阅读说明：本技术 一种含纳米银玻璃粉及其制备方法 (Glass powder containing nano silver and preparation method thereof ) 是由 许亚文 卢美军 廖维林 于 2019-11-11 设计创作，主要内容包括：本发明公开了一种含纳米银玻璃粉及其制备方法,首先将氧化物原料和助剂粉碎混合均匀,依次经热处理、再粉碎后获得玻璃粉粗品；然后将有机包覆剂包覆的纳米银分散于有机溶剂中后再加入玻璃粉粗品；最后经过球磨、离心、干燥、粉碎后即获得含纳米银玻璃粉。本发明以高度的分散均一性和较理想的收率制备获得了含纳米银玻璃粉,在制备过程中,不仅保证了体系中玻璃粉达到微米级的较高要求,同时避免了微纳米颗粒的团聚效应。制备获得的含纳米银玻璃粉效果优异,可以明显增加电池的接触,从而提高太阳能电池转换效率。(The invention discloses a glass powder containing nano silver and a preparation method thereof, which comprises the steps of firstly crushing and uniformly mixing an oxide raw material and an auxiliary agent, and obtaining a crude glass powder product after heat treatment and crushing in sequence; then dispersing the nano silver coated by the organic coating agent in an organic solvent, and then adding a glass powder crude product; and finally, ball milling, centrifuging, drying and crushing to obtain the glass powder containing the nano silver. The glass powder containing the nano silver is prepared and obtained with high dispersion uniformity and ideal yield, and in the preparation process, the glass powder in the system can meet the high requirement of micron level, and the agglomeration effect of micro-nano particles is avoided. The prepared glass powder containing nano silver has excellent effect, and can obviously increase the contact of a battery, thereby improving the conversion efficiency of the solar battery.)

1. The glass powder containing nano silver is characterized in that: the glass powder containing nano silver is prepared by the following method: firstly, crushing and uniformly mixing an oxide raw material and an auxiliary agent, and sequentially carrying out heat treatment and crushing to obtain a crude glass powder product; then dispersing the nano silver coated by the organic coating agent in an organic solvent, and then adding a glass powder crude product; and finally, ball milling, centrifuging, drying and crushing to obtain the glass powder containing the nano silver.

2. The nanosilver-containing glass powder of claim 1, wherein: the oxide raw material comprises TeO₂、PbO、Tl₂O₃、Bi₂O3、Li₂O, optionally also including WO₃、ZnO、MgO、B₂O₃、CaO、TiO₂、Fe₂O₃、Al₂O₃、Ag₂O、ZrO₂、Na₂O、K₂One or more of O and MoO; and/or

The auxiliary agent is an adhesion additive and a corrosion auxiliary agent; wherein the adhesion additive is selected from ZnO and WO₃、SiO₂、P₂O₅、B₂O₃、Ge₂O₃One or more of NiO and a mixture of NiO mixed in any proportion; and/or

The corrosion assistant is selected from Al₂O₃、Cr₂O₃、TiO₂、Al₂O₃、MnO₂、LiF、PbF₂、AlF₃、TiF₄、Ge₂O₃、Fe₂O₃One or more of CuO and MoO in any proportion; and/or

The organic coating agent is selected from one or more of polymer acids, polymer ethers, polymer ketones and polymer esters; preferably polymeric ketones and/or polymeric esters; more preferably polyvinylpyrrolidone (PVP) and/or an acryl resin; preferably, the molecular weight of the organic coating agent is 5000-.

3. The nanosilver-containing glass powder according to claim 1 or 2, characterized in that: the composition of the oxide raw material is 15-70% TeO₂、5-50％PbO、0.3-30％Tl₂O₃、3-40％Bi₂O₃0.5-15% of Li₂O、Na₂O and K₂Mixture of O, 0-15% of B₂O₃、0-10％CaO、0-15％SiO₂(ii) a Preferably 25-60% TeO₂、15-40％PbO、0.8-20％Tl₂O₃、8-30％Bi₂O₃1-12% of Li₂O、Na₂O and K₂Mixture of O, 0.5-12% of B₂O₃、0.5-8％CaO、0.8-12％SiO₂(ii) a More preferably 30-50% TeO₂、20-35％PbO、1.5-15％Tl₂O₃、12-25％Bi₂O₃3-10% of Li₂O、Na₂O and K₂Mixture of O, 1-10% of B₂O₃、1-6％CaO、1.5-10％SiO₂(ii) a And/or

The auxiliary agent comprises 1-50% of adhesion additive and 1-50% of corrosion auxiliary agent; preferably 10-40% of adhesion additive and 10-40% of corrosion assistant; more preferably 20-35% of adhesion additive and 20-35% of corrosion assistant; and/or

The mass ratio of the nano silver coated by the organic coating agent to the crude glass powder is 0.1-5.0:1, preferably 1-4.0:1, more preferably 1.5-3.0:1, and more preferably 2.0-2.5: 1; and/or

The mass ratio of the nano silver coated by the organic coating agent to the organic solvent is 0.1-2:1, preferably 0.3-1.8:1, and more preferably 0.5-1.5: 1; and/or

The silver content in the nano silver coated by the organic coating agent is 1% -12%, preferably 3% -10%, more preferably 5% -9%, and even more preferably 7% -8.5%.

4. The nanosilver-containing glass powder according to any one of claims 1 to 3, characterized in that: the particle size of the crude glass powder is less than 400 meshes, preferably less than 200 meshes, and more preferably less than 100 meshes; and/or

The dispersion mode is one or more of magnetic stirring, mechanical stirring and omnibearing ball milling; and/or

The temperature of the heat treatment is 700-1200 ℃, preferably 800-1100 ℃, and more preferably 900-1000 ℃; the heat treatment time is 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.

5. A method for producing the nano-silver-containing glass powder according to any one of claims 1 to 4, characterized by comprising: the method comprises the following steps:

1) crushing and uniformly mixing the oxide raw material and the auxiliary agent, and sequentially carrying out heat treatment and crushing and mixing to obtain a crude glass powder product;

2) coating nano silver with an organic coating agent, dispersing in an organic solvent, adding the crude glass powder obtained in the step 1), and uniformly mixing to obtain a nano silver-glass powder mixture;

3) and 3) carrying out ball milling, centrifuging, drying and crushing on the nano silver-glass powder mixture obtained in the step 2) in sequence to obtain the nano silver-containing glass powder.

6. The method of claim 5, wherein: the oxide raw material in the step 1) comprises TeO₂、PbO、Tl₂O₃、Bi₂O3、Li₂O, optionally also including WO₃、ZnO、MgO、B₂O₃、CaO、TiO₂、Fe₂O₃、Al₂O₃、Ag₂O、ZrO₂、Na₂O、K₂One or more of O and MoO; and/or

The auxiliary agent is an adhesion additive and a corrosion auxiliary agent; wherein the adhesion additive is selected from ZnO, WO₃、SiO₂、P₂O₅、B₂O₃、Ge₂O₃One or more of NiO and a mixture of NiO mixed in any proportion; and/or

The corrosion assistant is selected from Al₂O₃、Cr₂O₃、TiO₂、Al₂O₃、MnO₂、LiF、PbF₂、AlF₃、TiF₄、Ge₂O₃、Fe₂O₃One or more of CuO and MoO in any proportion; and/or

Preferably, the addition amount of the oxide raw material is 15-70% of TeO₂、5-50％PbO、0.3-30％Tl₂O₃、3-40％Bi₂O₃0.5-15% of Li₂O、Na₂O and K₂Mixture of O, 0-15% of B₂O₃、0-10％CaO、0-15％SiO₂(ii) a Preferably 25-60% TeO₂、15-40％PbO、0.8-20％Tl₂O₃、8-30％Bi₂O₃1-12% of Li₂O、Na₂O and K₂Mixture of O, 0.5-12% of B₂O₃、0.5-8％CaO、0.8-12％SiO₂(ii) a More preferably 30-50% TeO₂、20-35％PbO、1.5-15％Tl₂O₃、12-25％Bi₂O₃3-10% of Li₂O、Na₂O and K₂Mixture of O, 1-10% of B₂O₃、1-6％CaO、1.5-10％SiO₂(ii) a And/or

The addition amount of the additive is 1-50% of adhesion additive and 1-50% of corrosion additive; preferably 10-40% of adhesion additive and 10-40% of corrosion assistant; more preferably 20-35% of adhesion additive and 20-35% of corrosion assistant; and/or

The temperature of the heat treatment is 700-1200 ℃, preferably 800-1100 ℃, and more preferably 900-1000 ℃; the heat treatment time is 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.

7. The method according to claim 5 or 6, characterized in that: in the step 2), the mass ratio of the nano silver coated by the organic coating agent to the organic solvent is 0.1-2:1, preferably 0.3-1.8:1, and more preferably 0.5-1.5: 1; and/or

The mass ratio of the added nano silver coated by the organic coating agent to the added crude glass powder is 0.1-5.0:1, preferably 1-4.0:1, more preferably 1.5-3.0:1, and more preferably 2.0-2.5: 1; and/or

The organic coating agent is selected from one or more of polymer acids, polymer ethers, polymer ketones and polymer esters; preferably polymeric ketones and/or polymeric esters; more preferably polyvinylpyrrolidone (PVP) and/or an acryl resin; preferably, the molecular weight of the organic coating agent is 5000-; and/or

The silver content in the nano silver coated by the organic coating agent is 1% -12%, preferably 3% -10%, more preferably 5% -9%, and even more preferably 7% -8.5%; and/or

The particle size of the added crude glass powder is less than 400 meshes, preferably less than 200 meshes, and more preferably less than 100 meshes; and/or

The dispersion mode is one or more of magnetic stirring, mechanical stirring and omnibearing ball milling.

8. The method according to any one of claims 5-7, wherein: the step 1) is specifically as follows: fully crushing (for example, grinding) the oxide raw material, the adhesion additive and the corrosion assistant in proportion, uniformly mixing to obtain a mixture, then placing the mixture in a high-temperature furnace, firing for 0.5-10h (preferably 1-8h, more preferably 2-5h) at the temperature of 700-.

9. The method of claim 8, wherein: the step 2) is specifically as follows: coating the nano silver with an organic coating agent to obtain nano silver coated with the organic coating agent, dispersing the nano silver coated with the organic coating agent (in a dispersion mode of one or more of magnetic stirring, mechanical stirring and all-dimensional ball milling) in an organic solvent (such as an alcohol solvent), adding the glass powder crude product obtained in the step 1) into a dispersed nano silver organic system, and uniformly stirring to obtain a nano silver-glass powder mixture.

10. The method of claim 9, wherein: the step 3) is specifically as follows: adding agate balls into the nano silver-glass powder mixture obtained in the step 2), then carrying out ball milling (ball milling in an all-dimensional ball mill for 0.5-8h, preferably 1-6h, more preferably 2-4h), then separating the agate balls, adding a proper amount of solvent (for example, the addition amount is 0.5-1.5 times of the original solvent), then centrifuging (for example, for 2-3 times), drying, and sieving (for example, sieving through a 100-fold-mesh 700-mesh sieve, preferably sieving through a 300-fold-mesh 500-mesh sieve) to obtain the nano silver-containing glass powder.

Technical Field

The invention relates to a material for a solar cell, in particular to glass powder containing nano silver and a preparation method thereof, belonging to the technical field of cell materials.

Background

The front silver package of the solar cell mainly comprises three parts, namely silver powder, glass powder and an organic carrier. The proportion of the binder phase glass powder in the raw materials is small, but the influence on the adhesion between the electrode and the substrate and the photoelectric conversion efficiency of the battery is very large. In order to greatly improve the photoelectric conversion efficiency and reduce the cost, the solar cell is developing towards the directions of high sheet resistance, shallow junction and fine grid, and the solar cell puts higher performance requirements on glass powder used by front silver paste. The glass powder plays a role in high-temperature bonding, and also serves as a fluxing agent for silver powder sintering and a medium substance for silver-silicon ohmic contact, the front silver paste of the solar cell is printed into a front electrode pattern through screen printing, and in the subsequent sintering film-forming process, the glass powder softening corrosion candle penetrates through the antireflection film and is mutually fused and bridged with silver particles to form a compact electrode conductive network. The glass powder for front silver paste is required to have the performances of lower softening temperature, high penetration of an antireflection film during high-temperature sintering and high vitrification degree. The performance of the glass frit directly affects the electrical performance, tensile force, cell efficiency, etc. of the solar cell. At present, the influence of the glass powder characteristics on the electrical performance of the solar cell has become a focus of the current crystalline silicon solar cell. Therefore, the improvement of front silver paste glass powder is urgent.

One of the directions in which glass frits improve is the particle size problem. The size of the glass powder particle diameter directly influences the screen printing effect, the electrical performance characteristics of the crystalline silicon solar cell piece and the like. One of the methods for improving the particle size is to prevent the micro-nano particles from agglomerating, i.e. to add a coating agent in the glass preparation process. Meanwhile, in order to change the influence of the glass powder on the electrical performance of the solar cell, the addition of the composite component into the glass powder has been one of the focuses of research.

By combining the two points, the addition of the micro-nano silver powder into the glass powder has a relatively obvious influence on the electrical performance of the crystalline silicon solar cell. Especially in recent years, with the development of nanotechnology, nano silver has been increasingly regarded as a composite component. However, how to add the composite components into the glass powder can not cause agglomeration of micro-nano particles, but can significantly change the electrical properties of the solar cell? This problem is one of the key steps to be solved.

In addition, a ball mill is indispensable for the pulverization and grinding of solid powder. Compared with the common ball mill, the omnibearing planetary ball mill has the following advantages: (1) the phenomenon of sinking is not easy to generate during dry grinding, because the whole body rotates 360 degrees while rotating and revolving. (2) Normally, the grinding efficiency of the all-round ball mill is higher than that of the common ball mill by 50 percent or even more, and mainly depends on materials. But only partially, but mainly also other factors, such as: when the granularity reaches the level of micron and nanometer, some materials can generate static electricity in the grinding process, and the phenomenon of agglomeration can be caused.

Breaking the agglomeration phenomenon in the glass powder improvement process is a key target of the current technology. Except for improving the original production process, how to smoothly add the nano-scale composite components to change the electrical property of the solar cell piece is realized, and once the key factor is broken, the efficiency of the crystalline silicon solar cell is obviously improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the glass powder containing the nano silver and the preparation method thereof, the glass powder containing the nano silver is prepared and obtained by the method with high dispersion uniformity and more ideal yield, and in the preparation process, the glass powder in the system can meet the higher requirement of micron level, and the agglomeration effect of micro-nano particles is avoided. The glass powder containing the nano silver prepared by the method has excellent effect, and can obviously increase the contact of the cell, thereby improving the conversion efficiency of the solar cell.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

according to a first embodiment of the present invention, there is provided a nanosilver-containing glass powder, which is prepared by the following method: firstly, crushing and uniformly mixing an oxide raw material and an auxiliary agent, and sequentially carrying out heat treatment and crushing to obtain a crude glass powder product; then dispersing the nano silver coated by the organic coating agent in an organic solvent, and then adding a glass powder crude product; and finally, ball milling, centrifuging, drying and crushing to obtain the glass powder containing the nano silver.

Preferably, the oxidation is carried outThe raw material comprises TeO₂、PbO、Tl₂O₃、Bi₂O3、Li₂O, optionally also including WO₃、ZnO、MgO、B₂O₃、CaO、TiO₂、Fe₂O₃、Al₂O₃、Ag₂O、ZrO₂、Na₂O、K₂One or more of O and MoO. And/or

Preferably, the additives are adhesion additives and corrosion additives. Wherein the adhesion additive is selected from ZnO and WO₃、SiO₂、P₂O₅、B₂O₃、Ge₂O₃And NiO, or a mixture of a plurality of these components in an arbitrary ratio. And/or

Preferably, the corrosion aid is selected from Al₂O₃、Cr₂O₃、TiO₂、Al₂O₃、MnO₂、LiF、PbF₂、AlF₃、TiF₄、Ge₂O₃、Fe₂O₃One or more of CuO and MoO in any proportion. And/or

Preferably, the organic coating agent is selected from one or more of polymer acids, polymer ethers, polymer ketones, and polymer esters. The organic coating agent is preferably a polymer ketone and/or a polymer ester. The organic capping agent is more preferably polyvinylpyrrolidone (PVP) and/or acryl resin (i.e., ethyl acrylate/methyl methacrylate copolymer).

Preferably, the molecular weight of the organic coating agent is 5000-.

Preferably, the oxide raw material has a composition of 15 to 70% TeO₂、5-50％PbO、0.3-30％Tl₂O₃、3-40％Bi₂O₃0.5-15% of Li₂O、Na₂O and K₂Mixture of O, 0-15% of B₂O₃、0-10％CaO、0-15％SiO₂. Preferably 25-60% TeO₂、15-40％PbO、0.8-20％Tl₂O₃、8-30％Bi₂O₃1-12% of Li₂O、Na₂O and K₂Mixture of O, 0.5-12% of B₂O₃、0.5-8％CaO、0.8-12％SiO₂. More preferably 30-50% TeO₂、20-35％PbO、1.5-15％Tl₂O₃、12-25％Bi₂O₃3-10% of Li₂O、Na₂O and K₂Mixture of O, 1-10% of B₂O₃、1-6％CaO、1.5-10％SiO₂. And/or

Preferably, the composition of the auxiliary agent is 1-50% of adhesion additive and 1-50% of corrosion auxiliary agent. Preferably 10-40% of adhesion additive and 10-40% of corrosion assistant. More preferably 20-35% adhesion additive and 20-35% corrosion aid. And/or

Preferably, the mass ratio of the nano silver coated by the organic coating agent to the crude glass powder is 0.1-5.0:1, preferably 1-4.0:1, more preferably 1.5-3.0:1, and even more preferably 2.0-2.5: 1. And/or

Preferably, the mass ratio of the nano silver coated by the organic coating agent to the organic solvent is 0.1-2:1, preferably 0.3-1.8:1, and more preferably 0.5-1.5: 1. And/or

Preferably, the silver content in the nano silver coated by the organic coating agent is 1% -12%, preferably 3% -10%, more preferably 5% -9%, and even more preferably 7% -8.5%.

Preferably, the particle size of the crude glass powder is less than 400 meshes, preferably less than 200 meshes, and more preferably less than 100 meshes. And/or

Preferably, the dispersion method is one or more of magnetic stirring, mechanical stirring and all-round ball milling. And/or

Preferably, the temperature of the heat treatment is 700-1200 ℃, preferably 800-1100 ℃, and more preferably 900-1000 ℃.

Preferably, the heat treatment time is from 0.5 to 10 hours, preferably from 1 to 8 hours, more preferably from 2 to 5 hours.

According to a second embodiment of the present invention, there is provided a method for producing a nano silver-containing glass powder or the nano silver-containing glass powder described in the first embodiment, the method comprising the steps of:

1) the oxide raw material and the auxiliary agent are crushed and mixed uniformly, and then the crude product of the glass powder is obtained after heat treatment, crushing and mixing are carried out in sequence.

2) Coating the nano silver by using an organic coating agent, dispersing the coated nano silver in an organic solvent, adding the crude glass powder obtained in the step 1), and uniformly mixing to obtain a nano silver-glass powder mixture.

3) And 3) carrying out ball milling, centrifuging, drying and crushing on the nano silver-glass powder mixture obtained in the step 2) in sequence to obtain the nano silver-containing glass powder.

Preferably, in step 1), the oxide feedstock comprises TeO₂、PbO、Tl₂O₃、Bi₂O3、Li₂O, optionally also including WO₃、ZnO、MgO、B₂O₃、CaO、TiO₂、Fe₂O₃、Al₂O₃、Ag₂O、ZrO₂、Na₂O、K₂One or more of O and MoO. And/or

Preferably, the additives are adhesion additives and corrosion additives; wherein the adhesion additive is selected from ZnO, WO₃、SiO₂、P₂O₅、B₂O₃、Ge₂O₃And NiO, or a mixture of a plurality of these components in an arbitrary ratio. And/or

Preferably, the corrosion aid is selected from Al₂O₃、Cr₂O₃、TiO₂、Al₂O₃、MnO₂、LiF、PbF₂、AlF₃、TiF₄、Ge₂O₃、Fe₂O₃One or more of CuO and MoO in any proportion. And/or

Preferably, the addition amount of the oxide raw material is 15-70% of TeO₂、5-50％PbO、0.3-30％Tl₂O₃、3-40％Bi₂O₃0.5-15% of Li₂O、Na₂O and K₂0 to 15 percent of O mixtureB₂O₃、0-10％CaO、0-15％SiO₂. Preferably 25-60% TeO₂、15-40％PbO、0.8-20％Tl₂O₃、8-30％Bi₂O₃1-12% of Li₂O、Na₂O and K₂Mixture of O, 0.5-12% of B₂O₃、0.5-8％CaO、0.8-12％SiO₂. More preferably 30-50% TeO₂、20-35％PbO、1.5-15％Tl₂O₃、12-25％Bi₂O₃3-10% of Li₂O、Na₂O and K₂Mixture of O, 1-10% of B₂O₃、1-6％CaO、1.5-10％SiO₂. And/or

Preferably, the addition amount of the additive is 1-50% of the adhesion additive and 1-50% of the corrosion additive. Preferably 10-40% of adhesion additive and 10-40% of corrosion assistant. More preferably 20-35% adhesion additive and 20-35% corrosion aid. And/or

Preferably, the temperature of the heat treatment is 700-1200 ℃, preferably 800-1100 ℃, and more preferably 900-1000 ℃.

Preferably, the heat treatment time is 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.

Preferably, in the step 2), the mass ratio of the nano silver coated by the organic coating agent to the organic solvent is not 0.1-2:1, preferably 0.3-1.8:1, and more preferably 0.5-1.5: 1. And/or

Preferably, the mass ratio of the nano silver coated by the organic coating agent to the crude glass powder is 0.1-5.0:1, preferably 1-4.0:1, more preferably 1.5-3.0:1, and even more preferably 2.0-2.5: 1. And/or

Preferably, the organic coating agent is selected from one or more of polymer acids, polymer ethers, polymer ketones, and polymer esters. Preferably polymeric ketones and/or polymeric esters. More preferably polyvinylpyrrolidone (PVP) and/or an acrylic resin (i.e. an ethyl acrylate/methyl methacrylate copolymer).

Preferably, the molecular weight of the organic coating agent is 5000-. And/or

Preferably, the silver content in the nano silver coated by the organic coating agent is 1% -12%, preferably 3% -10%, more preferably 5% -9%, and even more preferably 7% -8.5%. And/or

Preferably, the particle size of the added crude glass powder is less than 400 meshes, preferably less than 200 meshes, and more preferably less than 100 meshes. And/or

Preferably, the dispersion method is one or more of magnetic stirring, mechanical stirring and all-round ball milling.

Preferably, step 1) is specifically: the oxide raw material, the adhesion additive and the corrosion assistant are fully crushed (for example, ground) according to a proportion and then uniformly mixed to obtain a mixture. Then the mixture is placed in a high temperature furnace to be fired for 0.5 to 10 hours (preferably 1 to 8 hours, more preferably 2 to 5 hours) at the temperature of 700-1200 ℃ (preferably 800-1100 ℃, more preferably 900-1000 ℃) to obtain a firing material. And finally, taking out the fired material, sequentially performing water quenching, drying and sieving (for example, sieving by a 100-mesh sieve), and uniformly mixing to obtain a crude glass powder.

Preferably, step 2) is specifically: the nano silver is coated by the organic coating agent to obtain the nano silver coated by the organic coating agent. And then dispersing the nano silver coated by the organic coating agent (in a dispersing mode of one or more of magnetic stirring, mechanical stirring and all-dimensional ball milling) in an organic solvent (such as an alcohol solvent). And then adding the crude glass powder obtained in the step 1) into a dispersed nano-silver organic system, and uniformly stirring to obtain a nano-silver-glass powder mixture.

Preferably, step 3) is specifically: adding agate balls into the nano silver-glass powder mixture obtained in the step 2), and then carrying out ball milling (ball milling in an all-dimensional ball mill for 0.5-8h, preferably 1-6h, and more preferably 2-4 h). And then separating the agate balls, adding a proper amount of solvent (for example, the addition amount is 0.5-1.5 times of the original solvent), centrifuging (for 1-5 times, preferably 2-3 times), drying, and sieving (for example, sieving by a 100-500-mesh sieve, preferably sieving by a 300-500-mesh sieve) to obtain the nano-silver-containing glass powder.

In the prior art, the ball milling and dispersing processes are carried out step by step in the preparation of the glass powder, so that the preparation time is long, in addition, the redundant organic coating agent cannot be well removed, and finally, solid powder is difficult to obtain or the yield of the solid powder is low.

In the invention, the organic coating nano silver coated by the organic coating agent is mixed with the crude glass powder, then the nano silver-glass powder system is prepared by adopting omnibearing ball milling and dispersion, then the redundant coating agent is removed by multiple times of centrifugation, and the final product is obtained by drying and sieving, thus the preparation time can be greatly shortened, and the agglomeration phenomenon of micro-nano particles is prevented.

In the invention, the nano silver coated by the organic coating agent is dispersed in the organic solvent by adopting an all-round ball milling dispersion method, the method is to respectively carry out 360-degree rotation high-speed mixing in the horizontal direction and the vertical direction, and the organic coating agent is uniformly dispersed while the grain diameter of the glass powder is ball milled, so that the agglomeration of micro-nano particles is prevented.

Compared with the prior art, the invention has the following technical effects:

the invention adopts the omnibearing ball milling dispersion to prepare the nano silver-glass powder system, then centrifugalizes to remove the redundant coating agent, dries and screens to obtain the final product. The glass powder prepared by the method can greatly increase the contact of the cell in the silver paste on the front surface of the solar cell, and the conversion efficiency of the cell is improved.

Detailed Description

The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.

Example 1

Weighing an oxide raw material of target glass powder (called BL001), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 100.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, then 20.00 g of glass powder crude product (BL001) is added, and after uniform stirring and mixing, a nano silver-glass powder mixture is obtained; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 2

Weighing an oxide raw material of target glass powder (called BL002), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 80.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, then 20.00 g of glass powder crude product (BL002) is added, and after uniform stirring and mixing, a nano silver-glass powder mixture is obtained; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 3

Weighing an oxide raw material of target glass powder (called BL003), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 60.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, 20.00 g of glass powder crude product (BL003) is added, and the mixture is stirred and mixed uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 4

Weighing an oxide raw material of target glass powder (called BL004), fully grinding, mixing, transferring into a high-temperature furnace, firing for 1 hour at 900 ℃, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then dispersing 40.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) in 60ml of ethanol solvent (magnetic stirring), then adding 20.00 g of glass powder crude product (BL004), and stirring and mixing uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 5

Weighing an oxide raw material of target glass powder (called BL005), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 20.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, then 20.00 g of glass powder crude product (BL005) is added, and after uniform stirring and mixing, a nano silver-glass powder mixture is obtained; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 6

Weighing an oxide raw material of target glass powder (called BL006), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving with a 100-mesh sieve to obtain a crude glass powder product; then dispersing 10.00 g of polyvinylpyrrolidone (PVP) coated nano silver (silver content 8%) in 60ml of ethanol solvent (magnetic stirring), then adding 20.00 g of glass powder crude product (BL006), and stirring and mixing uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 7

Weighing an oxide raw material of target glass powder (called BL007), fully grinding, mixing, transferring into a high-temperature furnace for firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude product of the glass powder; then 100.00 g of acrylic resin coated nano silver (silver content 8%) is dispersed (magnetic stirring) in 60ml of ethanol solvent, then 20.00 g of glass powder crude product (BL007) is added, and after uniform stirring and mixing, a nano silver-glass powder mixture is obtained; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 8

Weighing an oxide raw material of target glass powder (called BL008), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 80.00 g of acrylic resin coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, and then 20.00 g of glass powder crude product (BL008) is added, and after uniform stirring and mixing, a nano silver-glass powder mixture is obtained; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 9

Weighing an oxide raw material of target glass powder (called BL009), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 60.00 g of acrylic resin coated nano silver (silver content 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, 20.00 g of glass powder crude product (BL009) is added, and the mixture is stirred and mixed uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 10

Weighing an oxide raw material of target glass powder (called BL010), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, 40.00 g of acrylic resin-coated nano silver (with silver content of 8%) is dispersed (magnetically stirred) in 60ml of ethanol solvent, and then 20.00 g of glass powder crude product (BL010) is added, and the mixture is stirred and mixed uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 11

Weighing an oxide raw material of target glass powder (called BL011), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then, dispersing 20.00 g of acrylic resin-coated nano silver (with silver content of 8%) in 60ml of ethanol solvent (magnetic stirring), then adding 20.00 g of glass powder crude product (BL011), and stirring and mixing uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 12

Weighing an oxide raw material of target glass powder (called BL012), fully grinding, mixing, transferring into a high-temperature furnace, firing at 900 ℃ for 1 hour, pouring out water quenching, collecting a product, drying, and sieving by a 100-mesh sieve to obtain a crude glass powder product; then dispersing 10.00 g of acrylic resin coated nano silver (silver content 8%) in 60ml of ethanol solvent (magnetic stirring), then adding 20.00 g of glass powder crude product (BL012), and stirring and mixing uniformly to obtain a nano silver-glass powder mixture; and then adding agate balls phi 6 into the obtained nano silver-glass powder mixture: 150 g, φ 10: 30 particles are put into an all-directional ball mill to be ball-milled for 2 hours after being uniformly stirred, and agate balls are sieved to obtain a nano silver-glass powder suspension system; then adding 100ml of absolute ethyl alcohol into the nano silver-glass powder suspension system, uniformly stirring, centrifuging to remove supernatant (repeatedly adding 100ml of absolute ethyl alcohol, uniformly stirring, and centrifuging to remove supernatant until no solid particles exist in supernatant); drying and crushing the lower layer solid product, and sieving with a 500-mesh sieve to obtain the refined glass powder containing the nano silver.

Example 13

Example 3 was repeated except that the glass firing temperature was 1000 ℃ and held for 3 hours.

Example 14

Example 3 was repeated except that the glass firing temperature was 950 ℃ for 2 hours.

Example 15

Example 9 was repeated except that the glass firing temperature was 1000 ℃ and the incubation time was 3 hours.

Example 16

Example 9 was repeated except that the glass firing temperature was 950 ℃ for 2 hours.

Comparative examples

Comparing the application performance of the nano silver-glass powder BL003 (containing nano silver powder) obtained in example 3 with that of the glass powder BL 003' without nano silver, firstly, the prepared glass is prepared into slurry, and after screen printing, the main performance parameters of the solar cell are tested, and the results are as follows:

from the above table, the glass powder containing nano-silver prepared by the method of the invention can improve the cell contact, reduce Rs (series resistance) and improve the fill factor FF in the front silver paste of the solar cell, thereby helping to improve the conversion efficiency of the solar cell.

The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any way; those skilled in the art can now make changes and modifications to the disclosed technology, which are equivalent to those of the disclosed embodiments. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the invention without departing from the essential contents of the technical solution of the invention still belong to the protection scope of the technical solution of the invention.