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    A Patternable and In Situ Formed Polymeric Zinc Blanket for a Reversible Zinc Anode in a Skin-Mountable Microbattery
    (Weinheim : Wiley-VCH, 2021) Zhu, Minshen; Hu, Junping; Lu, Qiongqiong; Dong, Haiyun; Karnaushenko, Dmitriy D.; Becker, Christian; Karnaushenko, Daniil; Li, Yang; Tang, Hongmei; Qu, Zhe; Ge, Jin; Schmidt, Oliver G.
    Owing to their high safety and reversibility, aqueous microbatteries using zinc anodes and an acid electrolyte have emerged as promising candidates for wearable electronics. However, a critical limitation that prevents implementing zinc chemistry at the microscale lies in its spontaneous corrosion in an acidic electrolyte that causes a capacity loss of 40% after a ten-hour rest. Widespread anti-corrosion techniques, such as polymer coating, often retard the kinetics of zinc plating/stripping and lack spatial control at the microscale. Here, a polyimide coating that resolves this dilemma is reported. The coating prevents corrosion and hence reduces the capacity loss of a standby microbattery to 10%. The coordination of carbonyl oxygen in the polyimide with zinc ions builds up over cycling, creating a zinc blanket that minimizes the concentration gradient through the electrode/electrolyte interface and thus allows for fast kinetics and low plating/stripping overpotential. The polyimide's patternable feature energizes microbatteries in both aqueous and hydrogel electrolytes, delivering a supercapacitor-level rate performance and 400 stable cycles in the hydrogel electrolyte. Moreover, the microbattery is able to be attached to human skin and offers strong resistance to deformations, splashing, and external shock. The skin-mountable microbattery demonstrates an excellent combination of anti-corrosion, reversibility, and durability in wearables. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
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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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    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.