Preparation and properties of flexible high capacity composite fabric electrode
-
摘要: 随着科学技术的飞速发展,各种可穿戴智能电子设备随之兴起。这些电子设备对化学电源的性能提出了更高要求,如安全高效且柔性的电化学储能装置。目前,大量的研究致力于柔性储能器件,以满足各种可穿戴智能电子设备供能的需求。本文通过调控甲醇相法的沉积时间,将具有高比表面、高孔隙率的钴基金属有机框架(Co-MOF)和镍钴双氢氧化物(NiCo DH)巧妙地结合在镀镍织物(NF)上,制备出了高性能的柔性复合电极。该电极具有高比容量(22.6 μA·h·cm−2 (323 mA·h·g−1))、优异的循环性能(2 000次充放电后容量保持率为56%)及良好的倍率性能(电流增大50倍容量保持率为60%),并且该电极拥有优异的柔韧性,经过多次弯折,该电极的电性能几乎没有大的变化,能够满足服装的各类变形。因此,本文为可穿戴电子设备的能源供应提高了一条新的思路,在智能可穿戴领域有着广阔的前景。Abstract: With the rapid development of science and technology, a variety of wearable intelligent electronic devices rised. These electronic devices put forward higher requirements for the performance of chemical power supply, such as safe, efficient and flexible electrochemical energy storage devices. At present, a lot of research was devoted to flexible energy storage devices to meet the energy supply needs of various wearable intelligent electro-nic devices. By adjusting the deposition time of methanol phase method, cobalt based metal organic framework (Co-MOF) and nickel cobalt double hydroxide (NiCo DH) with high specific surface and high porosity were cleverly combined on nickel fabric (NF) to prepare high-performance flexible composite electrode. The electrode has a high specific capacity of 22.6 μA·h·cm−2 (323 mA·h·g−1), excellent cycle performance (the capacity retention rate is 56% after 2000 times of charge and discharge) and good rate performance (the current increases by 50 times, and the capacity retention rate is 60%), and the electrode has excellent flexibility. After many bends, the electrical perfor-mance of the electrode almost does not change greatly, which can meet all kinds of deformation of clothing. Therefore, this research improves a new idea for the energy supply of wearable electronic devices, and has broad prospects in the field of intelligent wearable.
-
Key words:
- composite fabric electrode /
- high capacity /
- flexibility /
- metal-organic framework /
- wearable /
- nickel zinc battery
-
表 1 不同条件下的复合电极材料
Table 1. Composite electrode materials under different conditions
Material Deposition material Deposition time/h Name Etching Name Ni fabric Co-metal organic
framework6 NF-MOF 6 Nickel cobalt
double hydroxideNF-NiCo DH 6 12 NF-MOF 12 NF-NiCo DH 12 18 NF-MOF 18 NF-NiCo DH 18 24 NF-MOF 24 NF-NiCo DH 24 30 NF-MOF 30 NF-NiCo DH 30 表 2 NF-NiCo DH 24电极同其他复合电极材料的电化学比容量对比
Table 2. Comparison of electrochemical specific capacity between NF-NiCo DH 24 electrode and other composite electrode materials
Electrode material Capacity/
(mA·h·g−1)Ref. Co3O4@carbon cloth 240.8 [32] Co3O4@carbon cloth 230.0 [33] Silver-coated nylon fiber@Ni@nickel-cobalt layered double hydroxides 275.0 [30] NiSe2@Ni foam 243.8 [34] Ni2P@carbon cloth 242.0 [35] Ni-NiO/carbon cloth 184.0 [36] Ni fabric-nickel cobalt double hydroxide 323.0 This work -
[1] 巩继贤. 智能服装的现状及展望[J]. 现代纺织技术, 2004, 12(1): 47-49.GONG Jixian. Current situation and prospect of smart clothing[J]. Modern Textile Technology, 2004, 12(1): 47-49(in Chinese). [2] YAN H, IP W S, LAU Y Y, et al. Weavable, conductive yarn-based NiCo//Zn textile battery with high energy density and rate capability[J]. ACS Nano,2017,11(9):8953-8961. doi: 10.1021/acsnano.7b03322 [3] ZHOU Y, BO L, LI Z. Recent progress in human body energy harvesting for smart bioelectronic system[J]. Fundamental Research, 2021, 1(3): 364-382. [4] HAN O Y, JIANG D J, FAN Y B, et al. Self-powered technology for next-generation biosensor[J]. Science Bulletin,2021,66(17):1709-1712. doi: 10.1016/j.scib.2021.04.035 [5] 刘高燕. 能源危机[J]. 能源与节能, 2015, 20(4): 123.LIU Gaoyan. Energy crisis[J]. Energy and Energy Conservation, 2015, 20(4): 123(in Chinese). [6] 乔宠如. 可再生能源危机[J]. 经济, 2015, 22: 32-36.QIAO Chongru. Renewable energy crisis[J]. Economy, 2015, 22: 32-36(in Chinese). [7] 谭杨. 基于MOF结构的Binder-free电极材料的制备及其电化学性能研究[D]. 成都: 电子科技大学, 2020.TAN Yang. Preparation and electrochemical properties of binder free electrode materials based on MOF structure[D]. Chengdu: University of Electronic Science and Technology, 2020(in Chinese). [8] ZHAO Y H, HE X Y, CHEN R R, et al. A flexible all-solid-state asymmetric supercapacitors based on hierarchical carbon cloth@CoMoO4 NiCo layered double hydroxide core-shell heterostructures[J]. Chemical Engineering Journal, 2018, 352: 29-38. [9] WANG C, HU K, LI W J, et al. Wearable wire-shaped symmetric supercapacitors based on activated carbon-coated graphite fibers[J]. ACS Applied Materials & Interfaces,2018,10(40):34302-34310. [10] HU P, WANG T S, ZHAO J W, et al. Ultrafast alkaline Ni/Zn battery based on Ni-foam-supported Ni3S2 nanosheets[J]. ACS Applied Materials & Interfaces,2015,7(48):26396-26399. [11] 王江林, 徐学良, 丁青青, 等. 锌镍电池在储能技术领域中的应用及展望[J]. 储能科学与技术, 2019, 8(3): 506-511.WAMG Jianglin, XU Xueliang, DING Qingqing, et al. Application and prospect of zinc nickel battery in energy storage technology[J]. Energy Storage Science and Technology, 2019, 8(3): 506-511(in Chinese). [12] 吴清真. 镍锌电池正极材料的研究[D]. 重庆: 重庆大学, 2016.WU Qingzhen. Research on cathode materials for nickel zinc batteries[D]. Chongqing: Chongqing University, 2016(in Chinese). [13] 郝志猛. 基于分级有序孔镍/氢氧化镍微电极的微型镍锌电池[D]. 武汉: 武汉理工大学, 2019.HAO Zhimeng. Micro nickel zinc battery based on graded ordered pore nickel/nickel hydroxide microelectrode[D]. Wuhan: Wuhan University of Technology, 2019(in Chinese). [14] 李先伟. 高性能水系锌离子电池三维柔性电极材料的研究[D]. 南昌: 东华理工大学, 2019.LI Xianwei. Research on three-dimensional flexible electrode materials for high-performance aqueous zinc ion batteries[D]. Nanchang: Donghua University of Technology, 2019(in Chinese). [15] LAI S B, JAMESH M I, WU X C, et al. A promising energy storage system: Rechargeable Ni-Zn battery[J]. Rare Metals,2017,36(5):381-396. [16] LIU J P, GUAN C, ZHOU C, et al. A flexible quasi-solid-state nickel-zinc battery with high energy and power densities based on 3D electrode design[J]. Advanced Materials,2016,28(39):8732-8739. doi: 10.1002/adma.201603038 [17] LIU J, NIE N Y, WANG J Q, et al. Initiating a wide-tempera-ture-window yarn zinc ion battery by a highly conductive iongel[J]. Materials Today Energy,2020,16:100372. doi: 10.1016/j.mtener.2019.100372 [18] ZHANG J, CHENG J P, LI M, et al. Flower-like nickel-cobalt binary hydroxides with high specific capacitance: Tuning the composition and asymmetric capacitor application[J]. Journal of Electroanalytical Chemistry,2015,743:38-45. doi: 10.1016/j.jelechem.2015.02.021 [19] XIA D D, CHEN H C, JIANG J J, et al. Facilely synthesized alpha phase nickel-cobalt bimetallic hydroxides: Tuning the composition for high pseudocapacitance[J]. Electrochimica Acta,2015,156:108-114. doi: 10.1016/j.electacta.2015.01.018 [20] LI M, YUAN P W, GUO S H, et al. Design and synthesis of Ni-Co and Ni-Mn layered double hydroxides hollow microspheres for supercapacitor[J]. International Journal of Hydrogen Energy,2017,42(8):28797-28806. [21] 吴茂琪. 纱线状镍电极及柔性镍锌织物电池的制备与性能研究[D]. 天津: 天津工业大学, 2020.WU Maoqi. Study on preparation and performance of yarn nickel electrode and flexible nickel zinc fabric battery[D]. Tianjin: Tianjin University of Technology, 2020(in Chinese). [22] 杨甜甜. 金属有机框架材料及其衍生物的制备和电容性能研究[D]. 绵阳: 西南科技大学, 2020.YANG Tiantian. Preparation and capacitive properties of metal organic framework materials and their derivatives[D]. Mianyang: Southwest University of Science and Technology, 2020(in Chinese). [23] 商梦莉. 金属有机骨架(ZIF-67)材料的制备、微结构调控及性能研究[D]. 保定: 河北大学, 2020.SHANG Mengli. Preparation, microstructure regulation and properties of metal organic framework (ZIF-67)[D]. Baoding: Hebei University, 2020(in Chinese). [24] HU C Z, XU J H, WANG Y Z, et al. Core-shell crystalline ZIF-67@amorphous ZIF for high-performance supercapaci-tors[J]. Journal of Materials Science,2020,55(34):16360-16373. doi: 10.1007/s10853-020-05163-8 [25] LIU M, ZHAO H T, XU X X. "Planting" MOF nanotube on Chinese Xuan Paper derived 3D carbon paper: An efficient positive electrode for Ni-Zn battery[J]. Journal of Solid State Chemistry,2020,289:121473. [26] ZHEN J, LI Z P, QIN Z H, et al. LDH nanocages synthesized with MOF templates and their high performance as supercapacitors[J]. Nanoscale,2013,5(23):11770-11775. doi: 10.1039/c3nr03829g [27] YIN K L, ZHANG H P, YAN Y. High efficiency of toluene adsorption over a novel ZIF-67 membrane coating on paper-like stainless steel fibers[J]. Journal of Solid State Che-mistry,2019,279:120976. [28] 杨静, 刘艳君. 石墨烯-棉针织物电极材料的制备及其性能[J]. 纺织学报, 2019, 40(3): 90-95.YANG Jing, LIU Yanjun. Preparation and properties of graphene cotton knitted fabric electrode materials[J]. Journal of Textiles, 2019, 40(3): 90-95(in Chinese). [29] 王胜, 张胜全. 金属-有机框架材料ZIF-8的合成机理研究[J]. 甘肃冶金, 2016, 38(6):44-48.WANG Sheng, ZHANG Shengquan. Study on synthesis mechanism of metal organic framework material ZIF-8[J]. Gansu Metallurgy,2016,38(6):44-48(in Chinese). [30] WU M Q, XIA Z P, MAO Z F, et al. Stretchable Ni-Zn fabric battery based on sewable core-shell SCNF@Ni@NiCo LDHs thread cathode for wearable smart garment[J]. Journal of Materials Science,2021,56(17):10537-10554. [31] PU X J, ZHAO D, FU C L, et al. Understanding and calibration of charge storage mechanism in cyclic voltammetry curves[J]. Angewandte Chemie, 2021, 133(39): 21480-21488. [32] LU Y Z, WANG J, ZENG S Q, et al. An ultrathin defect-rich Co3O4 nanosheet cathode for high-energy and durable aqueous zinc ion batteries[J]. Journal of Materials Che-mistry A,2019,7(38):21678-21683. doi: 10.1039/C9TA08625K [33] SHANG W X, YU W T, XIAO X, et al. Microstructure-tuned cobalt oxide electrodes for high-performance Zn-Co batteries[J]. Electrochimica Acta,2020,353:136535. doi: 10.1016/j.electacta.2020.136535 [34] ZHOU W H, HE J, ZHU D, et al. Hierarchical NiSe2 nanosheet arrays as a robust cathode toward superdurable and ultrafast Ni-Zn aqueous batteries[J]. ACS Applied Materials & Interfaces,2020,12(31):34931-34940. [35] WEN J, FENG Z, LIU H R, et al. In-situ synthesized Ni2P nanosheet arrays as the cathode for novel alkaline Ni//Zn rechargeable battery[J]. Applied Surface Science,2019,485:462-467. doi: 10.1016/j.apsusc.2019.04.222 [36] LI L, JIANG L L, YAN Q, et al. Manipulating nickel oxides in naturally derived cellulose nanofiber networks as robust cathodes for high-performance Ni-Zn batteries[J]. Jour-nal of Materials Chemistry A,2020,8(2):565-572. doi: 10.1039/C9TA09006A