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摘要: 近年来,微/纳米制造和集成微系统的快速发展受到越来越多的关注,因此对微型储能器件(MESDs),尤其是商业化的微型电池提出了更高的需求。锂离子微型电池(LIMBs)是研究最多的微型储能器件,但较低的负载和有待提高的能量密度仍阻碍了其进一步的应用。在此,通过基于挤出式的墨水直写和相应的后处理,设计并制备了3D打印的氮掺杂碳包覆硒化锌(ZnSe)纳米颗粒的复合电极。高容量的ZnSe纳米颗粒被限制在氮掺杂的碳中,其中氮掺杂的碳不仅能增强电导率,还可以充当缓冲层以减轻纳米材料的体积膨胀,并为电化学反应提供额外的活性位点。此外,3D打印电极的互连设计有利于快速传质和离子传输。因此,通过直接墨水书写的自支撑3D打印电极实现了3.15 mg cm−2的高负载量,在锂离子微型电池中表现出优异的能量密度和良好的可逆性。该工作为设计高性能电极和高负载量电极提供新的思路与策略,有望构建优异的微型储能器件。
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关键词:
- 微系统 /
- 微型电池 /
- ZnSe/NC微电极 /
- 高负载 /
- 3D打印
Abstract: The rapid development of micro/nanomanufactured integrated microsystems in recent years requires high performance micro energy storage devices (MESDs). Li-ion microbatteries (LIMBs) are the most studied MESDs, but the low mass loading of active materials and the less-than-perfect energy density hinder their further application. A 3D printed ZnSe/N-doped carbon (ZnSe/NC) composite electrode was designed and fabricated by extrusion-based 3D printing and a post-treatment strategy for use as the anode of LIMBs. The high capacity ZnSe nanoparticles are confined in the NC, where the NC not only improves the conductivity but also acts as a buffer layer to reduce the volume expansion and provide additional active sites for electrochemical reactions. The interconnected design of the 3D printed electrode is good for fast mass transfer and ion transport. A freestanding 3D printed ZnSe/NC electrode with a high mass loading of 3.15 mg cm−2 was achieved by direct ink printing, which had a superior energy density and decent reversibility in high-power LIMBs. This strategy can be used for other high-performance electrodes to achieve a high-mass-loading of active materials for microbatteries, opening up a new way to construct advanced MESDs.-
Key words:
- Microsystems /
- Microbatteries /
- ZnSe/NC microelectrode /
- High mass loading /
- 3D printing.
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Figure 1. (a) Schematic illustration of the 3D printed freestanding ZnSe/NC microelectrode. (b) SEM image of the ZnSe/NC composite electrode. (c) Digital photographs of the 3D printed ZnSe/NC microelectrode with different patterns on Cu foil. (d) Digital photographs of 3D printed ZnSe/NC microelectrode onto various substrates.
Figure 2. (a) Digital photographs of printable ink and 3D printed freestanding microelectrode patterns. SEM images of 3D printed ZnSe/NC microelectrode from (b) top view, (c) cross-sectional view, (d) magnified view, (e) XRD patterns of ZIF-8 precursor and ZnSe/NC composite, (f) TG curve of ZnSe/NC composite.
Figure 4. (a) CV curves of the ZnSe/NC anode in the first three cycles. (b) Rate capability of the ZnSe/NC anode at different current densities. (c) Cycling performance of the ZnSe/NC anode over 1 000 cycles at the current density of 1 000 mA g−1. (d) CV curves of the ZnSe/NC anode from 0.1 to 10 mV s−1. (e) Scale diagram of pseudocapacitive capacitance and diffusion-controlled capacitance contribution of the ZnSe/NC anode at various scan rates.
Figure 5. (a) CV curves of the 3D printed ZnSe/NC microelectrode with a high mass loading of 3.15 mg cm−2 from 0.01 to 3.0 V at 0.5 mV s−1. (b) EIS curve of the 3D printed ZnSe/NC microelectrode. (c) Cycling performance of the 3D printed ZnSe/NC microelectrode at the current density of 1 000 mA g−1.
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Supporting information-20220135-Zgh.pdf