WO2019056418A1 - 用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池 - Google Patents

用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池 Download PDF

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WO2019056418A1
WO2019056418A1 PCT/CN2017/105867 CN2017105867W WO2019056418A1 WO 2019056418 A1 WO2019056418 A1 WO 2019056418A1 CN 2017105867 W CN2017105867 W CN 2017105867W WO 2019056418 A1 WO2019056418 A1 WO 2019056418A1
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solar cell
glass frit
electrode
paste composition
teo
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PCT/CN2017/105867
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English (en)
French (fr)
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崔永郁
史卫利
张洪旺
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无锡帝科电子材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic 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
    • 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

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  • the present invention relates to the field of solar cell manufacturing technology, and in particular to a glass powder for preparing solar cell electrodes, a paste composition including the same, a solar cell electrode, and a solar cell.
  • Solar cells use the photovoltaic effect to convert the photons of sunlight into electricity through the p-n junction.
  • a front electrode and a rear electrode are respectively formed on upper and lower surfaces of a semiconductor wafer or substrate having a p-n junction. Then, the photoelectric effect of the p-n junction is induced by sunlight entering the semiconductor wafer, and electrons generated by the photoelectric effect of the p-n junction supply current to the outside through the electrode.
  • the composition for the electrode is placed on the wafer, patterned and baked to form an electrode of the solar cell.
  • the uppermost anti-reflective layer of the solar cell is a layer of silicon nitride.
  • the front electrode of the solar cell needs the glass frit component therein to etch away this layer of silicon nitride to conduct the current generated by the lower emitter.
  • the solar cells are connected to each other by a bonding tape to form a solar cell module.
  • insufficient adhesion between solar cell electrodes and electrodes and solder ribbons made of a typical component including a lead-containing glass powder and a solder strip resulting in a large series resistance of conversion efficiency and Reduced conversion efficiency.
  • the invention aims to provide a glass powder for preparing a solar cell electrode, a paste composition comprising the same, a solar cell electrode and a solar cell, so as to solve the problem of insufficient adhesion between the solar cell electrode and the solder ribbon in the prior art.
  • the low adhesion between the electrode and the ribbon causes a technical problem of high series resistance and deterioration of conversion efficiency.
  • a glass frit for preparing a solar cell electrode comprises 1.0 wt% to 90.0 wt% of lead oxide, 1.0 wt% to 90.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O, and the lead oxide is PbO and/or Pb 3 O 4 .
  • the mole percentage of TeO 2 in the glass frit is less than 35%.
  • the glass frit contains 1.0 wt% to 90.0 wt% of lead oxide, 1.0 wt% to 50.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O.
  • the glass frit contains 1.0 wt% to 50.0 wt% of lead oxide, 1.0 wt% to 45.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O.
  • the mole percentage of TeO 2 in the glass frit is less than 35%.
  • the glass frit further contains other oxides selected from the group consisting of Na 2 O, K 2 O, MgO, CaO, SrO, BaO, Bi 2 O 3 , P 2 O 5 , SiO 2 , B 2 O 3 .
  • the content of other oxides is from 1 to 25% by weight of the glass powder.
  • the glass powder has an average particle diameter D50 of 0.1 to 10 ⁇ m.
  • a paste composition for preparing a solar cell electrode contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • the conductive powder is silver powder.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the paste composition of the present invention can reduce the adverse effect of high surface resistance on the pn junction while reducing the contact resistance, thereby improving the efficiency of the solar cell and improving the performance of the electrode fabricated therefrom; the paste of the present invention
  • the solar cell electrodes prepared by the composition, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
  • FIG. 1 shows a schematic view of a solar cell fabricated using a paste composition in accordance with an embodiment of the present invention.
  • a glass frit for preparing a solar cell electrode comprises 1.0 wt% to 90.0 wt% of lead oxide, 1.0 wt% to 90.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O, and the lead oxide is PbO and/or Pb 3 O 4 .
  • PbO is a component which lowers the softening point of glass, and is a component which can be sintered at low temperature in a glass frit composition.
  • the bismuth glass has a low melting point, is highly durable, and easily dissolves silver in a solid solution.
  • Lithium oxide is called a low-resistivity accelerator, and a thick film containing a Li 2 O component in the glass is well bonded to a standard substrate such as alumina, and has a compact structure and excellent resistance to electric dissipation electrodes.
  • the paste composition of the present invention can reduce the adverse effect of high surface resistance on the pn junction while reducing the contact resistance, thereby improving the efficiency of the solar cell and improving the performance of the electrode fabricated therefrom; the paste of the present invention
  • the solar cell electrodes prepared by the composition, and the solder have excellent bond strength and minimize series resistance (Rs), thereby providing high conversion efficiency.
  • the bismuth glass has a lower melting point, excellent durability, and good silver fusion. However, due to the extremely low reactivity of germanium and silicon materials, if the content of germanium in the glass powder is too high, the etching ability of the glass to the anti-reflective layer of the battery is greatly reduced.
  • the mole percentage of TeO 2 in the glass powder Less than 35%.
  • the glass frit comprises 1.0 wt% to 90.0 wt% of lead oxide, 1.0 wt% to 50.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O, further preferably, while defining TeO 2 at The mole percentage in the glass frit is less than 35%.
  • glass powder comprising 1.0wt% ⁇ 50.0wt% of lead oxide, 1.0wt% ⁇ 45.0wt% of TeO 2, and 5.1wt% ⁇ 10wt% of Li 2 O.
  • the molar percentage of TeO 2 in the glass frit is simultaneously defined to be less than 35%.
  • the glass powder further contains other oxides, and other oxides are selected from the group consisting of Na 2 O, K 2 O, MgO, CaO, SrO, BaO, Bi 2 O 3 , P 2 O 5 , SiO. 2 , one or more of the group consisting of B 2 O 3 , ZnO, NiO, CuO, WO 3 , MoO 3 , CoO, RuO, and TiO 2 . More preferably, the other oxides are present in an amount of from 1 to 25% by weight of the glass powder.
  • the above oxides may each function differently, for example, an alkali metal oxide may reduce the contact resistance.
  • a paste composition for preparing a solar cell electrode contains 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of the above glass powder, and the balance of additives.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the components of the solar cell electrode include silver powder, lead oxide-yttria-lithium oxide based glass powder, and an organic vehicle.
  • the composition of the solar cell electrode of the present invention will now be described in more detail.
  • a paste composition for preparing a solar cell electrode contains silver powder as a conductive powder.
  • the particle size of the silver powder can be on the order of nanometers or micrometers.
  • the silver powder may have a particle size of several tens to several hundreds of nanometers, or several to several tens of micrometers.
  • the silver powder may be a mixture of two or more silver powders having different particle sizes.
  • the silver powder may have a spherical shape, a flake or an amorphous shape.
  • the silver powder preferably has an average particle diameter (D50) of from about 0.1 ⁇ m to about 10 ⁇ m, more preferably an average particle diameter (D50) of from about 0.5 ⁇ m to about 5 ⁇ m.
  • the average particle diameter can be measured using an apparatus such as Mastersize 2000 (Malvern Co., Ltd.) after the conductive powder is dispersed by ultrasonic wave in isopropyl alcohol (IPA) at 25 ° C for 3 minutes. Within this average particle size range, the composition can provide low contact resistance and low line resistance.
  • the silver powder may be present in an amount from about 60% to about 95% by weight, based on the total weight of the composition. Within this range, the conductive powder can prevent deterioration of conversion efficiency due to an increase in electrical resistance. More preferably, the electrically conductive powder is present in an amount of from about 70% by weight to about 95% by weight.
  • the glass powder is used to enhance the adhesion between the conductive powder and the wafer or the substrate, and the contact resistance is reduced by forming the silver crystal grains in the emitter region by etching the anti-reflection layer and melting the silver powder during the sintering of the conductive paste. .
  • the glass frit softens and lowers the sintering temperature during the sintering process.
  • the solar cells are connected to each other by a bonding tape to constitute a solar cell module.
  • the low adhesive strength between the solar cell electrode and the ribbon may cause the battery to detach or lower the reliability.
  • lead oxide-yttria-lithium oxide (Pb X O Y -TeO 2 -Li 2 O)-based glass powder is used. .
  • the lead oxide-yttria-lithium oxide based glass powder may comprise 1.0 wt% to 90.0 wt% of lead oxide, 1.0 to 90.0 wt% of TeO 2 and 5.1 to 10 wt% of Li 2 O, Preferably, the mole percent of TeO 2 in the glass frit is less than 35%. More preferably, the glass frit contains lead oxides of 1.0 wt% to 90.0 wt% of lead oxide, 1.0 wt% to 50.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O, further preferably, while TeO 2 is in the glass. The mole percentage in the powder is less than 35%.
  • lead oxide is 1.0 wt% to 50.0 wt% of lead oxide, 1.0 wt% to 45.0 wt% of TeO 2 and 5.1 wt% to 10 wt% of Li 2 O, further preferably, while TeO 2 is in the glass frit. With a mole percentage of less than 35%, the glass powder ensures excellent bond strength and excellent conversion efficiency.
  • the lead oxide-yttria-lithium oxide-based glass frit may further include a salt selected from the group consisting of sodium oxide (Na 2 O), potassium oxide (K 2 O), magnesium oxide (MgO), and calcium oxide ( CaO), strontium oxide (SrO), barium oxide (BaO), bismuth oxide (Bi 2 O 3 ), phosphorus oxide (P 2 O 5 ), silicon dioxide (SiO 2 ) oxide (B 2 O 3 ), oxidation Zinc (ZnO), nickel oxide (NiO), copper oxide (CuO), tungsten oxide (WO 3 ), cobalt oxide (CoO), ruthenium oxide (RuO) and titanium oxide (TiO 2 ).
  • a salt selected from the group consisting of sodium oxide (Na 2 O), potassium oxide (K 2 O), magnesium oxide (MgO), and calcium oxide ( CaO), strontium oxide (SrO), barium oxide (BaO), bismuth oxide (Bi 2 O 3 ), phosphorus oxide (P 2 O 5
  • the glass powder can be prepared from lead oxide, cerium oxide, lithium oxide and at least one of the above oxides by any typical method.
  • lead oxide-yttria-lithium oxide based oxide and other oxides are mixed in a predetermined ratio.
  • Mixing can be done using a ball mill or a planetary mill.
  • the combined composition melts at about 900-1400 ° C and is then quenched to about 25 ° C.
  • the obtained material is pulverized using a disc mill, a planetary mill or the like to provide a glass frit.
  • the glass powder may have an average particle diameter D50 of from about 0.1 ⁇ m to about 10 ⁇ m and an amount of from about 0.1% by weight to about 5% by weight based on the total amount of the composition.
  • the glass powder may have a spherical or amorphous shape.
  • the organic vehicle imparts suitable viscosity and rheological properties to the paste composition by mechanical mixing with the inorganic components of the composition for the solar cell electrodes.
  • the organic vehicle may be any typical organic vehicle used for the solar cell electrode composition, and may include a binder resin, a solvent, and the like.
  • the binder resin may be selected from an acrylate resin or a cellulose resin. Ethyl cellulose is usually used as the binder resin. Further, the binder resin may be selected from the group consisting of ethyl hydroxyethyl cellulose, nitrocellulose, a blend of ethyl cellulose and phenolic resin, alkyd resin, phenol, acrylate, xylene, polybutene, poly Ester, urea, melamine, vinyl acetate resin, wood rosin, alcohol of polymethacrylate, and the like.
  • the solvent may be selected, for example, from hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol dibutylate). Ether), butyl carbitol acetate (diethylene glycol monobutyl ether acetate), propylene glycol monomethyl ether, hexanediol, terpineol, methyl ethyl ketone, benzyl alcohol, ⁇ -butyrolactone , ethyl lactate and combinations thereof.
  • the organic vehicle may be present in an amount of from about 1% by weight to about 20% by weight, based on the total weight of the composition. Within this range, the organic vehicle can provide sufficient adhesive strength and excellent printability to the composition.
  • the composition may further include typical additives as needed to enhance flow properties, processability and stability.
  • the additive may include, but is not limited to, a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, and the like. These additives may be used singly or as a mixture thereof. These additives may be present in an amount of from about 0.1% to about 5% by weight of the composition, although the amount may be varied as desired.
  • the back electrode 210 and the front electrode 230 may be formed by printing a battery electrode composition on a wafer or substrate 100 including a p-layer 101 and an n-layer 102 serving as an emitter, and sintering.
  • a preliminary process for preparing a back electrode is carried out by printing a composition on the back side of a wafer and drying the printed composition at about 200 ° C to about 400 ° C for about 10 seconds to 60 seconds.
  • a preliminary process for preparing the front electrode can be performed by printing a paste on the front surface of the wafer and drying the printed composition.
  • the front electrode and the back electrode may be formed by sintering the wafer at about 400 ° C to about 950 ° C, preferably about 850 ° C to about 950 ° C for about 30 seconds to 50 seconds.
  • melt sintering was carried out at 900 to 1400 ° C to prepare a lead oxide-yttria-lithium oxide based glass frit having an average particle diameter (D50) of 2.0 ⁇ m.
  • ethyl cellulose As an organic binder, 1.0 wt% of ethyl cellulose was sufficiently dissolved in 9.0 wt% of butyl carbitol at 60 ° C, and 87.5 wt% of spherical silver powder having an average particle diameter of 1.5 ⁇ m, 2.0 wt. % of lead oxide-yttria-lithium oxide based glass frit and 0.5 wt% of thixotropic agent Thixatrol ST are added to the binder solution, and then mixed and ground in a three-roll mill, thereby preparing a solar cell electrode composition .
  • the electrode composition prepared as above was deposited by screen printing on a front surface of a single crystal silicon wafer in a predetermined pattern, followed by drying in an infrared drying oven. Then, the composition for preparing the back aluminum electrode was printed on the back surface of the wafer and dried in the same manner.
  • the cell sheet processed by the above procedure was fired in a belt firing furnace at 910 ° C for 40 seconds.
  • the solar energy efficiency tester PSS10, BERGER
  • the solar energy efficiency tester was used to measure the conversion efficiency (%) of the battery, the series resistance Rs (m ⁇ ), the open circuit voltage (Voc), and the like. Then, the electrode of the battery is welded to the ribbon with a solder using a soldering iron at 300 ° C to 400 ° C.
  • Examples 1 to 10 and Comparative Examples 1 to 5 were prepared using the composition of the glass frit as shown in Table 1, and the compositions for solar cell electrodes were prepared in the same manner, and physical properties were evaluated. It is to be noted that the examples and comparative examples in Table 1 are intended to highlight the features of one or more of the inventions, and are not intended to limit the scope of the invention, nor to illustrate that the comparative examples are outside the scope of the invention. Further, the inventive subject matter is not limited to the specific details described in the examples and the comparative examples.
  • the composition of the glass frit composition prepared in Examples 1-10 was used in the preferred range of the present invention as compared with Comparative Examples 1-5, and the solar cell electrode produced therefrom was opposed to the ribbon. It shows a fairly high bond strength and excellent series resistance (lower Rs). In contrast, Comparative Examples 1-5 show high series resistance or low tensile strength or both.
  • Comparative Examples 1 and 2 show that the glass frit has a low Li 2 O content compared to the embodiment of the present invention, and is not in the preferred range of the present invention, and the prepared solar electrode has a higher series resistance and a relatively higher tensile strength. low. While Comparative Example 3 shows that the glass frit contains a high Li 2 O content, the tensile strength of the prepared solar electrode is relatively high, but the series resistance of the prepared solar electrode is relatively higher as compared with the embodiment of the present invention. Similarly, Comparative Example 4 shows that the glass frit contains more than 35 mol% of high TeO 2 compared to the embodiment of the present invention, and the prepared solar electrode has a relatively high tensile strength, but the series resistance of the prepared solar electrode is relatively Higher. Comparative Example 5 shows that the Li 2 O content of the glass frit is not within the preferred range of the present invention, and the solar cell produced has a high series resistance.
  • the glass frit contains 1.0 to 90.0% by weight of lead oxide, 1.0 to 90.0% by weight of TeO 2 and 5.1 to 10% by weight of Li 2 O, and the molar % of TeO 2 is less than 35%. More preferably, the glass frit contains lead oxide of 1.0 to 90.0% by weight of lead oxide, TeO 2 of 1.0 to 50.0% by weight, and Li 2 O of 5.1 to 10% by weight, and the mol% of TeO 2 is 35% or less.
  • the glass powder composition of 1.0 ⁇ 50.0wt% lead oxide, of TeO 2 is 1.0 ⁇ 45.0wt%, Li 2 O is 5.1 ⁇ 10wt%, TeO 2 mol% of 35% or less, is formed Solar cells have better performance.

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Abstract

一种用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池。其中，所述玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～90.0wt％的TeO 2和5.1wt％～10wt％的Li 2O，铅氧化物为PbO和/或Pb 3O 4。所述糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述玻璃粉料，以及余量的添加剂。所述糊剂组合物在降低接触电阻的同时，能够降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能。

Description

用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池 技术领域
本发明涉及太阳能电池制造技术领域，具体而言，涉及一种用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池。
背景技术
太阳能电池通过p-n结利用光伏效应将太阳光的光子转换来产生电能。在太阳能电池中，前电极和后电极分别在具有p-n结的半导体晶片或基底的上下表面形成。然后，p-n结的光电效应由进入半导体晶片的太阳光诱导，进而由p-n结的光电效应产生的电子通过电极向外部提供电流。电极用组合物设置于晶片上，再经图案化和烘焙，形成太阳能电池的电极。
通过持续减小发射极厚度的方法来提高太阳能电池效率，反而有可能导致分流，这将使太阳能电池的性能变差。另外，太阳能电池已经逐渐增加面积以提高效率。然而，在这种情况下，可能存在由于太阳能电池的接触电阻的增加而导致的效率下降的问题。
太阳能电池最上面的抗反射层是一层氮化硅，太阳能电池的正面电极需要其中的玻璃粉组分刻蚀掉这层氮化硅，来导通下层发射极产生的电流。太阳能电池通过焊带彼此连接以形成太阳能电池组件。目前，通过由包括含铅玻璃粉料的典型组分和焊接条制成的太阳能电池电极和电极与焊接带之间的低粘合性的粘合力不足，导致转换效率的大的串联电阻和转换效率的降低。
发明内容
本发明旨在提供一种用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池，以解决现有技术中太阳能电池电极与焊带的粘合力不足，电极和焊带之间的低粘附性会导致高的串联电阻和转换效率的劣化的技术问题。
为了实现上述目的，根据本发明的一个方面，提供了一种用于制备太阳能电池电极的玻璃粉料。该玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～90.0wt％的TeO2和5.1wt％～10wt％的Li2O，铅氧化物为PbO和/或Pb3O4。
进一步地，TeO2在玻璃粉料中的摩尔百分数低于35％。
进一步地，玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～50.0wt％的TeO2和5.1wt％～10wt％的Li2O。
进一步地，玻璃粉料包含1.0wt％～50.0wt％的铅氧化物，1.0wt％～45.0wt％的TeO2和5.1wt％～10wt％的Li2O。
进一步地，TeO2在玻璃粉料中的摩尔百分数低于35％。
进一步地，玻璃粉料还包含其他氧化物，其他氧化物选自由Na2O、K2O、MgO、CaO、SrO、BaO、Bi2O3、P2O5、SiO2、B2O3、ZnO、NiO、CuO、WO3、MoO3、CoO、RuO和TiO2组成的组中的一种或多种。
进一步地，其他氧化物的含量占玻璃粉料的1～25wt％。
进一步地，玻璃粉料的平均粒径D50为0.1～10μm。
根据本发明的另一个方面，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述玻璃粉料，以及余量的添加剂。
进一步地，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。
进一步地，导电粉末为银粉。
根据本发明的再一个方面，提供一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。
根据本发明的又一方面，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。
本发明的糊剂组合物，其在降低接触电阻的同时，能够降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能；本发明的糊剂组合物制备的太阳能电池电极，和焊带有优异的粘合强度并且使串联电阻(Rs)最小化，从而提供高转换效率。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了根据本发明一实施方式中使用糊剂组合物制造的太阳能电池的示意图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的玻璃粉料。该玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～90.0wt％的TeO2和5.1wt％～10wt％的Li2O，铅氧化物为PbO和/或Pb3O4。
PbO是降低玻璃的软化点的成分，也是能够在玻璃料组合物中低温烧结的成分。碲玻璃具有低熔点，高度耐用并且容易地将银溶解在固溶体中。氧化锂被称为低电阻率促进剂，玻璃中含有Li2O成分的厚膜与氧化铝等标准基体良好结合，结构密实，耐电耗散电极的优异性能。本发明的糊剂组合物，其在降低接触电阻的同时，能够降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能；本发明的糊剂组合物制备的太阳能电池电极，和焊带有优异的粘合强度并且使串联电阻(Rs)最小化，从而提供高转换效率。
碲玻璃有较低的熔点，极好的耐久性，并且有很好的融银作用。但是由于碲和硅材料有极低的反应活性，如果玻璃粉中碲的含量过高会极大的降低玻璃对电池减反层的蚀刻能力，优选的，TeO2在玻璃粉料中的摩尔百分数低于35％。优选的，玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～50.0wt％的TeO2和5.1wt％～10wt％的Li2O，进一步优选的，同时限定TeO2在玻璃粉料中的摩尔百分数低于35％。更有选的，玻璃粉料包含1.0wt％～50.0wt％的铅氧化物，1.0wt％～45.0wt％的TeO2和5.1wt％～10wt％的Li2O。进一步优选的，同时限定TeO2在玻璃粉料中的摩尔百分数低于35％。
为了进一步改善玻璃粉料的性能，玻璃粉料还包含其他氧化物，其他氧化物选自由Na2O、K2O、MgO、CaO、SrO、BaO、Bi2O3、P2O5、SiO2、B2O3、ZnO、NiO、CuO、WO3、MoO3、CoO、RuO和TiO2组成的组中的一种或多种。更优选的，其他氧化物的含量占玻璃粉料的1～25wt％。上述氧化物可以分别起到不同的作用，例如碱金属氧化物可以降低接触电阻的作用。
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述玻璃粉料，以及余量的添加剂。其中，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。
根据本发明一种典型的实施方式，提供了一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。
根据本发明一种典型的实施方式，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。
根据本发明的典型的实施方式，太阳能电池电极的部件包括银粉、铅氧化物-氧化碲-氧化锂基玻璃粉料和有机载体。现在将更详细地描述本发明的太阳能电池电极的组成。
(A)银粉
根据本发明一种典型的实施方式，用于制备太阳能电池电极的糊剂组合物包含银粉作为导电粉末。银粉的粒度可以是纳米或微米级。例如，银粉可以具有几十至几百纳米，或几至几十微米的粒度。或者，银粉可以是具有不同粒径的两种或更多种银粉的混合物。
银粉可以具有球形、薄片或无定形形状。
银粉优选具有约0.1μm至约10μm的平均粒径(D50)，更优选约0.5μm至约5μm的平均粒径(D50)。平均粒径可以使用仪器，如Mastersize 2000(Malvern Co.，Ltd。)在将导电粉末在25℃下通过超声波分散在异丙醇(IPA)中3分钟之后测量。在该平均粒径范围内，组合物可以提供低接触电阻和低线电阻。
基于组合物的总重量，银粉可以约60wt％至约95wt％的量存在。在该范围内，导电粉末可以防止由于电阻的增加而导致的转换效率的劣化。更佳情况下，导电粉末以约70wt％至约95wt％的量存在。
(B)铅氧化物-氧化碲-氧化锂基玻璃粉料
玻璃粉料用于增强导电粉末与晶片或基板之间的粘附力，并且在导电浆料烧结过程中，通过蚀刻减反射层和熔化银粉而在发射极区域中形成银晶粒来降低接触电阻。此外，在烧结工艺期间，玻璃粉料软化并降低烧结温度。
当为了提高太阳能电池效率而增加太阳能电池的面积时，可能存在太阳能电池的接触电阻增加的问题。因此，需要最小化串联电阻(Rs)和对p-n结的影响。另外，随着使用具有不同表面电阻的各种晶片的适合烧结温度在宽范围内变化，玻璃粉料需要确保足够的热稳定性以耐受较大的烧结温度窗口。
太阳能电池通过焊带彼此连接以构成太阳能电池组件。在这种情况下，太阳能电池电极和焊带之间的低粘合强度有可能导致电池的脱离或降低可靠性。在本发明中，为了确保太阳能电池具有所需的电性能和物理性能如粘合强度，使用铅氧化物-氧化碲-氧化锂(PbXOY-TeO2-Li2O)基玻璃粉料。
在本发明中，铅氧化物-氧化碲-氧化锂基玻璃粉料可以包含1.0wt％～90.0wt％的铅氧化物，1.0～90.0wt％的TeO2和5.1～10wt％的Li2O，优选的，TeO2在玻璃粉料中的摩尔百分数低于35％。更优选玻璃粉料包含氧化铅1.0wt％～90.0wt％的铅氧化物，1.0wt％～50.0wt％的TeO2和5.1wt％～10wt％的Li2O，进一步优选，同时TeO2在玻璃粉料中的摩尔百分数低于35％。更优选氧化铅1.0wt％～50.0wt％的铅氧化物，1.0wt％～45.0wt％的TeO2和5.1wt％～10wt％的Li2O，进一步优选，同时TeO2在玻璃粉料中的摩尔百分数低于35％，玻璃粉料可以确保优异的粘合强度和优异的转换效率。
根据本发明的典型实施方案，铅氧化物-氧化碲-氧化锂基玻璃粉还可以包括选自氧化钠(Na2O)，氧化钾(K2O)，氧化镁(MgO)，氧化钙(CaO)，氧化锶(SrO)，氧化钡(BaO)，氧化铋(Bi2O3)，氧化磷(P2O5)，二氧化硅(SiO2)氧化物(B2O3)，氧化锌(ZnO)，氧化镍(NiO)，氧化铜(CuO)，氧化钨(WO3)，氧化钴(CoO)，氧化钌(RuO)和氧化钛(TiO2)。
玻璃粉料可以通过任何典型的方法由铅氧化物、氧化碲、氧化锂和至少一种上述氧化物制备。例如，铅氧化物-氧化碲-氧化锂基氧化物和其他氧化物以预定的比例混合。可以使用球磨机或行星式磨机进行混合。混合的组合物在约900-1400℃下熔化，然后淬火至约25℃。使用盘式磨机，行星式磨机等对所得到的材料进行粉碎，从而提供玻璃料。
玻璃粉料的平均粒径D50可以约0.1μm至约10μm，并且占基于组合物的总量的约0.1wt％至约5wt％的量。玻璃粉料可以具有球形或无定形形状。
(C)有机载体
有机载体通过与用于太阳能电池电极的组合物的无机组分的机械混合，赋予糊料组合物印刷适当的粘度和流变特性。
有机载体可以是用于太阳能电池电极组合物的任何典型的有机载体，并且可以包括粘合剂树脂，溶剂等。
粘合剂树脂可以选自丙烯酸酯树脂或纤维素树脂。通常使用乙基纤维素作为粘合剂树脂。此外，粘合剂树脂可以选自乙基羟乙基纤维素、硝化纤维素、乙基纤维素和酚醛树脂的共混物、醇酸树脂、苯酚、丙烯酸酯、二甲苯、聚丁烯、聚酯、尿素、三聚氰胺、乙酸乙烯酯树脂、木松香、聚甲基丙烯酸酯的醇等。
溶剂可以选自例如己烷、甲苯、乙基溶纤剂、环己酮、丁基溶纤剂、丁基卡必醇(二甘醇单丁醚)、二丁基卡必醇(二甘醇二丁醚)、丁基卡必醇乙酸酯(二甘醇单丁醚乙酸酯)、丙二醇单甲醚、己二醇、萜品醇、甲基乙基酮、苄醇、γ-丁内酯、乳酸乙酯及其组合。
基于组合物的总重量，有机载体可以以约1wt％至约20wt％的量存在。在该范围内，有机载体可以为组合物提供足够的粘合强度和优异的可印刷性。
(D)添加剂
根据需要，组合物可以进一步包括典型的添加剂，以增强流动性能，加工性能和稳定性。添加剂可以包括分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂、偶联剂等，但不限于此。这些添加剂可以单独使用或作为其混合物使用。这些添加剂可以以组合物中约0.1wt％至约5wt％的量存在，但该量可根据需要改变。
根据本发明一种典型的实施方式，使用糊剂组合物制造的太阳能电池。如图1所示，背面电极210和正面电极230可以通过印刷电池电极组分于包括p层101和用作发射极的n层102的晶片或基板100上，并经过烧结来形成。例如，通过在晶片的背面上印刷组合物并在约200℃至约400℃下干燥所印刷的组合物约10秒至60秒，来进行用于制备背面电极的预备工艺。此外，可以通过在晶片的前表面上印刷浆料并干燥印刷的组合物来进行用于制备前电极的初步工艺。然后，可以通过在约400℃至约950℃，优选约850℃至约950℃下烧结晶片约30秒至50秒来形成正面电极和背面电极。
接下来，本发明将通过参考实施例更详细地描述。然而，应当注意，这些实施例的提供仅用于说明本发明，不应以任何方式解释为限制本发明。
为了清楚的目的，省略了本领域技术人员清楚的详细描述。
实施例及对比例
根据表1所示的组成混合氧化物，在900-1400℃下进行熔融烧结，由此制备平均粒径(D50)为2.0μm的铅氧化物-氧化碲-氧化锂基玻璃料。
作为有机粘合剂，将1.0wt％的乙基纤维素在60℃下充分溶解于9.0wt％的丁基卡必醇中，87.5wt％的平均粒径为1.5μm的球形银粉末，2.0wt％的含氧化铅-氧化碲-氧化锂基玻璃粉和0.5wt％的触变剂Thixatrol ST加入到粘合剂溶液中，然后在三辊机中混合和研磨，由此制备太阳能电池电极组合物。
将如上所制备的电极组合物通过丝网印刷，以预定图案沉积在单晶硅片的前表面上，随后在红外干燥炉中干燥。然后，将用于制备背铝电极的组合物印刷在晶片的背面上并以相同的方式干燥。将通过以上步骤处理的电池片在带式烧成炉中，于910℃下烧成40秒。使用太阳能效率测试仪(PSS10，BERGER)来测量电池的转换效率(％)，串联电阻Rs(mΩ)，开路电压(Voc)等。然后，使用烙铁在300℃至400℃下用焊剂将电池的电极与焊带焊接。然后，电池电极与焊带的的粘合强度(N/mm)使用张力测试仪在180°的剥离角和50mm/min的拉伸速率下测量。测量的转换效率和拉力测试显示于表1中。
实施例1-10和对比例1-5
实施例1～10和对比例1～5采用如表1所示的玻璃粉的组成，以相同的方式制备用于太阳能电池电极的组合物，并评价物理性能。需要表明的是表1中的实施例和对比例是为了突出一个或多个发明例的特点，而不是为限制本发明的范围，也不是说明对比例在本发明的范围之外。此外，发明主体并不局限于实施例和对比例中所描述的特定细节。
表1
Figure PCTCN2017105867-appb-000001
Figure PCTCN2017105867-appb-000002
如表1所示，与对比例1-5相比，使用实施例1-10中制备的玻璃料组合物的成份组成在本发明优选的范围内，由其制造的太阳能电池电极相对于焊带显示出相当高的粘合强度以及优异的串联电阻(Rs较低)。相反的，对比例1-5显示高串联电阻或低拉强度或两者皆有。
对比例1和2表明，与本发明的实施例相比，玻璃料具有低的Li2O含量，不在本发明的优选范围内，所制备的太阳能电极的串联电阻较高、拉伸强度相对较低。而对比例3表明，玻璃料含有高Li2O含量，制备的太阳能电极的拉伸强度虽然相对较高，但与本发明的实施例相比，所制备的太阳能电极的串联电阻相对较高。类似地，对比例4表明，与本发明的实施例相比，玻璃料含有高于35mol％的高TeO2，制备的太阳能电极的拉伸强度相对较高，但是制备的太阳能电极的串联电阻相对较高。对比例5表明，玻璃料的Li2O含量不在本发明的优选范围内，所制备的太阳能电池的串联电阻高。
实施例表明玻璃料含有1.0～90.0wt％的铅氧化物，1.0～90.0wt％的TeO2和5.1～10wt％的Li2O，TeO2的摩尔％低于35％。更优选玻璃粉料包含氧化铅1.0～90.0wt％的铅氧化物，1.0～50.0wt％的TeO2和5.1～10wt％的Li2O，TeO2的摩尔％为35％以下。更优选玻璃粉料组合物为含铅的氧化物的1.0～50.0wt％，TeO2为1.0～45.0wt％，Li2O为5.1～10wt％，TeO2的摩尔％为35％以下，形成的太阳能电池具有更好的性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种用于制备太阳能电池电极的玻璃粉料，其特征在于，所述玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～90.0wt％的TeO2和5.1wt％～10wt％的Li2O，所述铅氧化物为PbO和/或Pb3O4。
  2. 根据权利要求1所述的玻璃粉料，其特征在于，TeO2在所述玻璃粉料中的摩尔百分数低于35％。
  3. 根据权利要求1所述的玻璃粉料，其特征在于，所述玻璃粉料包含1.0wt％～90.0wt％的铅氧化物，1.0wt％～50.0wt％的TeO2和5.1wt％～10wt％的Li2O。
  4. 根据权利要求1所述的玻璃粉料，其特征在于，所述玻璃粉料包含1.0wt％～50.0wt％的铅氧化物，1.0wt％～45.0wt％的TeO2和5.1wt％～10wt％的Li2O。
  5. 根据权利要求4所述的玻璃粉料，其特征在于，TeO2在所述玻璃粉料中的摩尔百分数低于35％。
  6. 根据权利要求1至5中任一项所述的玻璃粉料，其特征在于，所述玻璃粉料还包含其他氧化物，所述其他氧化物选自由Na2O、K2O、MgO、CaO、SrO、BaO、Bi2O3、P2O5、SiO2、B2O3、ZnO、NiO、CuO、WO3、MoO3、CoO、RuO和TiO2组成的组中的一种或多种。
  7. 根据权利要求6所述的玻璃粉料，其特征在于，所述其他氧化物的含量占所述玻璃粉料的1～25wt％。
  8. 根据权利要求1至5中任一项所述的玻璃粉料，其特征在于，所述玻璃粉料的平均粒径D50为0.1～10μm。
  9. 一种用于制备太阳能电池电极的糊剂组合物，其特征在于，包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的如权利要求1至8中任一项所述玻璃粉料，以及余量的添加剂。
  10. 根据权利要求9所述的糊剂组合物，其特征在于，所述添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。
  11. 根据权利要求9所述的糊剂组合物，其特征在于，所述导电粉末为银粉。
  12. 一种太阳能电池电极，其特征在于，由权利要求9至11中任一项所述的糊剂组合物制备而成。
  13. 一种太阳能电池，包括电极，其特征在于，所述电极为如权利要求12所述的太阳能电池电极。
PCT/CN2017/105867 2017-09-20 2017-10-12 用于制备太阳能电池电极的玻璃粉料、包括其的糊剂组合物、太阳能电池电极和太阳能电池 WO2019056418A1 (zh)

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