CN102701595B - A kind of lead-free glass powder and preparation method thereof - Google Patents
A kind of lead-free glass powder and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域 technical field
本发明涉及一种无铅玻璃粉及其制备方法，特别是用于太阳能电池正面电子浆料，属于玻璃粉及太阳能电池领域。 The invention relates to a lead-free glass powder and a preparation method thereof, in particular to the front electronic paste of solar cells, and belongs to the field of glass powder and solar cells.
背景技术 Background technique
随着全球经济的迅速发展，能源消耗以惊人的速度增大，世界已探明的主要矿物燃料储存量和开采量不容乐观，因此对新能源的开发利用已经成为迫在眉睫的重中之重。这也正给新能源的开发与利用提供了一个很广阔的市场，太阳能电池产业正以其强大的优势和前景占领着市场的主要份额。目前太阳能电池市场主要以硅太阳能电池为主。 With the rapid development of the global economy, energy consumption is increasing at an alarming rate, and the world's proven storage and mining of major fossil fuels are not optimistic. Therefore, the development and utilization of new energy has become an urgent priority. This is also providing a very broad market for the development and utilization of new energy. The solar cell industry is occupying a major share of the market with its strong advantages and prospects. At present, the solar cell market is mainly dominated by silicon solar cells.
在硅太阳能电池的制备过程中，将银导电浆料印刷在涂有减反膜的硅基片上，形成栅极，用来形成电池片间串并联引线电机并提高电池的转换率。 In the preparation process of silicon solar cells, the silver conductive paste is printed on the silicon substrate coated with anti-reflection film to form a grid, which is used to form a series-parallel lead motor between cells and improve the conversion rate of the cell.
银浆主要由银粉、玻璃粉、有机溶剂及其一些添加剂组成。玻璃粉的作用很重要，玻璃粉在热处理时熔化，将硅表面太阳光减反射层融化，使浆料中的银可以与硅面接触，同时玻璃粘结剂将金属粉末附着在硅片表面，形成致密均匀的导电膜。 Silver paste is mainly composed of silver powder, glass powder, organic solvent and some additives. The role of glass powder is very important. The glass powder melts during heat treatment and melts the solar anti-reflection layer on the silicon surface so that the silver in the paste can contact the silicon surface. At the same time, the glass binder attaches the metal powder to the surface of the silicon wafer. Form a dense and uniform conductive film.
目前市场上的太阳能银浆主要为含铅银浆，因为无铅玻璃粉的熔点高，但硅太阳能电池的烧结曲线周期短，一般无铅玻璃粉不能在极短的时间内熔融。同时含铅浆料还对环境造成大量的污染，不符合如今的环保理念。所以研制出太阳能电子浆料用无铅玻璃粉迫在眉睫。 The solar silver paste currently on the market is mainly lead-containing silver paste, because lead-free glass powder has a high melting point, but the sintering curve cycle of silicon solar cells is short, and generally lead-free glass powder cannot be melted in a very short time. At the same time, the lead-containing slurry also causes a large amount of pollution to the environment, which does not conform to today's environmental protection concept. Therefore, it is imminent to develop lead-free glass powder for solar electronic paste.
市场上现有的无铅玻璃粉，如Na-Ca系和钒玻璃等。相比较，本发明的Bi-B-Si系无铅玻璃粉具有更低的软化温度；烧结后可获得更加高的附着力，并且保证银电极与硅基片有良好的接触。 The existing lead-free glass powder on the market, such as Na-Ca series and vanadium glass. In comparison, the Bi-B-Si lead-free glass powder of the present invention has a lower softening temperature; after sintering, it can obtain higher adhesion and ensure good contact between the silver electrode and the silicon substrate.
发明内容 Contents of the invention
本发明提供一种无铅玻璃粉，解决现有技术中无铅玻璃粉的软化温度高，熔化温度高等问题。该玻璃粉的软化温度低，膨胀系数适宜，制的银浆后，烧结在硅基片上可获得良好的附着力，并使得银电极与硅基片有良好的接触。 The invention provides a lead-free glass powder, which solves the problems of high softening temperature and high melting temperature of the lead-free glass powder in the prior art. The glass powder has a low softening temperature and a suitable expansion coefficient. After the silver paste is prepared, it can be sintered on the silicon substrate to obtain good adhesion and make the silver electrode and the silicon substrate have good contact.
为实现上述目的，本发明的技术方案为：无铅玻璃粉的成分及质量百分比为：Bi2O3 30～50%，B2O3 10～40%，SiO2 1～10%，Al2O3 3～10%，ZnO 5～8%，TiO2 1～5%，MgO 1～5%，NaF 1～3%，MnO2 1～3%，SnO2 1～4%，SrCl2 0～2%。将无铅玻璃粉成分配料的混合料加热保温熔融后水淬，然后再进行球磨，最终制得无铅玻璃粉。具体制备步骤包括如下： In order to achieve the above object, the technical solution of the present invention is: the composition and mass percentage of the lead-free glass powder are: Bi 2 O 3 30-50%, B 2 O 3 10-40%, SiO 2 1-10%, Al 2 O 3 3～10%, ZnO 5～8%, TiO 2 1～5%, MgO 1～5%, NaF 1～3%, MnO 2 1～3%, SnO 2 1～4%, SrCl 2 0～ 2%. The mixture of lead-free glass powder ingredients is heated, kept and melted, quenched in water, and then ball-milled to finally obtain lead-free glass powder. Concrete preparation steps include as follows:
（1）按无铅玻璃粉的成分及质量百分比进行混合配料，加热保温使混合料充分熔融成玻璃液； (1) Mix ingredients according to the composition and mass percentage of lead-free glass powder, heat and keep warm to fully melt the mixture into glass liquid;
（2）将玻璃液倒入水中水淬，使其快速冷却形成玻璃颗粒； (2) Pour the molten glass into water and quench it to make it cool rapidly to form glass particles;
（3）将玻璃颗粒球磨成玻璃粉，即得到太阳能电池正面电子浆料用无铅玻璃粉。 (3) The glass particles are ball-milled into glass powder to obtain the lead-free glass powder for the front electronic paste of the solar cell.
所述步骤（1）的混料加热是从室温升温，800℃以前升温速度为5～8℃/min，800℃以后升温速度为3～5℃/min至1100℃～1300℃保温60～120分钟。 The heating of the mixture in the step (1) is to raise the temperature from room temperature, the heating rate is 5-8 °C/min before 800 °C, and the heating rate is 3-5 °C/min after 800 °C, and the temperature is kept at 1100 °C-1300 °C for 60-120 °C. minute.
所述玻璃颗粒球磨后的玻璃粉的粒径为1μm～5μm。 The particle size of the glass powder after the ball milling of the glass particles is 1 μm˜5 μm.
所述配制混合料使用的Bi2O3、B2O3、SiO2、Al2O3、ZnO、TiO2、MgO、NaF、MnO2、SnO2和SrCl2均为普通市售粉末，纯度为99.9wt%以上。 The Bi 2 O 3 , B 2 O 3 , SiO 2 , Al 2 O 3 , ZnO, TiO 2 , MgO, NaF, MnO 2 , SnO 2 and SrCl 2 used in the preparation of the mixture are all commercially available powders with a purity of It is more than 99.9wt%.
本发明的原理为：B2O3是玻璃中的主要玻璃形成剂，在玻璃中以层状结构存在，硼的加入可以降低软化温度和膨胀系数，使玻璃的化学性质稳定。 The principle of the present invention is: B 2 O 3 is the main glass-forming agent in glass, which exists in a layered structure in glass, adding boron can reduce softening temperature and expansion coefficient, and stabilize the chemical properties of glass.
铋与铅在元素周期表上处在相邻的位置，原子量相近，原子半径相差不大，二者电子能级相近，铋和铅都促进玻璃太的形成，所以，理论上Bi是代替Pb的最佳元素。随着Bi2O3含量的增加，[BO3]三角体被打破，[BiO4]四面体结果增多。由于外加氧化物的断键作用，使得[BO3]和[BiO4]为主的玻璃结构被弱化，玻璃的特征温度显著降低。 Bismuth and lead are in adjacent positions on the periodic table of the elements, with similar atomic weights and little difference in atomic radius. The electronic energy levels of the two are similar. Both bismuth and lead promote the formation of glass, so Bi is theoretically a substitute for Pb. best element. With the increase of Bi 2 O 3 content, [BO 3 ] triangles are broken and [BiO 4 ] tetrahedrons increase. Due to the bond breaking effect of the added oxide, the glass structure dominated by [BO 3 ] and [BiO 4 ] is weakened, and the characteristic temperature of the glass is significantly lowered.
SiO2和Al2O3的加入可以降低玻璃的析晶倾向，同时提高玻璃的化学稳定性，并且可以调节玻璃的线性膨胀系数。 The addition of SiO 2 and Al 2 O 3 can reduce the crystallization tendency of the glass, improve the chemical stability of the glass at the same time, and can adjust the linear expansion coefficient of the glass.
ZnO的加入可以增加玻璃的化学稳定性，同时降低玻璃的膨胀系数。 The addition of ZnO can increase the chemical stability of the glass while reducing the expansion coefficient of the glass.
本发明的优点和积极效果： Advantage and positive effect of the present invention:
（1）本发明的无铅玻璃粉与硅基片有较高的附着力和适宜的线性膨胀系数70×10-7/℃～78×10-7/℃，球磨后可得超细玻璃粉，与银粉、硅基片有良好的浸润性，浆料烧结时可有效穿透烧结膜与硅基片有良好的欧姆接触，可以取代传统的无铅玻璃粉，制备出无铅太阳能电子浆料； (1) The lead-free glass powder of the present invention has high adhesion to silicon substrates and a suitable linear expansion coefficient of 70×10 -7 /℃～78×10 -7 /℃, and ultrafine glass powder can be obtained after ball milling , has good wettability with silver powder and silicon substrate. When the paste is sintered, it can effectively penetrate the sintered film and have good ohmic contact with the silicon substrate. It can replace the traditional lead-free glass powder and prepare lead-free solar electronic paste. ;
（2）本发明最终得到软化温度最低可以达到为420℃，软化温度低于一般的玻璃粉，有利于玻璃粉在烧结的时候熔融充分包裹银颗粒，使银颗粒的导电网络更致密，导电性能更好； (2) The minimum softening temperature obtained by the present invention can reach 420°C, and the softening temperature is lower than that of ordinary glass powder, which is beneficial for the glass powder to melt and fully wrap the silver particles during sintering, so that the conductive network of the silver particles is denser and the conductive performance is improved. better;
（3）本发明得到的无铅玻璃粉化学性质稳定，烧结温度范围宽500℃～900℃，烧结后与硅基片的附着力为2.6 N～5.8 N。 (3) The chemical properties of the lead-free glass powder obtained in the present invention are stable, the sintering temperature range is wide from 500°C to 900°C, and the adhesion to the silicon substrate after sintering is 2.6 N to 5.8 N.
具体实施方式 Detailed ways
以下结合实施例对本发明作进一步描述，但本发明不限于以下所述范围。 The present invention will be further described below in conjunction with the examples, but the present invention is not limited to the scope described below.
实施例1：本发明制备的无铅玻璃粉具体成分为：Bi2O3 35%，B2O3 30%，SiO2 2.5%，Al2O3 10%，ZnO 8%，TiO2 2%，MgO 4%，NaF 1%，MnO2 3%，SnO2 2%，SrCl2 1%。 Example 1: The specific composition of the lead-free glass powder prepared by the present invention is: Bi 2 O 3 35%, B 2 O 3 30%, SiO 2 2.5%, Al 2 O 3 10%, ZnO 8%, TiO 2 2% , MgO 4%, NaF 1%, MnO 2 3%, SnO 2 2%, SrCl 2 1%.
本发明的无铅玻璃粉的制备方法如下： The preparation method of lead-free glass powder of the present invention is as follows:
（1）按上述无铅玻璃粉的成分及质量百分比进行混合配料，加热保温使混合料充分熔融成玻璃液；加热速率是从室温升温，800℃以前升温速度为5℃/min，800℃以后升温速度为3℃/min至1100℃保温120分钟。 (1) Mix ingredients according to the composition and mass percentage of the above-mentioned lead-free glass powder, heat and keep warm to fully melt the mixture into glass liquid; the heating rate is from room temperature to 5°C/min before 800°C, and after 800°C The heating rate is 3°C/min to 1100°C for 120 minutes.
（2）将玻璃液倒入去离子水中水淬，使其快速冷却形成玻璃颗粒； (2) Pour the glass liquid into deionized water and quench it to make it cool rapidly to form glass particles;
（3）将玻璃颗粒球磨成粒径为1μm～2μm的玻璃粉，即得到太阳能电池正面电子浆料用无铅玻璃粉。 (3) The glass particles are ball-milled into glass powder with a particle size of 1 μm to 2 μm to obtain lead-free glass powder for solar cell front electronic paste.
所得太阳能电池正面电子浆料用玻璃粉的软化温度420℃，烧结后与硅基片的附着力为3.8N。 The softening temperature of the obtained glass frit for the front electronic paste of the solar cell is 420° C., and the adhesion to the silicon substrate after sintering is 3.8N.
实施例2：本发明制备的无铅玻璃粉具体成分为：Bi2O3 50%，B2O3 10%，SiO2 10%，Al2O3 8%，ZnO 6%，TiO2 1%，MgO 1%，NaF 3%，MnO2 2%，SnO2 1%。 Example 2: The specific composition of the lead-free glass powder prepared by the present invention is: Bi 2 O 3 50%, B 2 O 3 10%, SiO 2 10%, Al 2 O 3 8%, ZnO 6%, TiO 2 1% , MgO 1%, NaF 3%, MnO 2 2%, SnO 2 1%.
本发明的无铅玻璃粉的制备方法如下： The preparation method of lead-free glass powder of the present invention is as follows:
（1）按上述无铅玻璃粉的成分及质量百分比进行混合配料，加热保温使混合料充分熔融成玻璃液；加热速率是从室温升温，800℃以前升温速度为6℃/min，800℃以后升温速度为4℃/min至1200℃保温60分钟。 (1) Mix the ingredients according to the composition and mass percentage of the above-mentioned lead-free glass powder, heat and keep warm to fully melt the mixture into glass liquid; the heating rate is from room temperature to 6 °C/min before 800 °C, and after 800 °C The heating rate is 4°C/min to 1200°C for 60 minutes.
（2）将玻璃液倒入去离子水中水淬，使其快速冷却形成玻璃颗粒； (2) Pour the glass liquid into deionized water and quench it to make it cool rapidly to form glass particles;
（3）将玻璃颗粒球磨成粒径为3μm～5μm的玻璃粉，即得到太阳能电池正面电子浆料用无铅玻璃粉。 (3) The glass particles are ball-milled into glass powder with a particle size of 3 μm to 5 μm to obtain the lead-free glass powder for the front electronic paste of the solar cell.
所得太阳能电池正面电子浆料用玻璃粉的软化温度483℃，烧结后与硅基片的附着力为3.6N。 The softening temperature of the obtained glass frit for the front electronic paste of the solar cell is 483°C, and the adhesion force to the silicon substrate after sintering is 3.6N.
实施例3：本发明制备的无铅玻璃粉具体成分为：Bi2O3 30%，B2O3 40%，SiO2 1%，Al2O3 3%，ZnO 5%，TiO2 5%，MgO 5%，NaF 2%，MnO2 1%，SnO2 4%，SrCl2 2%。 Example 3: The specific composition of the lead-free glass powder prepared by the present invention is: Bi 2 O 3 30%, B 2 O 3 40%, SiO 2 1%, Al 2 O 3 3%, ZnO 5%, TiO 2 5% , MgO 5%, NaF 2%, MnO 2 1%, SnO 2 4%, SrCl 2 2%.
本发明的无铅玻璃粉的制备方法如下： The preparation method of lead-free glass powder of the present invention is as follows:
（1）按上述无铅玻璃粉的成分及质量百分比进行混合配料，加热保温使混合料充分熔融成玻璃液；加热速率是从室温升温，800℃以前升温速度为8℃/min，800℃以后升温速度为5℃/min至1300℃保温80分钟。 (1) Mix ingredients according to the composition and mass percentage of the above-mentioned lead-free glass powder, heat and keep warm to fully melt the mixture into glass liquid; the heating rate is from room temperature to 8°C/min before 800°C, and after 800°C The heating rate is 5°C/min to 1300°C for 80 minutes.
（2）将玻璃液倒入去离子水中水淬，使其快速冷却形成玻璃颗粒； (2) Pour the glass liquid into deionized water and quench it to make it cool rapidly to form glass particles;
（3）将玻璃颗粒球磨成粒径为2μm～4μm的玻璃粉，即得到太阳能电池正面电子浆料用无铅玻璃粉。 (3) The glass particles are ball-milled into glass powder with a particle size of 2 μm to 4 μm to obtain the lead-free glass powder for the front electronic paste of the solar cell.
所得太阳能电池正面电子浆料用玻璃粉的软化温度487℃，烧结后与硅基片的附着力为3.3N。 The softening temperature of the obtained glass frit for solar cell front electronic paste is 487° C., and the adhesion force to the silicon substrate after sintering is 3.3N.
实施例4：本发明制备的无铅玻璃粉具体成分为：Bi2O3 40%，B2O3 20%，SiO2 10%，Al2O3 3%，ZnO 5%，TiO2 3%，MgO 5%，NaF 2%，MnO2 1%，SnO2 4%，SrCl2 2%。 Example 4: The specific composition of the lead-free glass powder prepared by the present invention is: Bi 2 O 3 40%, B 2 O 3 20%, SiO 2 10%, Al 2 O 3 3%, ZnO 5%, TiO 2 3% , MgO 5%, NaF 2%, MnO 2 1%, SnO 2 4%, SrCl 2 2%.
本发明的无铅玻璃粉的制备方法如下： The preparation method of lead-free glass powder of the present invention is as follows:
（1）按上述无铅玻璃粉的成分及质量百分比进行混合配料，加热保温使混合料充分熔融成玻璃液；加热速率是从室温升温，800℃以前升温速度为7℃/min，800℃以后升温速度为4℃/min至1220℃保温90分钟。 (1) Mix ingredients according to the composition and mass percentage of the above-mentioned lead-free glass powder, heat and keep warm to fully melt the mixture into glass liquid; the heating rate is from room temperature to 7 °C/min before 800 °C, and after 800 °C The heating rate is 4°C/min to 1220°C for 90 minutes.
（2）将玻璃液倒入去离子水中水淬，使其快速冷却形成玻璃颗粒； (2) Pour the glass liquid into deionized water and quench it to make it cool rapidly to form glass particles;
（3）将玻璃颗粒球磨成粒径为1μm～4μm的玻璃粉，即得到太阳能电池正面电子浆料用无铅玻璃粉。 (3) The glass particles are ball-milled into glass powder with a particle size of 1 μm to 4 μm to obtain the lead-free glass powder for the front electronic paste of the solar cell.
所得太阳能电池正面电子浆料用玻璃粉的软化温度439℃，烧结后与硅基片的附着力为3.3N。 The softening temperature of the obtained glass frit for the front electronic paste of the solar cell is 439° C., and the adhesion to the silicon substrate after sintering is 3.3N.
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| CN105347688A (en) * | 2015-12-14 | 2016-02-24 | 周妙思 | Preparation method of glass powder for electronic paste |
| CN105502952A (en) * | 2015-12-14 | 2016-04-20 | 周妙思 | Glass powder |
| CN105741907B (en) * | 2016-04-26 | 2017-07-07 | 江阴市天邦涂料股份有限公司 | A kind of unleaded silver paste used for solar batteries |
| CN105679410B (en) * | 2016-04-26 | 2017-02-15 | 江阴市天邦涂料股份有限公司 | High-adhesion-stability silver-aluminum slurry for solar battery |
| CN105810759B (en) * | 2016-04-26 | 2017-07-25 | 江阴市天邦涂料股份有限公司 | A kind of silver-aluminum paste for solar cell |
| CN107151099A (en) * | 2017-06-16 | 2017-09-12 | 北京市合众创能光电技术有限公司 | A kind of preparation method of conductive silver paste lead-free glass powder |
| CN110240414A (en) * | 2019-07-02 | 2019-09-17 | 黄山市晶特美新材料有限公司 | Acidproof environmentally friendly glass powder with low melting point of one kind and preparation method thereof |
| CN112551904A (en) * | 2020-12-18 | 2021-03-26 | 中国振华集团云科电子有限公司 | Acid-resistant glass powder for end coating of silver paste and preparation method thereof |
| CN115215544B (en) * | 2022-07-25 | 2023-07-25 | 昆明理工大学 | A semiconductor laser-induced color-changing lead-free glass and its preparation method and application |
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