晶格空位ZnO纳米棒的制备及其在镍锌电池中的应用

doi:10.15541/jim20190195

摘要/Abstract

摘要：

作为绿色、高功率密度的二次电池, 镍锌电池的应用往往受限于负极材料性能的不足。本工作以乌洛托品(HMT)为模板剂, 通过溶胶-凝胶法合成与热退火处理制备了高性能ZnO纳米棒。透射电子显微镜(TEM)、X射线衍射(XRD)和红外光谱(FT-IR)数据分别揭示了ZnO纳米棒的微观形貌、晶型结构和表面官能团。X射线光电子能谱(XPS)和电子顺磁共振(EPR)结果表明ZnO纳米棒中存在表层碳和晶格空位。Tafel曲线和电化学阻抗等测试表明: 与ZnO商品相比, ZnO纳米棒电极的腐蚀电流和电荷转移电阻分别降低了40%和62%。进一步研究发现, ZnO纳米棒构筑的镍锌电池具有更好的循环性能, 在1 A·g^-1下循环100圈后, ZnO纳米棒的容量保持率为92%, 显著优于市售的ZnO粉末(32%)。

关键词: 镍锌电池, 晶格空位, ZnO纳米棒, 负极材料, 电化学性能

Abstract:

As a type of environmental benign secondary battery with high power density, Ni-Zn battery is often limited by the weakness of negative electrode materials in the applications. In this work, ZnO nanorods (NRs) with high performance were synthesized by Sol-Gel process with hexamethylenetetramine (HMT) as template and subsequent thermal annealing treatment. Morphology, crystalline structure and surface functional groups of ZnO NRs were characterized by transmission electron microscope (TEM), X-ray powder diffraction (XRD) and Fourier-transform infrared spectroscope (FT-IR), respectively. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) measurements reveal that ZnO NRs have carbon layers on the surface and vacancies in the lattice. Tafel tests and electrochemical impedance spectroscopy (EIS) show that the corrosion current and charge transfer resistance of ZnO NRs-based electrodes are reduced by 40% and 62%, respectively, compared with commercial ZnO. Further investigation show that Ni-Zn batteries fabricated with ZnO NRs have better cycling performances. After 100 cycles at a current density of 1 A·g^-1, the capacity retention rate of ZnO NRs is 92%, which is significantly higher than that of commercial ZnO powder (32%).

Key words: nickel-zinc battery, lattice vacancy, ZnO nanorod, anode material, electrochemical performance

中图分类号:

TQ15

朱泽阳,魏济时,黄健航,董向阳,张鹏,熊焕明. 晶格空位ZnO纳米棒的制备及其在镍锌电池中的应用[J]. 无机材料学报, 2020, 35(4): 423-430.

ZHU Zeyang,WEI Jishi,HUANG Jianhang,DONG Xiangyang,ZHANG Peng,XIONG Huanming. Preparation of ZnO Nanorods with Lattice Vacancies and Their Application in Ni-Zn Battery[J]. Journal of Inorganic Materials, 2020, 35(4): 423-430.

图/表 11

图1 ZnO纳米棒的制备以及电池组成示意图, 插图为ZnO纳米棒粉末照片

Fig. 1 Schematic illustration of the preparation of ZnO NRs and the Ni-Zn battery with inset showing the photograph of ZnO NRs

图2 (a) ZnO商品和(b~d) ZnO纳米棒的透射电镜照片

Fig. 2 TEM images of (a) commercial ZnO and (b-d) ZnO NRs

图3 ZnO商品、ZnO纳米棒前驱体和ZnO纳米棒的(a)XRD图谱和(b)红外光谱图

Fig. 3 (a) XRD patterns, and (b) FT-IR spectra of commercial ZnO, ZnO NRs precursor and ZnO NRs

图4 ZnO纳米棒的(a)热重曲线和(b)拉曼光谱

Fig. 4 (a) Thermogravimetric analysis and (b) Raman spectrum of ZnO NRs

图5 ZnO商品和ZnO纳米棒的XPS高分辨谱((a) Zn 2p, (b) O 1s); (c) ZnO商品和ZnO纳米棒的电子顺磁共振谱

Fig. 5 HRXPS spectra of (a) Zn 2p and (b) O 1s for commercial ZnO and ZnO NRs, and (c) EPR spectra of commercial ZnO and ZnO NRs

图6 ZnO商品和ZnO纳米棒电极的电化学性能

Fig. 6 Electrochemical performances of commercial ZnO and ZnO NRs electrodes (a) CV curves at a scan rate of 10 mV·s-1; (b) Tafel plots; (c) Nyquist plots

表1 ZnO商品和ZnO纳米棒的Tafel曲线和电化学阻抗参数

Table 1 Parameters of Tafel plots and EIS for commercial ZnO and ZnO NRs

Electrode	Tafel plots		EIS
Electrode	E_corr/V (vs. Hg/HgO)	I_corr/(mA·cm^-2)	R_S/Ω	R_CT/Ω
Commercial ZnO	-1.327	5.01×10^-3	1.4	7.9
ZnO NRs	-1.311	3.01×10^-3	0.9	3.0

图7 以ZnO商品或ZnO纳米棒为负极、氢氧化镍为正极的镍锌电池的电化学性能

Fig. 7 Electrochemical performances of the Ni(OH)2//commercial ZnO and Ni(OH)2//ZnO NRs (a-d) Charge-discharge curves at different current densities; (e) Rate capabilities; (f) Cycling performances

表2 不同氧化锌负极材料的倍率性能

Table 2 Rate performances of different ZnO negative materials

Sample	Current density	Capacity retention/%
ZnO@Bi/C^[12]	1C-5C	~52.5
ZnO@RGO^[31]	1C-5C	~58.3
SnO₂@ZnO^[32]	1C-8C	~24.0
ZnO-N₂@C^[11]	1C-10C	~56.4
This work	1.5C-15C	~59.1

表3 不同氧化锌负极材料的循环性能

Table 3 Cycling performances of different ZnO negative materials

Sample	Capacity retention
Spherical ZnO^[33]	0.2C, 100 cycles, ~64%
ZnO/PPy_16.8%^[9]	1C, 100 cycles, ~74%
12wt% TPP-modified ZnO^[34]	1C, 50 cycles, ~89%
This work	1.5C, 100 cycles, ~92%

图8 在5 A·g-1电流密度下, (a, b)ZnO商品和(c, d)ZnO纳米棒100圈循环(a, c)前(b, d)后的扫描电镜照片

Fig. 8 SEM images of (a, b) commercial ZnO and (c, d) ZnO NRs (a, c) before and (b, d) after 100 cycles at 5 A·g-1

参考文献 34

[1]	CHEN L N, YAN M Y, MEI Z W , et al. Research progress and prospect of aqueous zinc ion battery. Journal of Inorganic Materials, 2017,32(3):225-234.
[2]	WEI X J, LI Y B, GAO S Y . Biomass-derived interconnected carbon nanoring electrochemical capacitors with high performance in both strongly acidic and alkaline electrolytes. Journal of Materials Chemistry A, 2017,5(1):181-188.
[3]	WEI X J, ZOU H L, GAO S Y . Chemical crosslinking engineered nitrogen-doped carbon aerogels from polyaniline-boric acid- polyvinyl alcohol gels for high-performance electrochemical capacitors. Carbon, 2017,123:471-480.
[4]	WEI X J, WEI J S, LI Y B , et al. Robust hierarchically interconnected porous carbons derived from discarded Rhus typhina fruits for ultrahigh capacitive performance supercapacitors. Journal of Power Sources, 2019,414:13-23.
[5]	MA G Q, JIANG Z M, CHEN H C , et al. Research process on novel electrolyte of lithium-ion battery based on lithium salts. Journal of Inorganic Materials, 2018,33(7):699-710.
[6]	TAN Y, XUE B . Research progress on lithium titanate as anode material in lithium-ion battery. Journal of Inorganic Materials, 2018,33(5):475-482.
[7]	OUYANG Y, GUO Y P, LI D , et al. Single additive with dual functional- ions for stabilizing lithium anodes. ACS Applied Materials & Interfaces, 2019,11(12):11360-11368.
[8]	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. Advanced Materials, 2016,28(39):8732-8739.
[9]	HUANG J H, YANG Z H, YANG B , et al. Ultrasound assisted polymerization for synthesis of ZnO/polypyrrole composites for zinc/nickel rechargeable battery. Journal of Power Sources, 2014,271:143-151.
[10]	WEN R J, YANG Z H, FAN X M , et al. Electrochemical performances of ZnO with different morphology as anodic materials for Ni/Zn secondary batteries. Electrochimica Acta, 2012,83:376-382.
[11]	LI J, ZHAO T H, SHANGGUAN E B , et al. Enhancing the rate and cycling performance of spherical ZnO anode material for advanced zinc-nickel secondary batteries by combined in-situ doping and coating with carbon. Electrochimica Acta, 2017,236:180-189.
[12]	ZHAO Z J, YANG K, PENG K , et al. Synergistic effect of ZnO@Bi/C sphere for rechargeable Zn-Ni battery with high specific capacity. Journal of Power Sources, 2019,410:10-14.
[13]	YANG H, YANG Z H, WEN X , et al. The in-situ growth of zinc-aluminum layered double hydroxides on graphene and its application as anode active materials for Zn-Ni secondary battery. Electrochimica Acta, 2017,252:507-515.
[14]	LAI S B, JAMESH M I, WU X C , et al. A promising energy storage system: rechargeable Ni-Zn battery. Rare Metals, 2017,36(5):381-396.
[15]	XIE Q S, LIU P F, ZENG D Q , et al. Dual electrostatic assembly of graphene encapsulated nanosheet-assembled ZnO-Mn-C hollow microspheres as a lithium ion battery anode. Advanced Functional Materials, 2018,28(19):1707433.
[16]	HUANG G Y, YANG Y, SUN H Y , et al. Defective ZnCo₂O₄ with Zn vacancies: synthesis, property and electrochemical application. Journal of Alloys and Compounds, 2017,724:1149-1156.
[17]	SHEN X Y, MU D B, CHEN S , et al. Enhanced electrochemical performance of ZnO-loaded/porous carbon composite as anode materials for lithium ion batteries. ACS Applied Materials & Interfaces, 2013,5(8):3118-3125.
[18]	KIM J, IM Y, PARK K S , et al. Improved cell performances in Ni/Zn redox batteries fabricated by ZnO materials with various morphologies synthesized using amine chelates. Journal of Industrial and Engineering Chemistry, 2017,56:463-471.
[19]	WU P Y, PIKE J, ZHANG F , et al. Low-temperature synthesis of zinc oxide nanoparticles. International Journal of Applied Ceramic Technology, 2006,3(4):272-278.
[20]	NOEI H, QIU H S, WANG Y M , et al. The identification of hydroxyl groups on ZnO nanoparticles by infrared spectroscopy. Physical Chemistry Chemical Physics, 2008,10(47):7092-7097.
[21]	N’KONOU K, HARIS M, LARE Y , et al. Effect of barium doping on the physical properties of zinc oxide nanoparticles elaborated via sonochemical synthesis method. Pramana-Journal of Physics, 2016,87(1):4.
[22]	KIM J G, LEE S H, KIM Y , et al. Fabrication of free-standing ZnMn₂O₄ mesoscale tubular arrays for lithium-ion anodes with highly reversible lithium storage properties. ACS Applied Materials & Interfaces, 2013,5(21):11321-11328.
[23]	LIU J P, LI Y Y, DING R M , et al. Carbon/ZnO nanorod array electrode with significantly improved lithium storage capability. Journal of Physical Chemistry C, 2009,113(13):5336-5339.
[24]	KAMBLE A, SINHA B, CHUNG K , et al. Facile linker free growth of CdS nanoshell on 1-D ZnO: solar cell application. Electronic Materials Letters, 2015,11(2):171-179.
[25]	ZENG Y X, LAI Z Z, HAN Y , et al. Oxygen-vacancy and surface modulation of ultrathin nickel cobaltite nanosheets as a high-energy cathode for advanced Zn-ion batteries. Advanced Materials, 2018,30(33):1802396.
[26]	NANDI P, DAS D . Photocatalytic degradation of rhodamine-B dye by stable ZnO nanostructures with different calcination temperature induced defects. Applied Surface Science, 2019,465:546-556.
[27]	XIA T, WALLENMEYER P, ANDERSON A , et al. Hydrogenated black ZnO nanoparticles with enhanced photocatalytic performance. RSC Advances, 2014,4(78):41654-41658.
[28]	DENG S J, ZHANG Y, XIE D , et al. Oxygen vacancy modulated Ti₂Nb₁₀O₂₉-_x embedded onto porous bacterial cellulose carbon for highly efficient lithium ion storage. Nano Energy, 2019,58:355-364.
[29]	CARBONE M . Zn defective ZnCo₂O₄ nanorods as high capacity anode for lithium ion batteries. Journal of Electroanalytical Chemistry, 2018,815:151-157.
[30]	YAN X Y, CHEN Z X, WANG Y , et al. In-situ growth of ZnO nanoplates on graphene for the application of high rate flexible quasi-solid-state Ni-Zn secondary battery. Journal of Power Sources, 2018,407:137-146.
[31]	SUN L S, YI Z, LIN J , et al. Fast and energy efficient synthesis of ZnO@RGO and its application in Ni-Zn secondary battery. Journal of Physical Chemistry C, 2016,120(23):12337-12343.
[32]	GUO W C, TIAN Z L, YANG C , et al. ZIF-8 derived nano-SnO₂@ZnO as anode for Zn/Ni secondary batteries. Electrochemistry Communications, 2017,82:159-162.
[33]	ZHAO T H, SHANGGUAN E B, LI Y , et al. Facile synthesis of high tap density ZnO microspheres as advanced anode material for alkaline nickel-zinc rechargeable batteries. Electrochimica Acta, 2015,182:173-182.
[34]	HUANG J H, YANG Z H, WANG T T . Evaluation of tetraphenylporphyrin modified ZnO as anode material for Ni-Zn rechargeable battery. Electrochimica Acta, 2014,123:278-284.