ZnCo_2O_4/N-3D石墨烯的制备及其电化学性能研究
|
摘要
通过简单的水热-煅烧裂解法,将氮掺杂的三维石墨烯与钴酸锌复合制备电极材料,在160℃分别反应3、4、5、6.5、8 h,样品平均比表面积为25 m2/g,平均孔径为14 nm左右,主要以介孔存在,有利于电解质与电极材料的有效接触和电解质离子的传输。经测试,材料在160℃反应5 h时比电容值最高,在电流密度为1和20 A/g下,比电容分别为304和217 F/g,保持率为71.4%。且三电极体系下充放电循环1 000次,材料表现出良好的循环稳定性;并且内阻较小为0.5Ω,表现出良好的阻抗行为。
The N doped 3D graphene/ZnCo_2O_4 was prepared by simple hydrothermal-calcination method, at 160 ℃reacting for 3, 4, 5, 6.5, 8 h. The specific surface area of the obtained material is about 25 m2/g, and the material contains a lot of mesoporous with the average pore size of 14 nm, which is good for the effective contact between electrolyte and electrode and the transportation of electrolyte ions. The test results show that the material reacting for5 h at 160 ℃ exhibits higher specific capacitance. Compared with 304 F/g at 1 A/g, the specific capacitance is still217 F/g at 20 A/g, indicating that the electrode material has great rate performance. After 1 000 times of chargedischarge cycles, the retention rate is 92%, meaning the material has excellent cycling stability.
The N doped 3D graphene/ZnCo_2O_4 was prepared by simple hydrothermal-calcination method, at 160 ℃reacting for 3, 4, 5, 6.5, 8 h. The specific surface area of the obtained material is about 25 m2/g, and the material contains a lot of mesoporous with the average pore size of 14 nm, which is good for the effective contact between electrolyte and electrode and the transportation of electrolyte ions. The test results show that the material reacting for5 h at 160 ℃ exhibits higher specific capacitance. Compared with 304 F/g at 1 A/g, the specific capacitance is still217 F/g at 20 A/g, indicating that the electrode material has great rate performance. After 1 000 times of chargedischarge cycles, the retention rate is 92%, meaning the material has excellent cycling stability.
引文
[1] XU Y X, SHENG K X, LI C, et al. Self-assembled graphene hydrogel via a one-step hydrothermal process[J]. ACS NANO, 2010,4(7):4324-4330.
[2] JIANG F, ZHAO S H, GUO J X, et al. ZnCo2O4nanoparticles/N-doped three-dimensional graphene composite with enhanced lithium-storage performance[J].Materials Letters, 2015,161:297-300.
[3] WANG T, WANG L X, WU D L, et al. Hydrothermal synthesis of nitrogen-doped graphene hydrogels using amino acids with different acidities as doping agents[J]. Journal of Materials Chemistry A,2014, 2(22):8352-8361.
[4] ZHANG Y Q, ZHAI Y. FexSnyMn1-x-yO2deposited on MCM-41 as electrode for electrochemical supercapacitor[J]. Electrochimica Acta, 2016, 192:328-339.
[5] ZANDI M, AMIRHOSEINY M, MOSAYYEBI A, et al. Nanoporous all metallic binder free Sn:Pb composite electrode for high performance supercapacitors[J]. Microelectronic Engineering, 2016, 157:31-34.
[6] JIANG L Y, SUI Y W, QI J Q, et al. Electrodeposition of Ni-Co double hydroxide composite nanosheets on Fe substrate for highperformance supercapacitor electrode[J]. Micro&Nano Letters,2016, 11(12):837-839.
[7] LI N, ZHI C Y, ZHANG H Y. High performance transparent and flexible asymmetric supercapacitor based on graphene-wrapped amorphous Fe OOH nanowire and Co(OH)2nanosheet transparent films produced at air-water interface[J]. Electrochimica Acta, 2016,220:618-627.
[8] LIU M X, MA X M, GAN L H, et al. A facile synthesis of a novel mesoporous Ge@C sphere anode with stable and high capacity for lithium ion batteries[J]. J Mater Chem A,2014, 2(40):17107-17114.
[9] GUAN B K, GUO D, HU L L, et al. Facile synthesis of Zn Co2O4nanowire cluster arrays on Ni foam for high-performance asymmetric supercapacitors[J]. J Mater Chem A, 2014, 38:16116-16123.
[10]詹亚利.超级电容器石墨烯基电极材料制备及电化学性能研究[D].保定:河北大学, 2017.
[11] HUMMERS W S, OFFEMAN R E. Preparation of graphitic oxide[J]. J Am Chem Soc, 1958, 80:1339.á?á?á?
[2] JIANG F, ZHAO S H, GUO J X, et al. ZnCo2O4nanoparticles/N-doped three-dimensional graphene composite with enhanced lithium-storage performance[J].Materials Letters, 2015,161:297-300.
[3] WANG T, WANG L X, WU D L, et al. Hydrothermal synthesis of nitrogen-doped graphene hydrogels using amino acids with different acidities as doping agents[J]. Journal of Materials Chemistry A,2014, 2(22):8352-8361.
[4] ZHANG Y Q, ZHAI Y. FexSnyMn1-x-yO2deposited on MCM-41 as electrode for electrochemical supercapacitor[J]. Electrochimica Acta, 2016, 192:328-339.
[5] ZANDI M, AMIRHOSEINY M, MOSAYYEBI A, et al. Nanoporous all metallic binder free Sn:Pb composite electrode for high performance supercapacitors[J]. Microelectronic Engineering, 2016, 157:31-34.
[6] JIANG L Y, SUI Y W, QI J Q, et al. Electrodeposition of Ni-Co double hydroxide composite nanosheets on Fe substrate for highperformance supercapacitor electrode[J]. Micro&Nano Letters,2016, 11(12):837-839.
[7] LI N, ZHI C Y, ZHANG H Y. High performance transparent and flexible asymmetric supercapacitor based on graphene-wrapped amorphous Fe OOH nanowire and Co(OH)2nanosheet transparent films produced at air-water interface[J]. Electrochimica Acta, 2016,220:618-627.
[8] LIU M X, MA X M, GAN L H, et al. A facile synthesis of a novel mesoporous Ge@C sphere anode with stable and high capacity for lithium ion batteries[J]. J Mater Chem A,2014, 2(40):17107-17114.
[9] GUAN B K, GUO D, HU L L, et al. Facile synthesis of Zn Co2O4nanowire cluster arrays on Ni foam for high-performance asymmetric supercapacitors[J]. J Mater Chem A, 2014, 38:16116-16123.
[10]詹亚利.超级电容器石墨烯基电极材料制备及电化学性能研究[D].保定:河北大学, 2017.
[11] HUMMERS W S, OFFEMAN R E. Preparation of graphitic oxide[J]. J Am Chem Soc, 1958, 80:1339.á?á?á?