Preparation and performance of silver micro-nanoparticles for electrode silver paste
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摘要: 以硝酸银为前驱体, 抗坏血酸为还原剂, 单宁为分散剂, 采用液相化学还原法制备了微纳米超细银颗粒。通过X射线衍射仪、扫描电子显微镜、激光粒度分析仪、振实密度仪及太阳能性能测试仪等设备研究了反应物浓度、分散剂剂量、pH值等工艺参数对银颗粒形貌、平均粒径及振实密度的影响。结果表明, 当硝酸银浓度为0.1mol·L-1, 抗坏血酸浓度为0.1mol·L-1, 单宁浓度为0.01mol·L-1, pH值为1, 反应温度为25℃时, 能够获得分散性良好的球状银颗粒; 将平均粒径为1.16μm和0.66μm的两种银粉按照一定质量比进行混合, 制备得到的混合银粉最高振实密度可达到6.1g·mL-1; 通过研究基于不同振实密度银粉的银电极表面形貌和电池性能, 可以得出基于振实密度6.1g·mL-1混合银粉所制的银电极相对密度最好, 太阳能电池的光电转换效率最高, 达到17.16%。Abstract: The silver particles in micro-nanometer size were prepared by solution chemical reduction method using AgNO3 as the precursor, C6H8O6 as the reducing agent, and tannin as the dispersant. The effects of reactant concentration, dispersant dosage, and pH value on the morphology, average particle size, and tap density of the silver powders were studied by X-ray diffractometer, scanning electron microscope, laser particle size analyzer, tapping apparatus, and solar energy performance tester. The results show that, the well-dispersed silver powders with spherical shape are synthesized under the optimal conditions as the pH value of 1, the AgNO3 concentration of 0.1 mol·L-1, the C6H8O6 concentration of 0.1 mol·L-1, the tannin concentration of 0.01 mol·L-1, and the reaction temperature of 25℃. The silver powders with the maximum tap density of 6.1 g·mL-1 can be obtained by mixing the silver powders in an average particle size of 1.16 μm and 0.66 μm. According to the surface morphology and battery performance of silver electrode, the silver electrode based on the mixed silver powders in the tap density of 6.1 g·mL-1 shows the best relative density, and the photoelectric conversion efficiency of the solar cell is the highest, reaching 17.16%.
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Key words:
- silver particles /
- micro-nanometer size /
- tap density /
- electrode /
- chemical reduction method
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图 1 不同硝酸银浓度所制备的银颗粒扫描电子显微形貌：（a)0.03 mol·L-1; (b)0.06 mol·L-1; (c)0.10 mol·L-1; (d)0.15 mol·L-1
Figure 1. SEM images of silver particles prepared by different AgNO3 concentrations: (a)0.03 mol·L-1; (b)0.06 mol·L-1; (c)0.10 mol·L-1; (d)0.15 mol·L-1
图 2 不同抗坏血酸浓度所制备的银颗粒扫描电子显微形貌：(a)0.10 mol·L-1; (b)0.15 mol·L-1; (c)0.20 mol·L-1; (d)0.25 mol·L-1
Figure 2. SEM images of silver particles prepared by different C6H8O6 concentrations: (a)0.10 mol·L-1; (b)0.15 mol·L-1; (c)0.20 mol·L-1; (d)0.25 mol·L-1
图 3 不同单宁浓度所制备的银颗粒扫描电子显微形貌：(a)0.01 mol·L-1; (b)0.05 mol·L-1; (c)0.10 mol·L-1; (d)0.20 mol·L-1
Figure 3. SEM images of silver particles prepared by different tannin concentrations: (a)0.01 mol·L-1; (b)0.05 mol·L-1; (c)0.10 mol·L-1; (d)0.20 mol·L-1
图 4 不同pH值所制备的银颗粒扫描电子显微形貌：(a)1;(b)3;(c)5;(d)7
Figure 4. SEM images of silver particles prepared in different pH values: (a)1;(b)3;(c)5;(d)7
图 5 最优条件下制备银颗粒的X射线衍射图
Figure 5. XRD pattern of silver particles prepared under the optimal conditions
图 6 基于不同振实密度银颗粒的银电极扫描电子显微形貌：(a)5.6 g·m L-1; (b)5.8 g·m L-1; (c)6. 1 g·m L-1
Figure 6. SEM images of silver electrodes based on the silver particles with different tap density: (a)5.6 g·m L-1; (b)5.8 g·m L-1; (c)6.1 g·m L-1
表 1 不同硝酸银浓度所制银粉特性
Table 1. Characteristics of silver powders prepared by different AgNO3 concentrations
硝酸银/(mol·L-1) 平均粒径/μm 振实密度/(g·mL-1) 0.03 0.66 4.10 0.06 0.96 4.43 0.10 1.16 5.20 0.15 2.35 4.95 
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表 2 不同抗坏血酸浓度所制银粉特性
Table 2. Characteristics of silver powders prepared by different C6H8O6 concentrations
抗坏血酸/(mol·L-1) 平均粒径/μm 振实密度/(g·mL-1) 0.10 1.16 5.20 0.15 0.66 4.50 0.20 0.43 3.60 0.25 0.25 3.10
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表 3 不同单宁浓度所制银粉的特性
Table 3. Characteristics of silver powders prepared by different tannin concentrations
单宁/(mol·L-1) 平均粒径/μm 振实密度/(g·mL-1) 0.01 1.16 5.20 0.05 0.87 4.20 0.10 0.95 3.80 0.20 1.25 3.20
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表 4 不同pH值所制银粉的特性
Table 4. Characteristics of silver powders prepared in different pH values
pH值 平均粒径/μm 振实密度/(g·mL-1) 1 1.16 5.20 3 1.07 4.00 5 0.90 3.50 7 0.78 2.80
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表 5 混合银粉的特性
Table 5. Characteristics of the mixed silver powders
银粉质量比* 平均粒径/μm 振实密度/(g·mL-1) 9:1 1.13 5.6 8:2 1.08 5.8 7:3 1.02 6.1 6:4 0.98 5.9 注：比号前面为平均粒径为1.16 μm的银粉，比号后面为平均粒径为0.66 μm的银粉
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表 6 用不同振实密度银粉所制的太阳能电池光电性能
Table 6. Photoelectric performances of the silicon solar cells based on the silver powders with different tap density
银粉振实密度/(g·mL-1) 开路电压/V 短路电流/A 串联电阻/Ω 填充因子/% 光电转换效率/% 5.6 0.6008 5.5773 0.0175 77.51 15.36 5.8 0.6278 5.6083 0.0156 72.61 16.39 6.1 0.6257 5.6198 0.0086 76.12 17.16
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