以山茶花瓣为模板合成多孔片层结构MnO2及其电化学性能
Preparation and Electrochemical Properties of Lamellar Porous MnO2 Synthesized by Using Camellia Petal as Biotemplates
摘 要
以山茶花瓣为模板, 以0.01,0.03,0.05,0.10 mol·L-1 MnNO3溶液为前驱体, 采用浸渍煅烧的方法合成了具有山茶花瓣微观形貌的多孔片层状MnO2, 并对它的结构和形貌进行了表征; 然后将MnO2作为负极材料安装成扣式锂离子电池, 测定了MnO2的电化学特性。结果表明: 合成的MnO2中均含有α、β和ε晶型的MnO2; 随着前驱体溶液浓度由0.01 mol·L-1增至0.10 mol·L-1, 制备的MnO2的比表面积由8.81 cm2·g-1增至39.82 cm2·g-1, 孔容由0.08 cm3·g-1增至0.26 cm3·g-1; 电池的首次库伦效率均大于22.56%, 经过10次循环后的可逆容量仍能保持70 mAh·g-1。
二氧化锰
多孔结构
生物模板
锂离子电池
电化学性能
camellia petal
MnO2
porous structure
biological template
lithium-ion battery
electrochemical property
Abstract
The biomorphic MnO2 materials with lamellar porous structure were successfully synthesized by using camellia petal as biotemplate and MnNO3 solution of 0.01,0.03,0.05,0.10 mol·L-1 as precursor. Their structure and morphology were characterized. And then lithium-ion battery was assembled by using MnO2 as negative electrode material, the electrochemical properties of MnO2 was tested. Results show that all MnO2 contained α, β and ε form MnO2 crystals. The specific surface area and pore volume of MnO2 respectively increased from 8.81 cm2·g-1 to 39.82 cm2·g-1 and from 0.08 cm3·g-1 to 0.26 cm3·g-1 with the concentration of precursor solution increased from 0.01 mol·L-1 to 0.10 mol·L-1. In addition, the first coulombic efficiency of lithium-ion battery was more than 22.56%, and the reversible capacity of the battery could still maintain 70 mAh·g-1 after 10 cycles.
中图分类号 TB34 DOI 10.11973/jxgccl201603011
所属栏目 材料性能及其应用
基金项目 国家自然科学基金资助项目(21103119, 21277094, 21407111); 江苏省高校自然科学研究面上项目(11KJB430012); 教育部留学回国人员科研启动经费资助项目(［2013］693); 江苏省环境功能材料重点实验室开放课题项目(SJHG1310); 江苏省高校研究生科研创新计划项目(CXZZ13_0855)
收稿日期 2015/2/1
修改稿日期 2015/12/13
网络出版日期
作者单位点击查看
备注王赛(1989-), 男, 江苏宿迁人, 硕士研究生。
引用该论文: WANG Sai,XU Song-song,WU Zheng-ying,YE Peng,CHEN Feng,LIU Cheng-bao,LI Ping,CHEN Zhi-gang. Preparation and Electrochemical Properties of Lamellar Porous MnO2 Synthesized by Using Camellia Petal as Biotemplates[J]. Materials for mechancial engineering, 2016, 40(3): 43～48
王赛,许松松,吴正颖,叶朋,陈丰,刘成宝,李萍,陈志刚. 以山茶花瓣为模板合成多孔片层结构MnO2及其电化学性能[J]. 机械工程材料, 2016, 40(3): 43～48
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参考文献
【1】DEBECKER D P, HUlEA V, MUTIN P H. Mesoporous mixed oxide catalysts via non-hydrolytic sol-gel: a review［J］. Applied Catalysis A: General, 2013, 451: 192-206.
【2】BIBBY A, MERCIER L. Adsorption and separation of water-soluble aromatic molecules by cyclodextrin-functionalized mesoporous silica［J］. Green Chemistry, 2003,5:15-19.
【3】POYRAZ A S, BISWAS S, GENUINO H C, et al. Bimodification of mesoporous silicon oxide by coupled "In situ oxidation at the interface and ion exchange" and its catalytic activity in the gas-phase toluene oxidation［J］. Chem Cat Chem,2012,5(4): 920-930.
【4】DE VOS D E, DAMS M, SELS B F, et al. Ordered mesoporous and microporous molecular sieves functionalized with transition metal complexes as catalysts for selective organic transformations［J］. Chemical Reviews, 2002, 102(10): 3615-3640.
【5】TAGUCHI A, SCHUTH F. Ordered mesoporous materials in catalysis［J］. Microporous Mesoporous Materials, 2005, 77(1): 1-45.
【6】POYRAZ A S, SONG W Q, KRIZ D, et al. Crystalline mesoporous K2-xMn8O16 and ε-MnO2 by mild transformations of amorphous mesoporous manganese oxides and their enhanced redox properties［J］. Applied Materials and Interfaces, 2014, 6(14): 10986-10991.
【7】HAN D D, JING X Y, XU P C, et al. Facile synthesis of hierarchical hollow ε-MnO2 spheresandtheir application in supercapacitor electrodes［J］. Journal of Solid State Chemistry, 2014, 218: 178-183.
【8】TITIRICI M M, ANTONIETTI M, THOMAS A, et al. A generalized synthesis of metal oxide hollow spheres using a hydrothermal approach［J］. Chemistry of Materials, 2006, 18(16): 3808-3812.
【9】MARK E D. Ordered porous materials for emerging applications［J］. Nature, 2002, 417: 813-821.
【10】YU P, ZHANG X, WANG D L, et al. Shape-controlled synthesis of 3D hierarchical MnO2 nanostructures for electrochemical supercapacitors［J］. Crystal Growth and Design, 2009, 9(1): 528-533.
【11】YOUSEFI T, GOLIKAND A N, MASHHADIZADEH M H, et al. Facile synthesis of α-MnO2 one-dimensional (1D) nanostructure and energy storage ability studies［J］. Journal of Solid State Chemistry, 2012, 190:202-207.
【12】MA N, SARGENT E H, KELLEY S O. Biotemplated nanostructures: directed assembly of electronic and optical materials using nanoscale complementarity［J］. Journal of Materials Chemistry, 2008, 18(9): 954-964.
【13】QIAN J C, CHEN F, ZHAO X B, et al. China rose petal as biotemplate to produce two-dimensional ceria nanosheets［J］. Journal of Nanoparticle Research, 2011, 13:7149-7158.
【14】SHIM H W, JIN Y H, SEO S D, et al. Highly reversible lithium storage in bacillus subtilis-directed porous Co3O4 nanostructures［J］. ACS Nano, 2010, 5(1): 443-449.
【15】LI X, FAN T, ZHOU H, et al. Enhanced light-harvesting and photocatalytic properties in morph-TiO2 from green-leaf biotemplates［J］. Advanced Functional Materials, 2009, 19(1): 45-56.
【16】KOSTOVSKI G, WHITE D, MITCHELL A, et al. Nanoimprinted optical fibres: biotemplated nanostructures for SERS sensing［J］. Biosensors and Bioelectronics, 2009, 24(5): 1531-1535.
【17】ZHANG W, ZHANG D, FAN T, et al. Novel photoanode structure templated from butterfly wing scales［J］. Chemistry of Materials, 2008, 21(1): 33-40.
【18】GREIL P. Biomorphous ceramics from lignocellulosics［J］. Journal of the European Ceramic Society, 2001, 21(2): 105-118.
【19】LIU Y K, WANG H, ZHU Y C, et al. Pyrolysis synthesis of magnetic ε- and β-MnO2 nanostructures and the polymorph discrimination［J］. Solid State Communications, 2009, 49(37/38): 1514-1518.
【20】HU X F, HAN X P, HU Y X, et al. ε-MnO2 nanostructures directly grown on Ni foam: a cathode catalyst for rechargeable LiO2 batteries［J］. Nanoscale, 2014, 6: 3522.
【21】杨建锋, 刘建华, 潘文硕, 等. 内热式回转炉处理电解MnO2技术的研究［J］. 电源技术, 2005, 29(8): 535-538.
【22】VCLAV , DANIELA K, FRANTIEK O, et al. Mesoporous manganese oxide for warfare agents degradation［J］. Microporous and Mesoporous Materials, 2012, 156: 224-232.
【23】WANG J G, YANG Y, HUANG Z H, et al. Interfacial synthesis of mesoporous MnO2/polyaniline hollow spheres and their application in electrochemical capacitors［J］. Journal of Power Sources, 2012, 204: 236-243.
【24】KARIMI A, MAHDIZADEH F, SALARI D, et al. Bio-deoxygenation of water using glucose oxidase immobilized in mesoporous MnO2［J］.Desalination,2011,275(1/3):148-153.
【25】ZHU J Y, HE J H. Facile synthesis of graphene-wrapped honeycomb MnO2 nanospheres and their application in supercapacitors［J］. Applied Materials and Interfaces, 2012, 4 (3): 1770-1776.
【26】FENG X M, YAN Z Z, CHEN N G, et al. The synthesis of shape-controlled MnO2/graphene composites via a facile one-step hydrothermal methodand their application in supercapacitors［J］. Journal of Materials Chemistry A, 2013, 47(1): 12818-12825.
【27】陈丰, 曹煜, 刘成宝, 等. 以滤纸为模板制备多孔CeO2纤维及其催化性能［J］. 机械工程材料, 2014, 38(8): 33-38.
【28】徐如人, 庞文琴. 分子筛与多孔材料化学［M］. 北京: 科学出版社, 2004:147-148.
【2】BIBBY A, MERCIER L. Adsorption and separation of water-soluble aromatic molecules by cyclodextrin-functionalized mesoporous silica［J］. Green Chemistry, 2003,5:15-19.
【3】POYRAZ A S, BISWAS S, GENUINO H C, et al. Bimodification of mesoporous silicon oxide by coupled "In situ oxidation at the interface and ion exchange" and its catalytic activity in the gas-phase toluene oxidation［J］. Chem Cat Chem,2012,5(4): 920-930.
【4】DE VOS D E, DAMS M, SELS B F, et al. Ordered mesoporous and microporous molecular sieves functionalized with transition metal complexes as catalysts for selective organic transformations［J］. Chemical Reviews, 2002, 102(10): 3615-3640.
【5】TAGUCHI A, SCHUTH F. Ordered mesoporous materials in catalysis［J］. Microporous Mesoporous Materials, 2005, 77(1): 1-45.
【6】POYRAZ A S, SONG W Q, KRIZ D, et al. Crystalline mesoporous K2-xMn8O16 and ε-MnO2 by mild transformations of amorphous mesoporous manganese oxides and their enhanced redox properties［J］. Applied Materials and Interfaces, 2014, 6(14): 10986-10991.
【7】HAN D D, JING X Y, XU P C, et al. Facile synthesis of hierarchical hollow ε-MnO2 spheresandtheir application in supercapacitor electrodes［J］. Journal of Solid State Chemistry, 2014, 218: 178-183.
【8】TITIRICI M M, ANTONIETTI M, THOMAS A, et al. A generalized synthesis of metal oxide hollow spheres using a hydrothermal approach［J］. Chemistry of Materials, 2006, 18(16): 3808-3812.
【9】MARK E D. Ordered porous materials for emerging applications［J］. Nature, 2002, 417: 813-821.
【10】YU P, ZHANG X, WANG D L, et al. Shape-controlled synthesis of 3D hierarchical MnO2 nanostructures for electrochemical supercapacitors［J］. Crystal Growth and Design, 2009, 9(1): 528-533.
【11】YOUSEFI T, GOLIKAND A N, MASHHADIZADEH M H, et al. Facile synthesis of α-MnO2 one-dimensional (1D) nanostructure and energy storage ability studies［J］. Journal of Solid State Chemistry, 2012, 190:202-207.
【12】MA N, SARGENT E H, KELLEY S O. Biotemplated nanostructures: directed assembly of electronic and optical materials using nanoscale complementarity［J］. Journal of Materials Chemistry, 2008, 18(9): 954-964.
【13】QIAN J C, CHEN F, ZHAO X B, et al. China rose petal as biotemplate to produce two-dimensional ceria nanosheets［J］. Journal of Nanoparticle Research, 2011, 13:7149-7158.
【14】SHIM H W, JIN Y H, SEO S D, et al. Highly reversible lithium storage in bacillus subtilis-directed porous Co3O4 nanostructures［J］. ACS Nano, 2010, 5(1): 443-449.
【15】LI X, FAN T, ZHOU H, et al. Enhanced light-harvesting and photocatalytic properties in morph-TiO2 from green-leaf biotemplates［J］. Advanced Functional Materials, 2009, 19(1): 45-56.
【16】KOSTOVSKI G, WHITE D, MITCHELL A, et al. Nanoimprinted optical fibres: biotemplated nanostructures for SERS sensing［J］. Biosensors and Bioelectronics, 2009, 24(5): 1531-1535.
【17】ZHANG W, ZHANG D, FAN T, et al. Novel photoanode structure templated from butterfly wing scales［J］. Chemistry of Materials, 2008, 21(1): 33-40.
【18】GREIL P. Biomorphous ceramics from lignocellulosics［J］. Journal of the European Ceramic Society, 2001, 21(2): 105-118.
【19】LIU Y K, WANG H, ZHU Y C, et al. Pyrolysis synthesis of magnetic ε- and β-MnO2 nanostructures and the polymorph discrimination［J］. Solid State Communications, 2009, 49(37/38): 1514-1518.
【20】HU X F, HAN X P, HU Y X, et al. ε-MnO2 nanostructures directly grown on Ni foam: a cathode catalyst for rechargeable LiO2 batteries［J］. Nanoscale, 2014, 6: 3522.
【21】杨建锋, 刘建华, 潘文硕, 等. 内热式回转炉处理电解MnO2技术的研究［J］. 电源技术, 2005, 29(8): 535-538.
【22】VCLAV , DANIELA K, FRANTIEK O, et al. Mesoporous manganese oxide for warfare agents degradation［J］. Microporous and Mesoporous Materials, 2012, 156: 224-232.
【23】WANG J G, YANG Y, HUANG Z H, et al. Interfacial synthesis of mesoporous MnO2/polyaniline hollow spheres and their application in electrochemical capacitors［J］. Journal of Power Sources, 2012, 204: 236-243.
【24】KARIMI A, MAHDIZADEH F, SALARI D, et al. Bio-deoxygenation of water using glucose oxidase immobilized in mesoporous MnO2［J］.Desalination,2011,275(1/3):148-153.
【25】ZHU J Y, HE J H. Facile synthesis of graphene-wrapped honeycomb MnO2 nanospheres and their application in supercapacitors［J］. Applied Materials and Interfaces, 2012, 4 (3): 1770-1776.
【26】FENG X M, YAN Z Z, CHEN N G, et al. The synthesis of shape-controlled MnO2/graphene composites via a facile one-step hydrothermal methodand their application in supercapacitors［J］. Journal of Materials Chemistry A, 2013, 47(1): 12818-12825.
【27】陈丰, 曹煜, 刘成宝, 等. 以滤纸为模板制备多孔CeO2纤维及其催化性能［J］. 机械工程材料, 2014, 38(8): 33-38.
【28】徐如人, 庞文琴. 分子筛与多孔材料化学［M］. 北京: 科学出版社, 2004:147-148.
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