High-performance Zn microbattteries based on a NiCo-LDH@ITO nanowire/carbon cloth composite
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摘要: 人类需求推动了微型储能器件的快速发展,开发高性能、绿色和安全的小型化电子器件势在必行。近年来,平面叉指型可充电锌微电池(MB)因其易于串并联集成、灵活性和可去除传统隔膜而受到广泛关注。本文使用激光蚀刻技术合成了一种水基高安全性的负极Zn、正极NiCo-LDH@ITO NWs@CC的微型锌电池。由于使用高导电性的ITO NWs@CC集流体,基于锌箔负极和NiCo-LDH正极的叉指型微型电池表现出优异的性能。平面叉指微型电池在碱性水系电解质中、电流密度1 mA cm−2 下具有453.5 mAh g−1(对应于0.56 mAh cm−2)的高比容量。值得注意的是,微型锌电池表现出优异的能量密度(798.4 μWh cm−2,对应于649.9 Wh kg−1)和功率密度(4.1 mW cm−2,对应于 3282.7 mW kg− 1)。微型电池也表现出非常好的长期循环稳定性(在5 mA cm−2 下经4 000次循环后容量保持率为216%)。此外,串并联测试进一步表明微型电池良好的一致性。Abstract: Following the fast growth of micro-energy storage devices, there is an urgent need to develop miniaturized electronic devices with excellent performance that are both green and safe. Planar interdigitated rechargeable Zn microbatteries (MBs) have gained widespread attention in recent years due to their ease of series-parallel integration, mechanical flexibility and no need for traditional separators. We prepared a patterned cathode of NiCo layered double hydroxide (LDH)@indium tin oxide (ITO) nanowires (NWs) @carbon cloth (CC) by the chemical vapor deposition of ITO NWs on the carbon fibers in a CC, laser patterning, and finally the electrodeposition of NiCo-LDH to coat the ITO NW@carbon fibers. The cathode was combined with a patterned Zn foil anode to form a planar MB. Because of the highly conductive ITO NWs@CC current collector, the interdigitated MB had a satisfactory performance. The planar MB has a high specific capacity of 453.5 mAh g−1 (corresponding to 0.56 mAh cm−2) in an alkaline water-based electrolyte at 1 mA cm−2. After 4 000 cycles the capacity increased to 216% of the initial value due to gradual penetration of electrolyte into the three-dimensional NiCo-LDH@ITO NW@CC network. It also had excellent energy (798.4 μWh cm−2, corresponding to 649.9 Wh kg−1) and power densities (4.1 mW cm−2, corresponding to 3 282.7 mW kg−1). Furthermore, MBs connected in series-parallel in lighting tests illustrate the excellent performance of the device. Therefore, these fast and simple Zn MBs with an in-plane interdigital structure provide a reference for next-generation high-performance, environmentally-friendly, and scalable planar micro-energy storage systems.
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Key words:
- Micro-energy storage devices /
- Micro batteries /
- Laser etching /
- ITO NWs /
- Carbon cloth
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Figure 4. The electrochemical behavior of the Zn//NiCo-LDH@ITO NWs@CC MBs: (a) CV profiles from 1 to 10 mV s−1. (b) Linear fitting of log (current) versus log (scan rate) at oxidation peaks. (c) Normalized contribution ratio of diffusion control and capacitance at various scan rates. (d) Charge/discharge profiles from 1 to 3 mA cm−2. (e) Rate performance and (f) Ragone plot. (g) CV and (h) GCD curves of 2 ZMBs in parallel and series. (i) Charge curve of two ZMBs in series at 3 mA cm−2 (inset: digital photo of two ZMBs in series lighting up 36 different parallel LEDs).
Figure 5. Cycling stability of Zn//NiCo-LDH@ITO NWs@CC MBs: (a) 1 mA cm−2, (b) 5 mA cm−2. (c) Charge-discharge curves of 1st, 1 000th, 2 000th, 3 000th, and 4 000th cycles at 5 mA cm−2. (d) GCD curve of the cycling process at 5 mA cm−2 (inset: charge-discharge curve (Ⅰ) from 210 to 220 h and (Ⅱ) from 390 to 400 h). (e-h) SEM images of the cathode after 4000 cycles.
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