镍掺杂聚苯胺/生物质炭复合材料的电化学性能

摘要/Abstract

摘要： 为制备高性能、低成本的电极材料,本文以八月瓜果皮生物质炭(BC)为基质,六水合硝酸镍、苯胺为原料,通过化学氧化聚合法合成了镍离子掺杂聚苯胺包覆生物质炭复合材料(Ni@PANI/BC)。通过扫描电镜(SEM)及能谱仪(EDS)、X射线光电子能谱(XPS)、热重分析(TG)、比表面积测试(BET)等表征手段对其结构进行表征,循环伏安法(CV)、恒电流充放电(GCD)测试和电化学阻抗谱(EIS)对其进行电化学性能测定,考察了镍离子掺杂对Ni@PANI/BC结构和电化学性能的影响。研究表明,镍离子掺杂聚苯胺包覆生物质炭形成了多孔交联网状结构、比表面积大、导电性能良好的复合材料。当六水合硝酸镍与苯胺、BC质量比为1.5∶5∶3时,所得的电极材料电化学性能最佳。在1 A/g电流密度下,Ni@PANI/BC质量比电容最高可达608.4 F/g,在10 A/g下,充放电循环5 000次,容量保持率为85.4%,该材料具有与文献报道相关材料相媲美的电化学性能。

关键词: 生物质炭, 聚苯胺, 化学氧化聚合法, 复合材料, 电容, 电化学性能

Abstract: In order to prepare high-performance and low-cost electrode materials, nickel ion-doped polyANI-coated biomass carbon composite materials (Ni@PANI/BC) were synthesized by chemical oxidation polymerization using August melon peel biomass carbon (BC) as the matrix, and nickel nitrate and aniline as raw materials. The structures of the Ni@PANI/BC composites were characterized by SEM, EDS, X-ray photoelectron energy spectrum (XPS), thermal weight analysis (TG) and specific surface area test (BET), and the electrochemical properties of the composites were measured by cyclic voltammetry (CV), constant current charge and discharge (GCD) test and electrochemical impedance spectroscopy (EIS). The effects of nickel ion doping on the structure and electrochemical properties of Ni@PANI/BC were investigated. It is shown that nickel ion doped BC forms a porous cross-linked mesh porous structure with large specific surface area and good electrical conductivity. When the mass ratio of nickel hydrate nitrate, aniline and BC is 1.5∶5∶3, the obtained electrode material has the best electrochemical performance. At 1 A/g current density, Ni@PANI/BC mass capacitance is up to 608.4 F/g, 5 000 cycles with a capacity retention rate of 85.4%, which demonstrates Ni@PANI/BC materials have electrochemical properties comparable to the relevant materials reported in the literature.

Key words: biomass carbon, polyaniline, chemical oxidation polymerization, composite, capacitance, electrochemical property

中图分类号:

TB332

张丹丹, 田满泽, 鄢波, 任俊鹏, 周进康. 镍掺杂聚苯胺/生物质炭复合材料的电化学性能[J]. 人工晶体学报, 2024, 53(7): 1280-1287.

ZHANG Dandan, TIAN Manze, YAN Bo, REN Junpeng, ZHOU Jinkang. Electrochemical Properties of Ni-Doped Polyaniline/Biomass Carbon Composites[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(7): 1280-1287.

参考文献

[1] SUPRIYONO, AMALIA E A, SOLIKHAH D N, et al. Porous biochar purification method from coconut shell by alkali roasting followed by leaching and its application as a lithium primary battery[J]. IOP Conference Series: Earth and Environmental Science, 2021, 749(1): 012036.
[2] ZHOU P F, WONG P K, NIU P D, et al. Anodized AlCoCrFeNi high-entropy alloy for alkaline water electrolysis with ultra-high performance[J]. Science China Materials, 2023, 66(3): 1033-1041.
[3] 张璐璐, 谭伯川, 李文坡. Cu²⁺掺杂MnO₂作为水系锌离子电池正极材料的合成与电化学性能[J]. 化工学报, 2021, 72(10): 5402-5411.
ZHANG L L, TAN B C, LI W P. Synthesis and electrochemical properties of Cu²⁺-doped MnO₂ as cathode materials for aqueous zinc ion batteries[J]. CIESC Journal, 2021, 72(10): 5402-5411 (in Chinese).
[4] KHAN N A, RAHMAN G, NGUYEN T M, et al. Recent development of nanostructured nickel metal-based electrocatalysts for hydrogen evolution reaction: a review[J]. Topics in Catalysis, 2023, 66(1): 149-181.
[5] PARSIMEHR H, EHSANI A, PAYAM S A. Electrochemical energy storage electrodes from rice biochar[J]. Biomass Conversion and Biorefinery, 2023, 13(14): 12413-12429.
[6] MEHDI R, NAQVI S R, KHOJA A H, et al. Biomass derived activated carbon by chemical surface modification as a source of clean energy for supercapacitor application[J]. Fuel, 2023, 348: 128529.
[7] 牛文娟, 邓继猛, 冯雨欣, 等. 不同温度下水稻秸秆多孔生物炭结构与电化学性能[J]. 农业工程学报, 2022, 38(2): 231-240.
NIU W J, DENG J M, FENG Y X, et al. Structure and electrochemical performances of porous biochar from rice straw at different temperatures[J]. Transactions of the Chinese Society of Agricultural Engineering, 2022, 38(2): 231-240 (in Chinese).
[8] LI C Y, FENG Y X, ZHONG F, et al. Optimization of microwave-assisted hydrothermal carbonization and potassium bicarbonate activation on the structure and electrochemical characteristics of crop straw-derived biochar[J]. Journal of Energy Storage, 2022, 55: 105838.
[9] DU Y Y, YING Z, ZHENG X Y, et al. Efficient anodic biochar oxidation over three-dimensional self-support nickel-iron nanosheet on nickel foam in biochar-assisted water electrolysis for hydrogen production[J]. International Journal of Hydrogen Energy, 2023, 48(3): 894-908.
[10] 费洋, 黄惠, 宋爽, 等. 接枝聚合法制备PANI/CeO₂-APTMS复合材料及其电化学性能[J]. 高分子材料科学与工程, 2017, 33(7): 81-87.
FEI Y, HUANG H, SONG S, et al. Graft preparation and electrochemical properties of PANI/CeO₂-APTMS composite[J]. Polymer Materials Science & Engineering, 2017, 33(7): 81-87 (in Chinese).
[11] MARTINS J C, DE M NETO J C, PASSOS R R, et al. Electrochemical behavior of polyaniline: a study by electrochemical impedance spectroscopy (EIS) in low-frequency[J]. Solid State Ionics, 2020, 346: 115198.
[12] LUCEÑO SÁNCHEZ J A, DÍEZ-PASCUAL A M, PEÑA CAPILLA R, et al. The effect of hexamethylene diisocyanate-modified graphene oxide as a nanofiller material on the properties of conductive polyaniline[J]. Polymers, 2019, 11(6): 1032.
[13] YAO M Y, ZHAO X, ZHANG Q H, et al. Polyaniline nanowires aligned on MOFs-derived nanoporous carbon as high-performance electrodes for supercapacitor[J]. Electrochimica Acta, 2021, 390: 138804.
[14] 王彪, 陈鼎智, 马安宁, 等. 聚苯胺纳米线复合材料的制备与储能性分析[J]. 中国表面工程, 2023, 36(3): 121-131.
WANG B, CHEN D Z, MA A N, et al. Synthesis and electrochemical properties of intercalated polyaniline nanowire composites[J]. China Surface Engineering, 2023, 36(3): 121-131 (in Chinese).
[15] FIRDA P B D, MALIK Y T, OH J K, et al. Enhanced chemical and electrochemical stability of polyaniline-based layer-by-layer films[J]. Polymers, 2021, 13(17): 2992.
[16] 王建明, 任治宇, 蔡鹤铭, 等. NiO-CuO纳米材料的制备及其电化学性能[J]. 微纳电子技术, 2022, 59(8): 771-777.
WANG J M, REN Z Y, CAI H M, et al. Preparation of NiO-CuO nanometer materials and their electrochemical properties[J]. Micronanoelectronic Technology, 2022, 59(8): 771-777 (in Chinese).
[17] 李欣蔚, 王丽英, 曹珍珠, 等. HP-CoFe₂O₄/C锂离子电池负极材料的制备及电化学性能研究[J]. 化工新型材料, 2022, 50(12): 121-128.
LI X W, WANG L Y, CAO Z Z, et al. Synthesis and electrochemical performance of HP-CoFe₂O₄/C anode material for lithiumion battery[J]. New Chemical Materials, 2022, 50(12): 121-128 (in Chinese).
[18] 徐惠, 李琦, 陈泳, 等. 过渡金属离子电化学掺杂聚苯胺的超级电容性能[J]. 高分子材料科学与工程, 2018, 34(1): 83-88.
XU H, LI Q, CHEN Y, et al. Polyaniline electrode doped with transition metal ions for electrochemical supercapacitors[J]. Polymer Materials Science & Engineering, 2018, 34(1): 83-88 (in Chinese).
[19] LIU Y C, CHEN Y Q, ZHANG X X, et al. A high-voltage aqueous rechargeable zinc-polyaniline hybrid battery achieved by decoupling alkali-acid electrolyte[J]. Chemical Engineering Journal, 2022, 444: 136478.
[20] 符刚, 张秀玲. 碳纳米管@聚苯胺/二硫化钼复合材料的制备及其电化学性能研究[J]. 现代化工, 2023, 43(6): 205-211.
FU G, ZHANG X L. Preparation of carbon nanotube@polyaniline/molybdenum disulfide composite for supercapacitor application[J]. Modern Chemical Industry, 2023, 43(6): 205-211 (in Chinese).
[21] 李海瑞, 李智芳, 纪帅, 等. PANI/MnOC生物质碳基电极材料的制备及电化学性能研究[J]. 功能材料, 2021, 52(8): 8118-8124.
LI H R, LI Z F, JI S, et al. Preparation and electrochemical properties of PANI/MnOC composite biomass carbon materials[J]. Journal of Functional Materials, 2021, 52(8): 8118-8124 (in Chinese).
[22] 韦会鸽, 彭紫芳, 陈安利, 等. 生物质基多级孔活性炭-聚苯胺复合材料的合成及其电化学储能性能[J]. 复合材料学报, 2022, 39(8): 4028-4036.
WEI H G, PENG Z F, CHEN A L, et al. Synthesis and electrochemical energy storage performance of biomass-based porous hierarchical activated carbon-polyaniline composites[J]. Acta Materiae Compositae Sinica, 2022, 39(8): 4028-4036 (in Chinese).
[23] CHEN Y C, XIE Y B. Electrochemical performance of manganese coordinated polyaniline[J]. Advanced Electronic Materials, 2019, 5(12): 1900816.
[24] 苏燕平. Ni-BTC MOFs衍生材料及其性能研究[D]. 合肥: 中国科学技术大学, 2017.
SU Y P. The synthesis and applications of Ni-BTC MOFs derivatives[D].Hefei: University of Science and Technology of China, 2017 (in Chinese).
[25] 冯准. 基于石墨烯电极的埃洛石/聚苯胺超高柔性复合电极储能材料与器件[J]. 储能科学与技术, 2023, 12(6): 1794-1803.
FENG Z. Ultra-flexible halloysite/polyaniline composite electrode based on graphene electrode[J]. Energy Storage Science and Technology, 2023, 12(6): 1794-1803 (in Chinese).
[26] 张亚婷, 任绍昭, 李景凯, 等. PANI/煤基石墨烯宏观体复合材料的制备及其电化学性能[J]. 化工学报, 2017, 68(11): 4316-4322.
ZHANG Y T, REN S Z, LI J K, et al. Fabrication and electrochemical capacitive performance of PANI/coal-based three-dimensional graphene[J]. CIESC Journal, 2017, 68(11): 4316-4322 (in Chinese).
[27] 张政, 刘洪达, 宋朝霞, 等. 聚苯胺包覆CoFe类普鲁士蓝复合材料的超电容性能[J]. 复合材料学报, 2020, 37(3): 731-739.
ZHANG Z, LIU H D, SONG Z X, et al. Supercapacitive performance of polyaniline coated CoFe Prussian blue analogue composite[J]. Acta Materiae Compositae Sinica, 2020, 37(3): 731-739 (in Chinese).
[28] LEI D Y, LI X D, RADHAKRISHNAN S, et al. Polyaniline decorated salt activated phenolic resin/PAN-based carbon nanofibers with remarkable cycle stability for energy storage applications[J]. Materials Letters, 2023, 333: 133688.