技术领域technical field
本发明是一种以银为导电介质的导电电子浆料，尤其是一种用于晶硅太阳能电池的水性环保高效导电银浆及其制备方法。The invention relates to a conductive electronic paste using silver as a conductive medium, in particular to a water-based environment-friendly and high-efficiency conductive silver paste used for crystalline silicon solar cells and a preparation method thereof.
背景技术Background technique
目前，现有晶硅太阳能电池生产厂商中应用的导电银浆，品牌型号较多，主要用于电池片的正面和背面导电及焊接组成组件，一般而言，导电银浆本身的成分为：结合有机树脂聚合物、溶剂、导电介质加上适量导电助剂，而现阶段仍然使用的合成树脂为有机溶剂溶解的聚合物，有机溶剂的量在树脂溶液中占有90%或以上（重量份），这与越来越高的环保要求不适应，因为有机溶剂是挥发物质，对人体及环境影响很大，已经被相继立法禁止或减少使用，而正在广泛使用的有机树脂聚合物作为导电银浆的粘结剂，目前被认为有不可替代的性能（附着力优异，有助导电性能、便于施工等特性）表现，所以一直没有办法找到既不含有机挥发物质（VOC）的，也能表现导电银浆性能的聚合物产品作为粘结剂。At present, there are many types of conductive silver pastes used in crystalline silicon solar cell manufacturers, and they are mainly used for conducting and welding components on the front and back of cells. Generally speaking, the composition of conductive silver paste itself is: combined Organic resin polymer, solvent, conductive medium plus an appropriate amount of conductive additives, and the synthetic resin still used at this stage is a polymer dissolved in an organic solvent, and the amount of the organic solvent accounts for 90% or more (parts by weight) of the resin solution. This is not suitable for the increasingly higher environmental protection requirements, because organic solvents are volatile substances that have a great impact on the human body and the environment, and have been banned or reduced by successive legislation, while organic resin polymers that are widely used as conductive silver paste Adhesives are currently considered to have irreplaceable properties (excellent adhesion, conductive properties, easy construction, etc.), so there has been no way to find one that does not contain volatile organic compounds (VOC) and can also perform conductive silver. Polymer products with pulp properties are used as binders.
发明内容Contents of the invention
本发明的目的在于改善银浆的环保性能及提高银浆用于晶硅太阳能电池的转换效率，使用水溶性聚合物生产出不含有机溶剂（VOC）的导电银浆，改善环境，符合环境法规要求，减少对人类健康的影响。The purpose of the present invention is to improve the environmental performance of silver paste and improve the conversion efficiency of silver paste used in crystalline silicon solar cells, use water-soluble polymers to produce conductive silver paste without organic solvents (VOC), improve the environment, and comply with environmental regulations Requirements to reduce the impact on human health.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve its technical problems is:
一种用于晶硅太阳能电池的水性环保高效导电银浆，其特征是，包含以下各组分及其质量百分比含量是：A water-based environment-friendly high-efficiency conductive silver paste for crystalline silicon solar cells is characterized in that it comprises the following components and their mass percentages are:
水溶性纤维素树脂1～10%；Water-soluble cellulose resin 1-10%;
去离子水5～20%；Deionized water 5~20%;
水性表面活性剂0.1～2%；Water-based surfactant 0.1-2%;
酞酸酯偶联剂0.1～2%；Phthalate coupling agent 0.1~2%;
丙三醇1～15%；Glycerol 1-15%;
银粉70～92%；Silver powder 70~92%;
无机粘结料0.1-3.5%。Inorganic binder 0.1-3.5%.
本发明还可以采用以下技术措施解决：The present invention can also adopt the following technical measures to solve:
所述水溶性纤维素树脂是羟丙基纤维素或水溶性丙烯酸树脂或水分散聚氨酯树脂中的其中一种。The water-soluble cellulose resin is one of hydroxypropyl cellulose, water-soluble acrylic resin or water-dispersible polyurethane resin.
所述银粉为球状银粉。The silver powder is spherical silver powder.
所述无机粘结料为玻璃粉或陶瓷粉。The inorganic binder is glass powder or ceramic powder.
本发明另一目的是提供一种制备用于晶硅太阳能电池的水性环保高效导电银浆的方法，其特征是，包括如下步骤：Another object of the present invention is to provide a method for preparing an aqueous environment-friendly high-efficiency conductive silver paste for crystalline silicon solar cells, which is characterized in that it comprises the following steps:
步骤一，将水溶性纤维素树脂与去离子（纯净水）水混合，通过加热至50℃-60℃溶解，静置2～5小时后，密封放置24小时后，得到作为导电银浆的粘结剂，备用；Step 1: Mix the water-soluble cellulose resin with deionized (purified water) water, dissolve it by heating to 50°C-60°C, let it stand for 2-5 hours, and seal it for 24 hours to obtain a conductive silver paste. Binder, spare;
步骤二，利用可加热的搅拌机，将步骤一制得的粘结剂与丙三醇混合搅拌分散，然后一边搅拌一边加入酞酸酯偶联剂后，再一边搅拌一边加入水性表面活性剂后，再加一边搅拌一边入银粉，一边搅拌一边加热持续20-40min，最后再加入无机粘结料，浆体能湿润均匀流动即可停止搅拌，得到浆体；Step 2: Utilize a heatable mixer to mix and disperse the binder prepared in step 1 with glycerol, then add the phthalate coupling agent while stirring, and then add the water-based surfactant while stirring, Add silver powder while stirring, and heat for 20-40 minutes while stirring, and finally add inorganic binder, the slurry can be wet and flow evenly, then stop stirring to obtain the slurry;
步骤三，让浆体自然冷却至常温，转入真空分散机进行脱泡，用0.07~0.09mpa真空度，搅拌速度为200转/min，搅拌脱泡30分钟；Step 3: Allow the slurry to cool naturally to room temperature, transfer to a vacuum disperser for degassing, use a vacuum degree of 0.07~0.09mpa, stir at a speed of 200 rpm, and stir for 30 minutes for degassing;
步骤四，用三辊研磨机研磨细度达到5～7微米的平均粒径，得到成品的导电银浆。Step 4, using a three-roll mill to grind the fineness to an average particle size of 5-7 microns to obtain a finished conductive silver paste.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明的一种用于晶硅太阳能电池的水性环保高效导电银浆及其制备方法，配方中采用羟丙基纤维素，与现有技术使用的乙基纤维素不同，羟丙基纤维素是水溶性高分子聚合物，而乙基纤维素则是油溶性聚合物，但两者干燥后成膜性能相当；而且本发明制得的银浆，可以提高银浆用于晶硅太阳能电池的转换效率，使用水溶性高分子聚合物生产出不含有机溶剂（VOC）的导电银浆，改善环境，符合环境法规要求，减少对人类健康的影响。A kind of water-based environment-friendly high-efficiency conductive silver paste for crystalline silicon solar cells of the present invention and its preparation method, adopt hydroxypropyl cellulose in the formula, different from the ethyl cellulose used in the prior art, hydroxypropyl cellulose is Water-soluble polymers, and ethyl cellulose are oil-soluble polymers, but the film-forming properties of the two are equivalent after drying; and the silver paste prepared by the present invention can improve the conversion of silver paste for crystalline silicon solar cells High efficiency, using water-soluble polymers to produce conductive silver paste without organic solvents (VOC), improving the environment, complying with environmental regulations, and reducing the impact on human health.
具体实施方式detailed description
下面结合实施例对本发明进一步说明。Below in conjunction with embodiment the present invention is further described.
一种用于晶硅太阳能电池的水性环保高效导电银浆，包含以下各组分及其质量百分比含量是：A water-based environment-friendly high-efficiency conductive silver paste for crystalline silicon solar cells, comprising the following components and their mass percentages:
水溶性纤维素树脂2%；Water-soluble cellulose resin 2%;
去离子水5%；Deionized water 5%;
水性表面活性剂0.5%；Water-based surfactant 0.5%;
酞酸酯偶联剂0.5%；Phthalate coupling agent 0.5%;
丙三醇3%；Glycerol 3%;
银粉88%；Silver powder 88%;
无机粘结料1%。Inorganic binder 1%.
所述水溶性纤维素树脂是羟丙基纤维素或水溶性丙烯酸树脂或水分散聚氨酯树脂中的其中一种。The water-soluble cellulose resin is one of hydroxypropyl cellulose, water-soluble acrylic resin or water-dispersible polyurethane resin.
所述银粉为球状银粉。The silver powder is spherical silver powder.
所述无机粘结料为玻璃粉或陶瓷粉。The inorganic binder is glass powder or ceramic powder.
本发明另一目的是提供一种制备用于晶硅太阳能电池的水性环保高效导电银浆的方法，包括如下步骤：Another object of the present invention is to provide a method for preparing an aqueous environment-friendly and efficient conductive silver paste for crystalline silicon solar cells, comprising the steps of:
步骤一，将水溶性纤维素树脂与去离子（纯净水）水混合，通过加热至50℃-60℃溶解，静置2～5小时后，密封放置24小时后，得到作为导电银浆的粘结剂，备用；Step 1: Mix the water-soluble cellulose resin with deionized (purified water) water, dissolve it by heating to 50°C-60°C, let it stand for 2-5 hours, and seal it for 24 hours to obtain a conductive silver paste. Binder, spare;
步骤二，利用可加热的搅拌机，将步骤一制得的粘结剂与丙三醇混合搅拌分散，然后一边搅拌一边加入酞酸酯偶联剂后，再一边搅拌一边加入水性表面活性剂后，再加一边搅拌一边入银粉，一边搅拌一边加热持续20-40min，最后再加入无机粘结料，浆体能湿润均匀流动即可停止搅拌，得到浆体；Step 2: Utilize a heatable mixer to mix and disperse the binder prepared in step 1 with glycerol, then add the phthalate coupling agent while stirring, and then add the water-based surfactant while stirring, Add silver powder while stirring, and heat for 20-40 minutes while stirring, and finally add inorganic binder, the slurry can be wet and flow evenly, then stop stirring to obtain the slurry;
步骤三，让浆体自然冷却至常温，转入真空分散机进行脱泡，用0.07~0.09mpa真空度，搅拌速度为200转/min，搅拌脱泡30分钟；Step 3: Allow the slurry to cool naturally to room temperature, transfer to a vacuum disperser for degassing, use a vacuum degree of 0.07~0.09mpa, stir at a speed of 200 rpm, and stir for 30 minutes for degassing;
步骤四，用三辊研磨机研磨细度达到5～7微米的平均粒径，得到成品的导电银浆。Step 4, using a three-roll mill to grind the fineness to an average particle size of 5-7 microns to obtain a finished conductive silver paste.
成品后，用丝网印刷的方法制作于晶硅太阳能电池产品的正面银线，作为导电线路引导光生电子到相关的设备，具体的使用方法如下：After the finished product is finished, the silver wire on the front side of the crystalline silicon solar cell product is made by screen printing, and used as a conductive line to guide the photo-generated electrons to related equipment. The specific usage method is as follows:
设计好丝网印刷图案并制成网版，选适用的聚酯刮刀，刮印银浆在晶硅电池片的正面，经红外线或热风式加热炉280℃烘烤5分钟，浆料干燥固化成性能优异的导线或网状导线产品，再经820℃高温烧结5秒（此过程用美国BTU烧结炉即可完成整个加工过程），即为晶硅电池片成品。Design a screen printing pattern and make a screen, select a suitable polyester scraper, scrape and print the silver paste on the front of the crystalline silicon cell, and bake it in an infrared or hot air furnace at 280°C for 5 minutes, and the paste is dried and solidified into a The wire or mesh wire products with excellent performance are then sintered at 820°C for 5 seconds (this process can be completed with an American BTU sintering furnace), and the finished crystalline silicon cell is obtained.
通常情况下，选择水溶性树脂对浆料的成膜性影响加大，很难达到其它油溶性树脂（现有技术采用的）的成膜性能，但本技术要点是采用钛酸酯偶联剂作为成膜增强剂，可以达到促进水溶性树脂的成膜强度，同时用了丙三醇作为助溶剂，将水溶性树脂的柔韧性发挥出来；现有技术中水溶性树脂的使用会使表面张力增大，使得浆料用于丝网印刷就会有下墨量不良，形成虚印，同时会影响线条的导电性，本发明的配方加入表面活性剂后，可以将导电银浆的表面张力降低到适合丝网印刷的数值，同时达到了油溶性树脂的表面张力，使丝印性能同样出色。加入导电介质后，水会与银粉的亲和性不好，同样地使用表面活性剂，即可解决该问题。这几个配方上的改进使有机聚合物与无机导电介质结合紧密，在印刷后，加热固化的过程中，有机大分子收缩固化，将导电粉体介质捕获，紧密粘结在一起，同时粘附在晶硅电池产品底材上，形成牢固的整体，最后经过高温烧结，分解了有机物，包括水溶性树脂成膜物，留下玻璃粉或陶瓷粉作为高温熔融后粘结在晶硅太阳能电池片上的无机粘结料，与银粉形成一个整体，作为导线。Under normal circumstances, the choice of water-soluble resin has a greater impact on the film-forming properties of the slurry, and it is difficult to achieve the film-forming properties of other oil-soluble resins (used in the prior art), but the key point of this technology is to use titanate coupling agent As a film-forming enhancer, it can promote the film-forming strength of water-soluble resins, and at the same time, glycerol is used as a cosolvent to bring out the flexibility of water-soluble resins; the use of water-soluble resins in the prior art will make the surface tension If the paste is used for screen printing, the amount of ink will be poor, forming a false print, and will affect the conductivity of the line. After the surfactant is added to the formula of the present invention, the surface tension of the conductive silver paste can be reduced. It reaches the value suitable for screen printing, and at the same time reaches the surface tension of oil-soluble resin, so that the screen printing performance is also excellent. After adding a conductive medium, the affinity between water and silver powder is not good, and the same problem can be solved by using a surfactant. Improvements in these formulas make the organic polymer and the inorganic conductive medium tightly combined. After printing, during the heating and curing process, the organic macromolecules shrink and solidify, capture the conductive powder medium, and stick together tightly. On the substrate of crystalline silicon solar cell products, a solid whole is formed, and finally sintered at high temperature to decompose organic matter, including water-soluble resin film-forming substances, leaving glass powder or ceramic powder as high-temperature melting and bonding on crystalline silicon solar cells The inorganic binder, and the silver powder form a whole, as a wire.
以上所述的具体实施例，仅为本发明较佳的实施例而已，举凡依本发明申请专利范围所做的等同设计，均应为本发明的技术所涵盖。The specific embodiments described above are only preferred embodiments of the present invention, and all equivalent designs made according to the patent scope of the present invention should be covered by the technology of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510873694.4ACN105551568A (en) | 2015-12-03 | 2015-12-03 | Water-based environmental efficient conductive silver paste for crystalline silicon solar cells and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
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| CN201510873694.4ACN105551568A (en) | 2015-12-03 | 2015-12-03 | Water-based environmental efficient conductive silver paste for crystalline silicon solar cells and preparation method thereof |
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| CN105551568Atrue CN105551568A (en) | 2016-05-04 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201510873694.4APendingCN105551568A (en) | 2015-12-03 | 2015-12-03 | Water-based environmental efficient conductive silver paste for crystalline silicon solar cells and preparation method thereof |
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