Hao Tingting, Wang Shen, Xu Hongbo, Zhang Xiang, Magdassi Shlomo, Pan Lei, Song Ying, Li Yao, Zhao Jiupeng
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001, People's Republic of China.
Center for Composite Materials and Structure, Harbin Institute of Technology, Harbin, Heilongjiang 150001, People's Republic of China.
ACS Appl Mater Interfaces. 2022 May 11;14(18):21613-21622. doi: 10.1021/acsami.1c25002. Epub 2022 Apr 28.
The application of flexible indium tin oxide (ITO)-free electrochromic devices (FCDs) has always been a research hotspot in flexible electronics. Recently, a silver nanowire (AgNW)-based transparent conductive film has raised great interest as an ITO-free substrate for FCDs. However, several challenges, such as the weak binding of AgNWs to the substrate, high junction resistance, and oxidation of AgNWs, remain. In this paper, a novel method for surface modification of AgNWs with -aminoethyl-γ-aminopropyltrimethoxysilane [Si(NH)] solution is proposed to enhance the bonding with the flexible substrates and the active materials, thereby inhibiting the delamination of AgNWs from the substrate and reducing the high junction resistance between nanowires. The TiO/AgNW-Si(NH)/poly(ethylene terephthalate) (PET) films show outstanding mechanical properties, of which the resistance remains almost unchanged after mechanical bending of 5000 cycles (Δ/ ≈ 3.6%) and repeated peeling off cycles with 3M tape 100 times (Δ/ ≈ 6.0%). In addition, we found that the oxygen-containing groups on the TiO/AgNW-Si(NH)/PET surface form hydrogen bonds with the TiO sol, resulting in tight contact between the TiO sol and the AgNWs, which prevents the AgNWs from oxidation. As a result, the TiO/AgNW-Si(NH)/PET film exhibited long-time aging (Δ/ ≈ 4.9% in the air for 100 days) stability. A FCD was constructed with the TiO/AgNW-Si(NH)/PET film, which showed excellent electrochromic performance (94% retention) after 5000 bending cycles, indicating high stability and mechanical flexibility. These results present a promising solution to the transparent conductive films for flexible energy devices.
柔性氧化铟锡(ITO)无机电致变色器件(FCDs)的应用一直是柔性电子学领域的研究热点。近来,一种基于银纳米线(AgNW)的透明导电膜作为FCDs的无ITO衬底引起了极大关注。然而,仍存在一些挑战,如AgNWs与衬底的结合力弱、结电阻高以及AgNWs的氧化等问题。本文提出了一种用γ-氨丙基三甲基硅烷[Si(NH)]溶液对AgNWs进行表面改性的新方法,以增强其与柔性衬底和活性材料的结合,从而抑制AgNWs从衬底上分层,并降低纳米线之间的高结电阻。TiO/AgNW-Si(NH)/聚对苯二甲酸乙二酯(PET)薄膜表现出优异的机械性能,在5000次机械弯曲循环(Δ/R≈3.6%)和用3M胶带反复剥离100次循环(Δ/R≈6.0%)后,其电阻几乎保持不变。此外,我们发现TiO/AgNW-Si(NH)/PET表面的含氧基团与TiO溶胶形成氢键,导致TiO溶胶与AgNWs紧密接触,从而防止AgNWs氧化。结果,TiO/AgNW-Si(NH)/PET薄膜表现出长时间老化(在空气中放置100天,Δ/R≈4.9%)稳定性。用TiO/AgNW-Si(NH)/PET薄膜构建了一个FCD,在5000次弯曲循环后显示出优异的电致变色性能(保留率94%),表明具有高稳定性和机械柔韧性。这些结果为柔性能量器件的透明导电膜提供了一个有前景的解决方案。