Preparation and thermoelectric properties of N type Ag2Te@PEDOT:PSS composite films
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摘要: 利用一步热还原法制备了聚3, 4-乙烯二氧噻吩:聚苯乙烯磺酸包覆的Te纳米线(Te@PEDOT:PSS)复合膜，然后将其浸入不同浓度的AgNO3溶液中，通过Ag+与Te的反应使Te向Ag2Te转变，从而使热电材料由P型的Te@PEDOT:PSS复合膜转化为N型的Ag2Te@PEDOT:PSS复合膜。通过FESEM、TEM、XPS、XRD等表征手段揭示了掺杂过程中AgNO3与Te@PEDOT:PSS复合膜的作用机制，探究了掺杂浓度对Ag2Te@PEDOT:PSS复合膜热电性能的影响。反应中Ag2Te@PEDOT:PSS复合膜的电导率随着AgNO3溶液浓度的增加呈先增大后减小的趋势，主要是由于AgNO3浓度较大时生成TeO2造成的，Seebeck系数随着AgNO3浓度增大而迅速减小，主要是由于反应生成的Ag2Te为N型传导，当Ag2Te所提供的电子数量超过Te提供的空穴数量时，材料的传导机制由P型变为N型，即Seebeck系数由正变负，随着AgNO3浓度的增大，Seebeck系数的绝对值变大，当AgNO3溶液浓度为10 mmol时，Seebeck系数为(−55.9±3.3) μV/K。当AgNO3溶液浓度为20 mmol时，N型Ag2Te@PEDOT:PSS复合膜的功率因子达最大值，为(8.4±0.7) μW/(m·K2)。Abstract: The poly(3,4-ethyl-enedioxythiophene): polystyrenesulfonate functionalized Te nanowires (Te@PEDOT:PSS) composite films were in situ synthesized using a one-step thermal reduction process. Then the Te@PEDOT:PSS composite films were immersed into AgNO3 solutions with different concentration to prepare Ag2Te@PEDOT:PSS composite films. By introducing Ag+ into the Te@PEDOT:PSS composite films, P type Te@PEDOT:PSS composite films was transformed to N type Ag2Te@PEDOT:PSS composite films. FESEM, TEM, XPS, and XRD were used to analysis the reaction mechanism between AgNO3 and Te@PEDOT:PSS composite films. Also, the thermoelectric properties of the Ag2Te@PEDOT:PSS composite films as a function of AgNO3 concentration were measured. The electrical conductivity of Ag2Te@PEDOT:PSS composite films first increases as the increasing AgNO3 concentration, and then decreases due to the formation of TeO2. The Seebeck coefficient of the Ag2Te@PEDOT:PSS composite films decreases significantly with the increasing concentration of AgNO3. The phenomenon can be contributed to the N type conduction of Ag2Te, and when the amount of electron provided by Ag2Te is larger than the amount of hole from Te, the conduction mechanism changes from P type to N type. As the further increasing concentration of AgNO3, the absolute value of Seebeck coefficient of the Ag2Te@PEDOT:PSS composite films increases. And the value reaches (−55.9±3.3) μV/K when the concentration of AgNO3 is 10 mmol. The N type Ag2Te@PEDOT:PSS composite film shows a maximum power factor of (8.4±0.7) μW/(m·K2) with 20 mmol AgNO3.
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Key words:
- PEDOT:PSS /
- Ag2Te /
- composites /
- thermoelectric properties /
- film /
- Seebeck coefficient
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图 1 聚3, 4-乙烯二氧噻吩:聚苯乙烯磺酸包覆的Te纳米线(Te@PEDOT:PSS)复合膜及不同AgNO3浓度的Ag2Te@PEDOT:PSS复合膜的FESEM图像: (a) Te@PEDOT:PSS; (b) 0.1 mmol AgNO3; (c) 5 mmol AgNO3; (d) 10 mmol AgNO3
Figure 1. FESEM images of poly(3,4-ethyl-enedioxythiophene): polystyrenesulfonate functionalized Te nanowires (Te@PEDOT:PSS) composite film and Ag2Te@PEDOT:PSS composite films immersed in different concentration of AgNO3:(a) Te@PEDOT:PSS; (b) 0.1 mmol AgNO3; (c) 5 mmol AgNO3; (d) 10 mmol AgNO3
图 2 低倍下5 mmol (a)和10 mmol (b) AgNO3浸泡后Ag2Te@PEDOT:PSS复合膜的FESEM图像
Figure 2. Low resolution FESEM images of Ag2Te@PEDOT:PSS composite films immersed in 5 mmol (a) and 10 mmol (b) AgNO3
图 3 不同AgNO3浓度掺杂后Ag2Te@PEDOT:PSS复合膜的XRD图谱
Figure 3. XRD patterns of Ag2Te@PEDOT:PSS composite films doped by AgNO3 with different concentration
图 4 Te@PEDOT:PSS复合膜(a)和不同浓度AgNO3溶液掺杂后Ag2Te@PEDOT:PSS复合膜((b) 0.1 mmol AgNO3, (c) 5 mmol AgNO3,(d) 10 mmol AgNO3)的TEM图像及不同浓度AgNO3溶液掺杂后Ag2Te@PEDOT:PSS复合膜的EDS图谱((e) 0.1 mmol AgNO3, (f) 5 mmol AgNO3, (g) 10 mmol AgNO3; 对应 TEM图像中(b), (c), (d)的圈内成分)
Figure 4. TEM images of Te@PEDOT:PSS composite film (a) and Ag2Te@PEDOT:PSS composite films doped by AgNO3 with different concentration ((b) 0.1 mmol AgNO3, (c) 5 mmol AgNO3, (d) 10 mmol AgNO3) and EDS spectra of Ag2Te@PEDOT:PSS composite films doped by AgNO3 with different concentration ((e) 0.1 mmol AgNO3, (f) 5 mmol AgNO3, (g) 10 mmol AgNO3; Corresponding to circle part of TEM images in (b), (c) and (d))
图 5 不同浓度AgNO3溶液掺杂后Ag2Te@PEDOT:PSS复合膜的XPS图谱: (a)全谱; (b) Te; (c) S
Figure 5. XPS spectra of Ag2Te@PEDOT:PSS composite films by AgNO3 with different concentration: (a) Survey; (b) Te; (c) S
图 6 不同浓度的AgNO3溶液掺杂后Ag2Te@PEDOT:PSS复合膜的热电性能
Figure 6. Thermoelectric properties of Ag2Te@PEDOT:PSS composite films by AgNO3 with different concentration
σ—Electrical conductivity; S—Seebeck coefficient; P—Power factor
表 1 5 mmol AgNO3浸泡后Ag2Te@PEDOT:PSS复合膜表层结晶物元素含量
Table 1. Element contents of crystal on surface of Ag2Te@ PEDOT:PSS composite film immersed in 5 mmol AgNO3
Element Mass fraction/% Atomic fraction/% O 7.80 40.10 Ag 3.95 3.01 Te 88.25 56.89 
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表 2 0.1 mmol AgNO3浸泡后Ag2Te@PEDOT:PSS复合膜的元素含量
Table 2. Element contents of Ag2Te@PEDOT:PSS composite film immersed in 0.1 mmol AgNO3
Element Mass fraction/% Atomic fraction/% S 0.5 2.1 Ag 2.8 3.3 Te 96.6 94.6
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表 3 5 mmol AgNO3浸泡后Ag2Te@PEDOT:PSS复合膜的元素含量
Table 3. Element contents of Ag2Te@PEDOT:PSS composite film immersed in 5 mmol AgNO3
Element Mass fraction/% Atomic fraction/% S 0.4 1.5 Ag 57.6 60.9 Te 42.0 37.6
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表 4 10 mmol AgNO3浸泡后Ag2Te@PEDOT:PSS复合膜的元素含量
Table 4. Element contents of Ag2Te@PEDOT:PSS composite film immersed in 10 mmol AgNO3
Element Mass fraction/% Atomic fraction/% S 0.3 1.0 Ag 59.9 63.4 Te 39.9 35.7
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