發(fā)布時間：2018-03-25 05:28

  本文選題：熱電材料　切入點：熱電復合材料　出處：《浙江理工大學》2017年碩士論文

【摘要】：熱電材料是一類利用固體內部載流子的移動來實現電能和熱能相互轉化的材料,在溫控、溫差發(fā)電、汽車尾氣和工業(yè)余熱的回收利用等領域具有非常廣闊的應用前景。聚合物材料具有本征低熱導率,很好的溶液加工性能,原材料來源豐富、價格低廉等優(yōu)勢,因而引起了熱電領域研究者們的廣泛關注。其中聚苯胺作為一種易合成、易加工的導電聚合物,被認為是最具有發(fā)展?jié)摿Φ木酆衔餆犭姴牧现�。然�?目前聚苯胺材料的熱電性能還遠遠達不到實際應用要求。為進一步提升聚苯胺熱電性能,以達到實際應用目標,將其作為基體,引入高性能低維納米材料制備復合材料來優(yōu)化材料的熱電性能成為目前的研究熱點。本文以碳納米管(CNTs)和還原態(tài)氧化石墨烯(RGO)作為填充模板,以導電聚合物聚3,4-乙烯二氧噻吩:聚苯乙烯磺酸(PEDOT:PSS)作為分散穩(wěn)定物質均勻的分散填充物,再采用化學原位聚合的方式合成有序分子鏈結構的PANI進而制得三種復合材料即CNTs/PEDOT:PSS/PANI,RGO/PEDOT:PSS/PANI與CNTs/RGO/PEDOT:PSS/PANI。采用XRD、FE-SEM對復合材料的結構進行表征,并測試了復合材料的電導率、Seebeck系數、熱導率等熱電性能參數。同時,本文也探究了填充物(CNTs/RGO)與PEDOT:PSS的比例,填充物CNTs與RGO的比例及填充物含量對材料熱電性能的影響,得出以下結論:(1)在CNTs/PEDOT:PSS/PANI復合材料中,PEDOT:PSS作為分散穩(wěn)定物質,隨著其與CNTs比例的的提升,CNTs分散程度得以提升,復合材料熱電性能得到一定程度的提升。當CNTs與PEDOT:PSS的比例達到1:4時,最大ZT值為1.21×10-6。隨著CNTs含量的提升,填充物接觸距離減小,利于載流子傳輸,提升電導率。同時,由于復合材料界面的能量滲濾效應和聲子散射效應,提升了Seebeck系數,降低了熱導率,進而提升了ZT。CNTs含量為50%時,最大值ZT為2.09×10-5,相對于純的PANI提升了約31倍。(2)采用原位聚合的方式制備RGO/PEDOT:PSS/PANI復合材料。隨著RGO的提升,復合材料引入更大的界面區(qū)域,能量滲濾效應增強,有效提升了Seebeck系數,而填充含量的增加也可促進電導率的提升,最終熱電性能得以提升。當RGO含量為50%時,復合材料的最大ZT值為7.25×10-6,相比于純的PANI提升了約10.5倍。(3)采用原位聚合的方式制備CNTs/RGO/PEDOT:PSS/PANI復合材料。一維的CNTs與二維的RGO之間有強烈的相互作用,進而引發(fā)協(xié)同效應。當CNTs與RGO的比例為2:1時,協(xié)同效果較為明顯。隨著填充物(CNTs/RGO)含量的提升,復合材料的電導率、Seebeck系數及ZT也隨之提升。當填充物含量為50%時,一維/二維協(xié)同復合材料的最大ZT值為2.38×10-5,與CNTs含量為50%的CNTs/PEDOT:PSS/PANI相比,提升了約1.2倍,與RGO含量50%的RGO/PEDOT:PSS/PANI相比,提升了約3.3倍,而相對于PANI提升了約36倍。
[Abstract]:Thermoelectric materials are a kind of materials that use the movement of carriers in solids to realize the mutual conversion of electric energy and heat energy. The application prospect of automobile exhaust gas and industrial waste heat recovery is very broad. Polymer materials have the advantages of intrinsic low thermal conductivity, good solution processing performance, abundant raw material sources, low price, etc. As a kind of conductive polymer, Polyaniline is considered as one of the most potential polymer thermoelectric materials. At present, the thermoelectric properties of Polyaniline materials are still far from the practical application requirements. In order to further improve the thermoelectric properties of Polyaniline in order to achieve the practical application goal, the Polyaniline is used as the matrix. In order to optimize the thermoelectric properties of high performance low-dimensional nanocomposites, CNTsand reduced graphene oxide (RGOO) were used as filling templates. A conductive polymer, poly (3o 4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT: PSS), was used as a uniform dispersive filler with stable dispersion. Then the PANI with ordered molecular chain structure was synthesized by chemical in-situ polymerization, and three kinds of composites, CNTs / PEDOT: PSSP / PSSP / PSSP / PSSP / pani and CNTsR / RGOP / PEDOT / PSSP / PANI, were prepared. The structure of the composites was characterized by XRDX FE-SEM, and the conductivity of the composites was measured by Seebeck coefficient. At the same time, the ratio of filler CNTs / RGO to PEDOT:PSS, the ratio of filler CNTs to RGO and the effect of filler content on the thermoelectric properties of the material were also investigated. The following conclusion is drawn: (1) in CNTs/PEDOT:PSS/PANI composites, PEDOT: PSS is used as a dispersion stabilizer. The thermoelectric properties of CNTs/PEDOT:PSS/PANI composites are improved to a certain extent with the increase of the ratio of CNTs to CNTs. When the ratio of CNTs to PEDOT:PSS reaches 1:4, The maximum ZT value is 1.21 脳 10 ~ (-6). With the increase of CNTs content, the contact distance of the filler decreases, which is beneficial to carrier transport and increase the conductivity. At the same time, the Seebeck coefficient is increased because of the energy percolation effect and phonon scattering effect at the interface of the composite. When the content of ZT.CNTs is 50, the maximum ZT value is 2.09 脳 10 ~ (-5), which is about 31 times higher than that of pure PANI, and the RGO/PEDOT:PSS/PANI composite is prepared by in-situ polymerization. With the increase of RGO, the interface area of the composite is larger. The energy percolation effect is enhanced, the Seebeck coefficient is increased effectively, and the electrical conductivity is promoted by the increase of the filling content. Finally, the thermoelectric properties are improved when the RGO content is 50. The maximum ZT value of the composite is 7.25 脳 10 ~ (-6), which is about 10.5 times higher than that of pure PANI.) CNTs/RGO/PEDOT:PSS/PANI composites are prepared by in-situ polymerization. There is a strong interaction between one-dimensional CNTs and two-dimensional RGO. When the ratio of CNTs to RGO is 2:1, the synergistic effect is obvious. With the increase of the content of CNTs / RGO, the conductivity and ZT of composites also increase. The maximum ZT value of one-dimensional / two-dimensional synergistic composites is 2.38 脳 10 ~ (-5), which is about 1.2 times higher than that of CNTs/PEDOT:PSS/PANI with 50% CNTs content, 3.3 times higher than RGO/PEDOT:PSS/PANI with 50% RGO content, and 36 times higher than that of PANI.
【學位授予單位】：浙江理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB34

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