锂离子电池CoO多孔纳米片阵列/碳布柔性负极材料

摘要/Abstract

摘要： 可穿戴、可折叠电子设备日益受到人们的关注,开发与之配套的柔性电极材料成为当下的研究热点。本研究采用水热法制备前驱体/碳布复合材料,将其在高纯氩气气氛下煅烧,得到柔性的CoO多孔纳米片阵列/碳布负极材料。这种多孔与三维网状立体结构能够有效缓解充放电过程中材料的体积效应,而且多孔结构还增加了活性物质CoO纳米片的比表面积,有利于电极材料储锂容量的提升。电化学性能测试表明,该CoO多孔纳米片阵列/碳布负极材料在100 mA·cm^-2的恒电流下, 首次放电容量1 862.8 mAh·cm^-2,首次循环库伦效率87.8%,在700 mA·cm^-2的电流密度下,经过100次的充放电循环后,材料的放电比容量仍保持在1 428.9 mAh·cm^-2。在1 000 mA·cm^-2的电流密度下,仍然有1 353.8 mAh·cm²的容量。该方法简便易行且原料成本低廉,可以降低锂离子电池柔性负极材料的成本。

关键词: CoO多孔纳米片, 碳布, 柔性电极材料, 负极材料, 水热法, 电化学性能

Abstract: In recent years, flexible electronics is an emerging and promising technology for next generation of optoelectronic devices. The study of new inexpensive, flexible and lightweight electrode materials has triggered a gold rush. Herein, hierarchical porous CoO nanosheets arrays/carbon cloth composites successfully synthesized were using a hydrothermal reaction followed by calcination. The three-dimensional network structure can accommodate large mechanical strains by providing the gaps to alleviate volume change. The porous structure can improve the specific surface area of the active substance CoO, which is conducive to the improvement of lithium storage capacity of electrode materials. When investigated as flexible anode for lithium-ion batteries, the CoO porous nanosheets array/carbon cloth materials achieve an initial charge capacity of 1 862.8 mAh·cm^-2 with coulombic efficiency of 87.8% at constant current of 100 mA·cm^-2. The reversible capacity is 1 428.9 mAh·cm^-2 after 100 cycles at current density of 700 mA·cm^-2. And it is capable to retain a capacity of 1 353.8 mAh·cm^-2 even at current density of 1 000 mA·cm^-2. The excellent electrochemical performance of the composites could be attributed to the unique morphology, structure of the CoO porous nanosheets, as well as directly grown on current collector. Thus, this work introduces an easy and economic method for fabrication CoO porous nanosheets array/carbon cloth materials for high-performance flexible lithium ion battery.

Key words: CoO porous nanosheet, carbon cloth, flexible electrode material, anode material, hydrothermal method, electrochemical performance

中图分类号:

O734

望军, 赵雨, 范保艳, 张均, 邢安, 刘晓燕. 锂离子电池CoO多孔纳米片阵列/碳布柔性负极材料[J]. 人工晶体学报, 2021, 50(11): 2150-2155.

WANG Jun, ZHAO Yu, FAN Baoyan, ZHANG Jun, XING An, LIU Xiaoyan. CoO Porous Nanosheets Array/Carbon Cloth as Flexible Anode Material for Lithium-Ion Batteries[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(11): 2150-2155.

参考文献

[1] PENG H J, HUANG J Q, ZHANG Q. A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries[J]. Chemical Society Reviews, 2017, 46(17): 5237-5288.
[2] DIRICAN M, YANILMAZ M, FU K, et al. Carbon-enhanced electrodeposited SnO₂/carbon nanofiber composites as anode for lithium-ion batteries[J]. Journal of Power Sources, 2014, 264: 240-247.
[3] WEN L, LI F, CHENG H M. Carbon nanotubes and graphene for flexible electrochemical energy storage: from materials to devices[J]. Advanced Materials, 2016, 28(22): 4306-4337.
[4] DE ZHU Y, HUANG Y, WANG M Y, et al. Novel carbon coated core-shell heterostructure NiCo₂O₄@NiO grown on carbon cloth as flexible lithium-ion battery anodes[J]. Ceramics International, 2018, 44(17): 21690-21698.
[5] WANG L L, GU X L, ZHAO L Y, et al. ZnO@TiO₂ heterostructure arrays/carbon cloth by charge redistribution enhances performance in flexible anode for Li ion batteries[J]. Electrochimica Acta, 2019, 295: 107-112.
[6] REN W N, WANG C, LU L F, et al. SnO₂@Si core-shell nanowire arrays on carbon cloth as a flexible anode for Li ion batteries[J]. Journal of Materials Chemistry A, 2013, 1(43): 13433.
[7] 戴剑锋,朱晓军,刘骥飞,等.Co₃O₄/C纳米纤维锂离子电池负极材料性能研究[J].人工晶体学报,2018,47(10):2004-2008+2021.
DAI J F, ZHU X J, LIU J F, et al. Research on the performance of Co₃O₄/C nanofibers as anode material for lithium ion battery[J]. Journal of Synthetic Crystals, 2018, 47(10): 2004-2008+2021(in Chinese).
[8] 田海,钟艳君,吴振国,等.中空分级结构Fe₃O₄@C/rGO复合材料的合成及其储锂性能[J].无机化学学报,2020,36(7):1309-1317.
TIAN H, ZHONG Y J, WU Z G, et al. Synthesis and lithium storage properties of hollow hierarchical structure Fe₃O₄@C/rGO composites[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(7): 1309-1317(in Chinese).
[9] 赵赛花.钴铁氧化物纳米复合材料的制备及在(柔性)锂离子电池负极材料上的应用[D].金华:浙江师范大学,2016.
ZHAO S H. Preparation of iron and cobalt oxide nanocomposite and their application as anode materials for (flexible) lithium ion batteries[D]. Jinhua: Zhejiang Normal University, 2016(in Chinese).
[10] AVVARU V S, FERNANDEZ I J, FENG W L, et al. Extremely pseudocapacitive interface engineered CoO@3D-NRGO hybrid anodes for high energy/power density and ultralong life lithium-ion batteries[J]. Carbon, 2021, 171: 869-881.
[11] WANG L H, TENG X L, QIN Y F, et al. High electrochemical performance and structural stability of CoO nanosheets/CoO film as self-supported anodes for lithium-ion batteries[J]. Ceramics International, 2021, 47(4): 5739-5746.
[12] 柏大伟,何雨石,阳炳检,等.石墨烯纳米片-氧化亚钴负极材料制备与表征[J].电源技术,2011,35(2):170-172.
BAI D W, HE Y S, YANG B J, et al. Synthesis and characterization of graphene nanosheets-cobalt oxide composites as anode material[J]. Chinese Journal of Power Sources, 2011, 35(2): 170-172(in Chinese).
[13] LONG H, SHI T L, HU H, et al. Growth of hierarchal mesoporous NiO nanosheets on carbon cloth as binder-free anodes for high-performance flexible lithium-ion batteries[J]. Scientific Reports, 2014, 4: 7413.
[14] ZHAN L, WANG S Q, DING L X, et al. Binder-free Co-CoO_x nanowire arrays for lithium ion batteries with excellent rate capability and ultra-long cycle life[J]. Journal of Materials Chemistry A, 2015, 3(39): 19711-19717.
[15] ZHOU L, WU H B, ZHU T, et al. Facile preparation of ZnMn₂O₄hollow microspheres as high-capacity anodes for lithium-ion batteries[J]. J Mater Chem, 2012, 22(3): 827-829.
[16] ZHANG Z C, CHEN Y F, HE S, et al. Hierarchical Zn/Ni-MOF-2 nanosheet-assembled hollow nanocubes for multicomponent catalytic reactions[J]. Angewandte Chemie International Edition, 2014, 53(46): 12517-12521.
[17] 罗雯,黄磊,关豆豆,等.空心碳球负载二硫化硒复合材料作为锂离子电池正极材料[J].物理化学学报,2016,32(8):1999-2006.
LUO W, HUANG L, GUAN D D, et al. A selenium disulfide-impregnated hollow carbon sphere composite as a cathode material for lithium-ion batteries[J]. Acta Physico-Chimica Sinica, 2016, 32(8): 1999-2006(in Chinese).
[18] 甄绪,郭雪静.三维介孔钴酸锌立方体的制备及其优异的储锂性能[J].物理化学学报,2017,33(4):845-852.
ZHEN X, GUO X J. Synthesis and lithium storage performance of three-dimensional mesostructured ZnCo₂O₄ cubes[J]. Acta Physico-Chimica Sinica, 2017, 33(4): 845-852(in Chinese).
[19] VARZI A, BRESSER D, ZAMORY J V, et al. ZnFe₂O₄-C/LiFePO₄ -CNT: a novel high-power lithium-ion battery with excellent cycling performance[J]. Advanced Energy Materials, 2014, 4: 1-9.
[20] YAO D, WANG F L, LEI W, et al. Oxygen vacancies boosting ultra-stability of mesoporous ZnO-CoO@N-doped carbon microspheres for asymmetric supercapacitors[J]. Science China Materials, 2020, 63(10): 2013-2027.