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    Imperceptible Supercapacitors with High Area-Specific Capacitance
    (Weinheim : Wiley-VCH, 2021) Ge, Jin; Zhu, Minshen; Eisner, Eric; Yin, Yin; Dong, Haiyun; Karnaushenko, Dmitriy D.; Karnaushenko, Daniil; Zhu, Feng; Ma, Libo; Schmidt, Oliver G.
    Imperceptible electronics will make next-generation healthcare and biomedical systems thinner, lighter, and more flexible. While other components are thoroughly investigated, imperceptible energy storage devices lag behind because the decrease of thickness impairs the area-specific energy density. Imperceptible supercapacitors with high area-specific capacitance based on reduced graphene oxide/polyaniline (RGO/PANI) composite electrodes and polyvinyl alcohol (PVA)/H2SO4 gel electrolyte are reported. Two strategies to realize a supercapacitor with a total device thickness of 5 µm—including substrate, electrode, and electrolyte—and an area-specific capacitance of 36 mF cm−2 simultaneously are implemented. First, the void volume of the RGO/PANI electrodes through mechanical compression is reduced, which decreases the thickness by 83% while retaining 89% of the capacitance. Second, the PVA-to-H2SO4 mass ratio is decreased to 1:4.5, which improves the ion conductivity by 5000% compared to the commonly used PVA/H2SO4 gel. Both advantages enable a 2 µm-thick gel electrolyte for planar interdigital supercapacitors. The impressive electromechanical stability of the imperceptible supercapacitors by wrinkling the substrate to produce folds with radii of 6 µm or less is demonstrated. The supercapacitors will be meaningful energy storage modules for future self-powered imperceptible electronics.
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    Stamping Fabrication of Flexible Planar Micro‐Supercapacitors Using Porous Graphene Inks
    (Hoboken : Wiley, 2020) Li, Fei; Qu, Jiang; Li, Yang; Wang, Jinhui; Zhu, Minshen; Liu, Lixiang; Ge, Jin; Duan, Shengkai; Li, Tianming; Bandari, Vineeth Kumar; Huang, Ming; Zhu, Feng; Schmidt, Oliver G.
    High performance, flexibility, safety, and robust integration for micro‐supercapacitors (MSCs) are of immense interest for the urgent demand for miniaturized, smart energy‐storage devices. However, repetitive photolithography processes in the fabrication of on‐chip electronic components including various photoresists, masks, and toxic etchants are often not well‐suited for industrial production. Here, a cost‐effective stamping strategy is developed for scalable and rapid preparation of graphene‐based planar MSCs. Combining stamps with desired shapes and highly conductive graphene inks, flexible MSCs with controlled structures are prepared on arbitrary substrates without any metal current collectors, additives, and polymer binders. The interdigitated MSC exhibits high areal capacitance up to 21.7 mF cm−2 at a current of 0.5 mA and a high power density of 6 mW cm−2 at an energy density of 5 µWh cm−2. Moreover, the MSCs show outstanding cycling performance and remarkable flexibility over 10 000 charge–discharge cycles and 300 bending cycles. In addition, the capacitance and output voltage of the MSCs are easily adjustable through interconnection with well‐defined arrangements. The efficient, rapid manufacturing of the graphene‐based interdigital MSCs with outstanding flexibility, shape diversity, and high areal capacitance shows great potential in wearable and portable electronics.
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    Stress‐Actuated Spiral Microelectrode for High‐Performance Lithium‐Ion Microbatteries
    (2020) Tang, Hongmei; Karnaushenko, Dmitriy D.; Neu, Volker; Gabler, Felix; Wang, Sitao; Liu, Lixiang; Li, Yang; Wang, Jiawei; Zhu, Minshen; Schmidt, Oliver G.
    Miniaturization of batteries lags behind the success of modern electronic devices. Neither the device volume nor the energy density of microbatteries meets the requirement of microscale electronic devices. The main limitation for pushing the energy density of microbatteries arises from the low mass loading of active materials. However, merely pushing the mass loading through increased electrode thickness is accompanied by the long charge transfer pathway and inferior mechanical properties for long‐term operation. Here, a new spiral microelectrode upon stress‐actuation accomplishes high mass loading but short charge transfer pathways. At a small footprint area of around 1 mm2, a 21‐fold increase of the mass loading is achieved while featuring fast charge transfer at the nanoscale. The spiral microelectrode delivers a maximum area capacity of 1053 µAh cm−2 with a retention of 67% over 50 cycles. Moreover, the energy density of the cylinder microbattery using the spiral microelectrode as the anode reaches 12.6 mWh cm−3 at an ultrasmall volume of 3 mm3. In terms of the device volume and energy density, the cylinder microbattery outperforms most of the current microbattery technologies, and hence provides a new strategy to develop high‐performance microbatteries that can be integrated with miniaturized electronic devices.
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    Perovskite Origami for Programmable Microtube Lasing
    (Weinheim : Wiley-VCH, 2021) Dong, Haiyun; Saggau, Christian Niclaas; Zhu, Minshen; Liang, Jie; Duan, Shengkai; Wang, Xiaoyu; Tang, Hongmei; Yin, Yin; Wang, Xiaoxia; Wang, Jiawei; Zhang, Chunhuan; Zhao, Yong Sheng; Ma, Libo; Schmidt, Oliver G.
    Metal halide perovskites are promising materials for optoelectronic and photonic applications ranging from photovoltaics to laser devices. However, current perovskite devices are constrained to simple low-dimensional structures suffering from limited design freedom and holding up performance improvement and functionality upgrades. Here, a micro-origami technique is developed to program 3D perovskite microarchitectures toward a new type of microcavity laser. The design flexibility in 3D supports not only outstanding laser performance such as low threshold, tunable output, and high stability but also yields new functionalities like 3D confined mode lasing and directional emission in, for example, laser “array-in-array” systems. The results represent a significant step forward toward programmable microarchitectures that take perovskite optoelectronics and photonics into the 3D era. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.
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    Antifreezing Hydrogel with High Zinc Reversibility for Flexible and Durable Aqueous Batteries by Cooperative Hydrated Cations
    (Weinheim : Wiley-VCH, 2020) Zhu, Minshen; Wang, Xiaojie; Tang, Hongmei; Wang, Jiawei; Hao, Qi; Liu, Lixiang; Li, Yang; Zhang, Kai; Schmidt, Oliver G.
    Hydrogels are widely used in flexible aqueous batteries due to their liquid-like ion transportation abilities and solid-like mechanical properties. Their potential applications in flexible and wearable electronics introduce a fundamental challenge: how to lower the freezing point of hydrogels to preserve these merits without sacrificing hydrogels' basic advantages in low cost and high safety. Moreover, zinc as an ideal anode in aqueous batteries suffers from low reversibility because of the formation of insulative byproducts, which is mainly caused by hydrogen evolution via extensive hydration of zinc ions. This, in principle, requires the suppression of hydration, which induces an undesirable increase in the freezing point of hydrogels. Here, it is demonstrated that cooperatively hydrated cations, zinc and lithium ions in hydrogels, are very effective in addressing the above challenges. This simple but unique hydrogel not only enables a 98% capacity retention upon cooling down to −20 °C from room temperature but also allows a near 100% capacity retention with >99.5% Coulombic efficiency over 500 cycles at −20 °C. In addition, the strengthened mechanical properties of the hydrogel under subzero temperatures result in excellent durability under various harsh deformations after the freezing process. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim