金属有机骨架衍生NiCo2O4/rGO复合材料的制备及其超级电容性能
Preparation and Supercapacitive Performance of Metal-Organic Framework Derived NiCo2O4/rGO Composites
摘 要
采用溶剂热法，按照镍和钴金属盐与氧化石墨稀（GO）质量比分别为1：0.05，1：0.07，1：0.09的配比制备镍钴金属有机骨架（Ni-Co-MOF）/GO前驱体，并将其超声喷涂在加热的泡沫镍基底上制备NiCo2O4/rGO （还原氧化石墨烯）复合电极材料，研究了该复合材料的微观结构和电化学性能。结果表明：NiCo2O4/rGO复合材料由褶皱石墨烯及其表面均匀分布的NiCo2O4纳米颗粒构成；在2 A·g-1电流密度下，盐与GO质量比为1：0.07时复合材料的比电容高达991 F·g-1，在20 A·g-1电流密度下充放电30 000次后，初始电容保持率仍高达126％。组装而成的NiCo2O4/rGO//AC非对称超级电容器的能量密度可达到41 W·h·kg-1，对应的功率密度为1 604 W·kg-1，在20 A·g-1的电流密度下经过25 000次充电/放电循环后仍可实现100％以上的电容保持率，表现出超长的循环寿命。
复合电极材料
超声喷涂
超级电容性能
NiCo2O4/rGO composite
composite electrode material
ultrasonic spray
supercapacitive performance
Abstract
Nickel-cobalt metal-organic framework(Ni-Co-MOF)/graphene oxide(GO) precursors were prepared by solvothermal synthesis with mass ratios of nickel and cobalt metal salts to GO of 1：0.05, 1：0.07, and 1：0.09, respectively, and then were ultrasonically sprayed on the heated nickel foam substrate to obtain NiCo2O4/reduced graphene oxide(rGO) composite electrode materials. The microstructure and electrochemical properties of the composites were studied. The results show that the NiCo2O4/rGO composite was composed of wrinkled graphene and NiCo2O4 nanoparticles uniformly distributed on graphene surface. When the mass ratio of salt to GO was 1：0.07, the composite had a high specific capacitance of 991 F·g-1 at a current density of 2 A·g-1; after 30 000 cycles of charge and discharge at a current density of 20 A·g-1, the initial capacitance retention was still as high as 126%. The assembled NiCo2O4/rGO//AC asymmetric supercapacitor had an energy density of 41 W·h·kg-1 at a power density of 1 604 W·kg-1, and achieved capacitance retention greater than 100% after 25 000 charge/discharge cycles, showing an ultra-long cycle life.
中图分类号 TM242 DOI 10.11973/jxgccl202207008
所属栏目 新材料 新工艺
基金项目 上海市自然科学基金资助项目（21ZR1445700）
收稿日期 2021/4/6
修改稿日期 2022/5/5
网络出版日期
作者单位点击查看
备注石中婷(1996-),女,江苏南通人,硕士研究生通信作者(导师):赵斌教授
引用该论文: SHI Zhongting,MIAO Tianyu,ZHAO Bin. Preparation and Supercapacitive Performance of Metal-Organic Framework Derived NiCo2O4/rGO Composites[J]. Materials for mechancial engineering, 2022, 46(7): 38～46
石中婷,缪天宇,赵斌. 金属有机骨架衍生NiCo2O4/rGO复合材料的制备及其超级电容性能[J]. 机械工程材料, 2022, 46(7): 38～46
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【3】肖谧,宿玉鹏,杜伯学.超级电容器研究进展[J].电子元件与材料,2019,38(9):1-12. XIAO M,SU Y P,DU B X.Research progress of supercapacitors[J].Electronic Components and Materials,2019,38(9):1-12.
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【5】JEONG J H, KIM Y H, ROH K C, et al. Effect of thermally decomposable spacers on graphene microsphere structure and restacking of graphene sheets during electrode fabrication[J]. Carbon, 2019, 150:128-135.
【6】PARK J, KO T H, BALASUBRAMANIAM S, et al. Enhancing the performance and stability of NiCo2O4 nanoneedle coated on Ni foam electrodes with Ni seed layer for supercapacitor applications[J]. Ceramics International, 2019, 45(10):13099-13111.
【7】ZHOU Y,WEN L L,ZHAN K,et al.Three-dimensional porous graphene/nickel cobalt mixed oxide composites for high-performance hybrid supercapacitor[J].Ceramics International,2018,44(17):21848-21854.
【8】WU Z B,ZHU Y R,JI X B.NiCo2O4-based materials for electrochemical supercapacitors[J].Journal of Materials Chemistry A,2014,2(36):14759-14772.
【9】GUAN C,LIU X M,REN W N,et al.Rational design of metal-organic framework derived hollow NiCo2O4 arrays for flexible supercapacitor and electrocatalysis[J].Advanced Energy Materials,2017,7(12):1602391.
【10】GUAN B Y,KUSHIMA A,YU L,et al.Coordination polymers derived general synthesis of multishelled mixed metal-oxide particles for hybrid supercapacitors[J].Advanced Materials,2017,29(17):1605902.
【11】CHEN L F,LU Y,YU L,et al.Designed formation of hollow particle-based nitrogen-doped carbon nanofibers for high-performance supercapacitors[J].Energy & Environmental Science,2017,10(8):1777-1783.
【12】GHOSH S,SAMANTA P,SAMANTA P,et al.Investigation of electrochemical charge storage efficiency of NiCo2Se4/RGO composites derived at varied duration and its asymmetric supercapacitor device[J].Energy & Fuels,2020,34(10):13056-13066.
【13】JEONG G H,BAEK S,LEE S,et al.Metal oxide/graphene composites for supercapacitive electrode materials[J].Chemistry:an Asian Journal,2016,11(7):949-964.
【14】BORENSTEIN A,HANNA O,ATTIAS R,et al.Carbon-based composite materials for supercapacitor electrodes:A review[J].Journal of Materials Chemistry A,2017,5(25):12653-12672.
【15】CAO X H,ZHENG B,SHI W H,et al.Reduced graphene oxide-wrapped MoO3 composites prepared by using metal-organic frameworks as precursor for all-solid-state flexible supercapacitors[J]. Advanced Materials, 2015, 27:4695-4701.
【16】MA T Y,RAN J R,DAI S,et al.Phosphorus-doped graphitic carbon nitrides grown in situ on carbon-fiber paper:Flexible and reversible oxygen electrodes[J].Angewandte Chemie,2015,127(15):4729-4733.
【17】GUO M J,SONG S Y,ZHANG S S,et al.Fe-doped Ni-Co phosphide nanoplates with planar defects as an efficient bifunctional electrocatalyst for overall water splitting[J].ACS Sustainable Chemistry & Engineering,2020,8(19):7436-7444.
【18】LUO Y Z,ZHANG H M,GUO D,et al.Porous NiCo2O4-reduced graphene oxide (rGO) composite with superior capacitance retention for supercapacitors[J].Electrochimica Acta,2014,132:332-337.
【19】FAN Y C,LIU S T,HAN X,et al.Ni-Co-based nanowire arrays with hierarchical core-shell structure electrodes for high-performance supercapacitors[J].ACS Applied Energy Materials,2020,3(8):7580-7587.
【20】WANG Y J,HUANG S B,LU Y,et al.High-rate-capability asymmetric supercapacitor device based on lily-like Co3O4 nanostructures assembled using nanowires[J].RSC Advances,2017,7(7):3752-3759.
【21】JO E H,CHANG H,KIM S K,et al.One-step synthesis of Pt/graphene composites from Pt acid dissolved ethanol via microwave plasma spray pyrolysis[J].Scientific Reports,2016,6:33236.
【22】WANG Y Y,ZHANG Z Y,LIU X,et al.MOF-derived NiO/NiCo2O4 and NiO/NiCo2O4-rGO as highly efficient and stable electrocatalysts for oxygen evolution reaction[J].ACS Sustainable Chemistry & Engineering,2018,6(9):12511-12521.
【23】HONG J,PARK S J,KIM S.Synthesis and electrochemical characterization of nanostructured Ni-Co-MOF/graphene oxide composites as capacitor electrodes[J].Electrochimica Acta,2019,311:62-71.
【24】BEKA L G,BU X R,LI X,et al.A 2D metal-organic framework/reduced graphene oxide heterostructure for supercapacitor application[J].RSC Advances,2019,9(62):36123-36135.
【25】LEE C M,JO E H,KIM S K,et al.Electrochemical performance of crumpled graphene loaded with magnetite and hematite nanoparticles for supercapacitors[J].Carbon,2017,115:331-337.
【26】YANG Y J,LI W K.Hierarchical Ni-Co double hydroxide nanosheets on reduced graphene oxide self-assembled on Ni foam for high-energy hybrid supercapacitors[J].Journal of Alloys and Compounds,2019,776:543-553.
【27】KAMBLE G P,KASHALE A A,RASAL A S,et al.Marigold micro-flower like NiCo2O4 grown on flexible stainless-steel mesh as an electrode for supercapacitors[J].RSC Advances,2021,11(6):3666-3672.
【28】HA Y,SHI L X,YAN X X,et al.Multifunctional electrocatalysis on a porous N-doped NiCo2O4@C nanonetwork[J].ACS Applied Materials & Interfaces,2019,11(49):45546-45553.
【29】SHEN L F,CHE Q,LI H S,et al.Mesoporous NiCo2O4 nanowire arrays grown on carbon textiles as binder-free flexible electrodes for energy storage[J].Advanced Functional Materials,2014,24(18):2630-2637.
【30】ZHU Y D,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.
【31】LAHEÄÄR A,PRZYGOCKI P,ABBAS Q,et al.Appropriate methods for evaluating the efficiency and capacitive behavior of different types of supercapacitors[J].Electrochemistry Communications,2015,60:21-25.
【32】JI C C,LIU F Z,XU L,et al.Urchin-like NiCo2O4 hollow microspheres and FeSe2 micro-snowflakes for flexible solid-state asymmetric supercapacitors[J].Journal of Materials Chemistry A,5:5568-5576.
【33】HOU S J,XU X T,WANG M,et al.Carbon-incorporated Janus-type Ni2P/Ni hollow spheres for high performance hybrid supercapacitors[J].Journal of Materials Chemistry A,2017,5(36):19054-19061.
【34】RONG H,CHEN T,SHI R,et al.Hierarchical NiCo2O4@NiCo2S4 nanocomposite on Ni foam as an electrode for hybrid supercapacitors[J].ACS Omega,2018,3(5):5634-5642.
【35】WANG S,SUN S M,LI S D,et al.Time and temperature dependent multiple hierarchical NiCo2O4 for high-performance supercapacitors[J].Dalton Transactions,2016,45(17):7469-7475.
【36】CHEN W Q,WANG J,MA K Y,et al.Hierarchical NiCo2O4@Co-Fe LDH core-shell nanowire arrays for high-performance supercapacitor[J].Applied Surface Science,2018,451:280-288.
【37】LUO J H,WANG J,LIU S,et al.Graphene quantum dots encapsulated tremella-like NiCo2O4 for advanced asymmetric supercapacitors[J].Carbon,2019,146:1-8.
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