Wang Ningzhen, van Turnhout Jan, Daniels Robert, Wu Chao, Huo Jindong, Gerhard Reimund, Sotzing Gregory, Cao Yang
Electrical Insulation Research Center, Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269, United States.
Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628CD Delft, The Netherlands.
ACS Appl Mater Interfaces. 2022 Sep 21;14(37):42705-42712. doi: 10.1021/acsami.2c12185. Epub 2022 Sep 13.
In contrast to molecular-dipole polymers, such as PVDF, ferroelectrets are a new class of flexible spatially heterogeneous piezoelectric polymers with closed or open voids that act as deformable macro-dipoles after charging. With a spectrum of manufacturing processes being developed to engineer the heterogeneous structures, ferroelectrets are made with attractive piezoelectric properties well-suited for applications, such as pressure sensors, acoustic transducers, etc. However, the sources of the macro-dipole charges have usually been the same, microscopic dielectric barrier discharges within the voids, induced when the ferroelectrets are under a large electric field typically via a so-called corona poling, resulting in the separation and trapping of opposite charges into the interior walls of the voids. Such a process is inherently self-limiting, as the reverse internal field from the macro-dipoles eventually extinguishes the microdischarges, resulting in limited density of ions and not too high overall piezoelectric performance. Here, a new method to form ferroelectrets with gigantic electroactivity is proposed and demonstrated with the aid of an external ion booster. A laminate consisting of expanded polytetrafluoroethylene (ePTFE) and fluorinated-ethylene-propylene (FEP) was prefilled with bipolar ions produced externally by an ionizer and sequentially poled to force the separation of positive and negative ions into the open fibrous structure, rendering an impressive piezoelectric coefficient of 1600 pC/N─an improvement by a factor of 4 in comparison with the of a similar sandwich poled with nonenhanced corona poling. The (pre)filling clearly increases the ion density in the open voids significantly. The charges stored in the open-cell structure stays at a high level for at least 4 months. In addition, an all-organic nanogenerator was made from an ePTFE-based ferroelectret, with conducting poly(3,4-ethylene dioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) coated fabric electrodes. When poled with this ion-boosting process, it yielded an output power twice that of a similar sample poled in a conventional corona-only process. The doubling in output power is mainly brought about by the significantly higher charge density achieved with the aid of external booster. Furthermore, aside from the bipolar ions, extra monopolar ions can during the corona poling be blown into the open pores by using for instance a negative ionic hair dryer to produce a unipolar ePTFE-based ferroelectret with its coefficient enhanced by a factor of 3. Ion-boosting poling thus unleashes a new route to produce bipolar or unipolar open-cell ferroelectrets with highly enhanced piezoelectric response.
与分子偶极聚合物(如聚偏氟乙烯)不同,铁电驻极体是一类新型的柔性空间异质压电聚合物,具有封闭或开放的空隙,在充电后这些空隙可作为可变形的宏观偶极子。随着一系列用于设计异质结构的制造工艺的发展,铁电驻极体具有吸引人的压电特性,非常适合诸如压力传感器、声换能器等应用。然而,宏观偶极电荷的来源通常相同,即空隙内的微观介质阻挡放电,当铁电驻极体处于强电场下时,通常通过所谓的电晕极化诱导产生这种放电,导致相反电荷分离并捕获到空隙的内壁。这样的过程本质上是自我限制的,因为宏观偶极子产生的反向内场最终会熄灭微放电,导致离子密度有限且整体压电性能不太高。在此,提出并借助外部离子增强器演示了一种形成具有巨大电活性的铁电驻极体的新方法。一种由膨化聚四氟乙烯(ePTFE)和氟化乙烯丙烯(FEP)组成的层压板预先填充有由离子发生器外部产生的双极离子,并依次极化以迫使正离子和负离子分离到开放的纤维结构中,产生了令人印象深刻的1600 pC/N的压电系数——与采用非增强电晕极化的类似三明治结构相比提高了4倍。这种(预)填充明显显著增加了开放空隙中的离子密度。存储在开孔结构中的电荷至少在4个月内保持在高水平。此外,一种基于ePTFE的铁电驻极体制成了全有机纳米发电机,其织物电极涂覆有导电聚(3,4 - 亚乙二氧基噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)。当采用这种离子增强极化工艺时,其输出功率是采用传统仅电晕极化工艺的类似样品的两倍。输出功率翻倍主要是由于借助外部增强器实现了显著更高的电荷密度。此外,除了双极离子外,在电晕极化过程中,例如可以使用负离子吹风机将额外的单极离子吹入开放孔中,以生产基于ePTFE的单极铁电驻极体,其压电系数提高了3倍。因此,离子增强极化开辟了一条生产具有高度增强压电响应的双极或单极开孔铁电驻极体的新途径。