and tear the slurry with 3M glue to observe whether the powder falls off, and evaluate the abrasion resistance (scratch times) of the slurry. The abrasion resistance test method is: The slurry is evenly coated on the substrate, and the thickness of the electrode is ≤25μm. After curing according to the process conditions, a friction rod with a smooth circular bottom (diameter of 1mm) is selected. If it falls off, record the friction times. The more times, the better the wear resistance. The test results are shown in Table 1.
表1性能测试结果Table 1 Performance test results
从表1中可知，实施例1～5所述银浆的综合性能最好，既具有良好的电性能，同时粘结性及耐磨性也较好，而实施例6～7中均只含有球形银粉、片状银粉和纳米银粉中的两种，导电性比实施例1～5差，但仍然具有较好的粘结性能和耐磨性。对比例1使用的是未改性的酚醛树脂，虽然电性能较好，但耐磨性明显差于实施例1～7，无法长期使用。It can be seen from Table 1 that the silver pastes described in Examples 1-5 have the best comprehensive properties, not only have good electrical properties, but also have good adhesion and wear resistance, while Examples 6-7 only contain Two of the spherical silver powder, the flake silver powder and the nanometer silver powder have worse electrical conductivity than Examples 1 to 5, but still have good bonding performance and wear resistance. Comparative example 1 uses unmodified phenolic resin, although the electrical properties are good, but the abrasion resistance is obviously worse than that of examples 1-7, and it cannot be used for a long time.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，但并不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
- 一种异质结电池用银浆，其特征在于，包含如下重量份的成分：银粉16～95份、银包铜粉15～85份、树脂A 1～5份、固化剂0.1～2份、促进剂0.05～0.5份、分散剂0.5～1.5份和树脂B 0.5～1.5份；所述树脂A包含聚酯树脂、环氧树脂中的至少一种；所述树脂B为白炭黑改性酚醛树脂。A silver paste for a heterojunction battery, characterized in that it comprises the following components by weight: 16-95 parts of silver powder, 15-85 parts of silver-coated copper powder, 1-5 parts of resin A, 0.1-2 parts of curing agent, 0.05-0.5 part of accelerator, 0.5-1.5 part of dispersant and 0.5-1.5 part of resin B; the resin A includes at least one of polyester resin and epoxy resin; the resin B is silica modified phenolic resin.
- 如权利要求1所述的异质结电池用银浆，其特征在于，所述银粉包含如下重量份的成分：片状银粉5～35份、纳米银粉1～10份和球形银粉10～50份；所述银包铜粉包含如下重量份的成分：球形银包铜粉10～50份和片状银包铜粉5～35份。The silver paste for a heterojunction battery according to claim 1, wherein the silver powder comprises the following components 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 flake silver-coated copper powder.
- 如权利要求2所述的异质结电池用银浆，其特征在于，所述银粉包含如下重量份的成分：片状银粉15～30份、纳米银粉5～8份和球形银粉20～35份；所述银包铜粉包含如下重量份的成分：球形银包铜粉15～35份和片状银包铜粉5～20份。The silver paste for a heterojunction battery according to claim 2, wherein the silver powder comprises the following components 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 flake silver-coated copper powder.
- 如权利要求2所述的异质结电池用银浆，其特征在于，所述片状银粉的径厚比为5～20；所述纳米银粉的粒度为30～100nm；所述球形银粉的D50粒径为1～5μm；所述银包铜粉中银含量为15～25wt.％；所述球形银包铜粉的D50粒径为0.5～3.5μm；所述片状银包铜粉的振实密度为2～2.2g/cm 3，D50粒径为1～8μm。 The silver paste for a heterojunction battery according to claim 2, wherein the diameter-to-thickness ratio of the flake silver powder is 5-20; the particle size of the nano-silver powder is 30-100 nm; the D50 of the spherical silver powder is 30-100 nm. The particle size is 1-5 μm; the silver content 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 μm; The density is 2 to 2.2 g/cm 3 , and the D50 particle size is 1 to 8 μm.
- 如权利要求1所述的异质结电池用银浆，其特征在于，所述固化剂包含异氰酸酯类固化剂、氨基树脂类固化剂中的至少一种；所述促进剂包含环烷酸钴、环烷酸铅中的至少一种。The silver paste for a heterojunction battery 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 accelerator comprises cobalt naphthenate, At least one of lead naphthenate.
- 一种如权利要求1～5任一项所述的异质结电池用银浆的制备方法，其特征在于，所述方法为：将银粉、银包铜粉加入混料机中，再加入树脂A、固化剂、促进剂、分散剂、树脂B，以混料机混合均匀，再经三辊研磨机进行研磨，轧制，得到所述异质结电池用银浆。A method for preparing silver paste for heterojunction batteries according to any one of claims 1 to 5, wherein the method is: adding silver powder and silver-coated copper powder into a mixer, and then adding resin A. The curing agent, the accelerator, the dispersant, and the resin B are mixed uniformly with a mixer, then ground and rolled by a three-roll mill to obtain the silver paste for heterojunction batteries.
- 一种如权利要求1～5任一项所述的异质结电池用银浆在异质结电池中的 应用方法，其特征在于，将所述银浆通过丝网印刷涂覆于异质结电池上，烘干、固化。A method for applying a silver paste for a heterojunction battery in a heterojunction battery according to any one of claims 1 to 5, wherein the silver paste is coated on the heterojunction cell by screen printing On the battery, dry and cure.
- 如权利要求7所述的异质结电池用银浆在异质结电池中的应用方法，其特征在于，烘干温度为180～220℃，烘干时间为5～10min；固化温度为180～200℃，固化时间为10～20min。The method for applying silver paste for a heterojunction battery in a heterojunction battery according to claim 7, wherein the drying temperature is 180-220° C., the drying time is 5-10 min, and the curing temperature is 180-220° C. 200℃, the curing time is 10-20min.
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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 |
| CN116913576A (en) * | 2023-07-10 | 2023-10-20 | 乐凯胶片股份有限公司 | Conductive paste and heterojunction solar cell |
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