Synthesis of MnO_2/N-doped ultramicroporous carbon nanospheres for high-performance supercapacitor electrodes
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摘要
We demonstrate a simple and highly efficient strategy to synthesize MnO_2/nitrogen-doped ultramicroporous carbon nanospheres(MnO_2/N-UCNs) for supercapacitor application.MnO_2/N-UCNs were fabricated via a template-free polymerization of resorcinol/formaldehyde on the surface of phloroglucinol/terephthalaldehyde colloids in the presence of hexamethylenetetramine,followed by carbonization and then a redox reaction between carbons and KMnO_4.As-prepared MnO_2/N-UCNs exhibits regular ultramicropores,high surface area,nitrogen heteroatom,and high content of MnO_2.A typical MnO_2/N-UCNs with 57 wt.%MnO_2 doping content(denoted as MnO_2(57%)/N-UCNs) makes the most use of the synergistic effect between carbons and metal oxides.MnO_2(57%)/N-UCNs as a supercapacitor electrode exhibits excellent electrochemical performance such as a high specific capacitance(401 F/g at 1.0 A/g) and excellent charge/discharge stability(86.3%of the initial capacitance after 10,000 cycles at 2.0 A/g) in 1.0 mol/L Na_2SO_4 electrolyte.The well-designed and high-performance MnO_2/N-UCNs highlight the great potential for advanced supercapacitor applications.
We demonstrate a simple and highly efficient strategy to synthesize MnO_2/nitrogen-doped ultramicroporous carbon nanospheres(MnO_2/N-UCNs) for supercapacitor application.MnO_2/N-UCNs were fabricated via a template-free polymerization of resorcinol/formaldehyde on the surface of phloroglucinol/terephthalaldehyde colloids in the presence of hexamethylenetetramine,followed by carbonization and then a redox reaction between carbons and KMnO_4.As-prepared MnO_2/N-UCNs exhibits regular ultramicropores,high surface area,nitrogen heteroatom,and high content of MnO_2.A typical MnO_2/N-UCNs with 57 wt.%MnO_2 doping content(denoted as MnO_2(57%)/N-UCNs) makes the most use of the synergistic effect between carbons and metal oxides.MnO_2(57%)/N-UCNs as a supercapacitor electrode exhibits excellent electrochemical performance such as a high specific capacitance(401 F/g at 1.0 A/g) and excellent charge/discharge stability(86.3%of the initial capacitance after 10,000 cycles at 2.0 A/g) in 1.0 mol/L Na_2SO_4 electrolyte.The well-designed and high-performance MnO_2/N-UCNs highlight the great potential for advanced supercapacitor applications.
We demonstrate a simple and highly efficient strategy to synthesize MnO_2/nitrogen-doped ultramicroporous carbon nanospheres(MnO_2/N-UCNs) for supercapacitor application.MnO_2/N-UCNs were fabricated via a template-free polymerization of resorcinol/formaldehyde on the surface of phloroglucinol/terephthalaldehyde colloids in the presence of hexamethylenetetramine,followed by carbonization and then a redox reaction between carbons and KMnO_4.As-prepared MnO_2/N-UCNs exhibits regular ultramicropores,high surface area,nitrogen heteroatom,and high content of MnO_2.A typical MnO_2/N-UCNs with 57 wt.%MnO_2 doping content(denoted as MnO_2(57%)/N-UCNs) makes the most use of the synergistic effect between carbons and metal oxides.MnO_2(57%)/N-UCNs as a supercapacitor electrode exhibits excellent electrochemical performance such as a high specific capacitance(401 F/g at 1.0 A/g) and excellent charge/discharge stability(86.3%of the initial capacitance after 10,000 cycles at 2.0 A/g) in 1.0 mol/L Na_2SO_4 electrolyte.The well-designed and high-performance MnO_2/N-UCNs highlight the great potential for advanced supercapacitor applications.
引文
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[3](a)H.Chang,H.Wu,Graphene-based nanocomposites:preparation,functionalization,and energy and environmental applications,Energy Environ.Sci.6(2013)3483-3507;(b)K.Pinkert,L.Giebeler,M.Herklotz,et al.,Functionalised porous nanocomposites:a multidisciplinary approach to investigate designed structures for supercapacitor applications,J.Mater.Chem.A 1(2013)4904-4910.
[4](a)M.Liu,L.Can,W.Xiong,et al.,Development of MnO_2/porous carbon microspheres with a partially graphitic structure for high performance supercapacitor electrodes,J.Mater.Chem.A 2(2014)2555-2562;(b)H.Yu,J.Wu,L.Fan,et al.,An efficient redox-mediated organic electrolyte for high-energy supercapacitor,J.Power Sources 248(2014)1123-1126;(c)M.Liu,M.Shi,D.Zhu,et al.,Core-shell reduced graphene oxide/MnOx@carbon hollow nanospheres for high performance supercapacitor electrodes,Chem.Eng.J.313(2017)518-526.
[5]G.Wang,L.Zhang.J.Zhang,A review of electrode materials for electrochemical supercapacitors,Chemlnform 41(2012)797-828.
[6](a)L.Zhang,X.Zhao,Carbon-based materials as supercapacitor electrodes,Chem.Soc.Rev.38(2009)2520-2531;(b)W.Qu,Y.Xu,A.Lu,et al.,Converting biowaste corncob residue into high value added porous carbon for supercapacitor electrodes,Bioresour.Technol.189(2015)285-291.
[7](a)D.Qu,S.Hang,Studies of activated carbons used in double-layer capacitors,J.Power Sources 74(1998)99-107;(b)M.Liu,J.Qian,Y.Zhao,et al.,Core-shell ultramicroporous@microporous carbon nanospheres as advanced supercapacitor electrodes,J.Mater.Chem.A3(2015)11517-11526;(c)D.Zhu,Y.Wang,W.Lu,et al.,A novel synthesis of hierarchical porous carbons from interpenetrating polymer networks for high performance supercapacitor electrodes,Carbon 111(2016)667-674.
[8]E.Frackowiak,F.Beguin,Carbon materials for the electrochemical storage of energy in capacitors Carbon 39(2001)937-950.
[9](a)J.Chmiola,G.Yushin,Y.Gogotsi,et al.,Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer,Science 313(2006)1760-1763;(b)C.Vix-Guterl,E.Frackowiak,K.Jurewicz,et al.,Electrochemical energy storage in ordered porous carbon materials,Carbon 43(2005)1293-1302.
[10]U.Jeong,Y.L.Wang,M.Ibisate,et al.,Some new developments in the synthesis,functionalization,and utilization of monodisperse colloidal spheres,Chemlnform 15(2006)1907-1921.
[11](a)H.K.Jeong,M.Jin,E.J.Ra,et al.,Enhanced electric double layer capacitance of graphite oxide intercalated by poly(sodium 4-styrensulfonate)with high cycle stability,ACS Nano 4(2010)1162-1166;(b)D.Wang,F.Li,2.Chen,et al.,Synthesis and electrochemical property of boron-doped mesoporous carbon in supercapacitor,Chem.Mater.20(2008)7195-7200;(c)Q,Shi,R.Zhang,Y.Lv,et al.,Nitrogen-doped ordered mesoporous carbons based on cyanamide as the dopant for supercapacitor.Carbon 84(2015)335-346;(d)L.Miao,H.Duan,M.Liu,et al.,Poly(ionic liquid)-derived,N,S-codoped ultramicroporous carbon nanoparticles for supercapacitors,Chem.Eng.J.317(2017)651-659;(e)L.Wang,C.Yang,S.Dou,et al.,Nitrogen-doped hierarchically porous carbon networks:synthesis and applications in lithium-ion battery,sodium-ion battery and zinc-air battery,Electrochim.Acta 219(2016)592-603.
[12](a)CD.Lokhande,D.P.Dubai,O.S.Joo,Metal oxide thin film based supercapacitors,Curr.Appl.Phys.11(2011)255-270;(b)R.Bi,X.Wu,F.Cao,et al.,Highly dispersed RuO_2 nanoparticles on carbon nanotubes:facile synthesis and enhanced supercapacitance performance,J.Phys.Chem.C 114(2010)2448-2451.
[13](a)J.Ge,H.Yao,W.Hu,et al.,Facile dip coating processed graphene/MnO_2,nanostructured sponges as high performance supercapacitor electrodes Nano Energy 2(2013)505-513;(b)P.Wang,Y.Zhao,L.Wen,et al.,Ultrasound-microwave-assisted synthesis of MnO_2 supercapacitor electrode materials,Ind.Eng.Chem.Res.53(2014)20116-20123.
[14](a)S.Li,C.Wang,Design and synthesis of hierarchically porous MnO_2/carbon hybrids for high performance electrochemical capacitors,J.Colloid Interface Sci.438(2015)61-67;(b)Z.Lei,J.Zhang,X.Zhao,Ultrathin MnO_2 nanofibers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes,J.Mater.Chem.22(2011)153-160.
[15](a)L.Li,R.Li,S.Gai,et al.,MnO_2 nanosheets grown on nitrogen-doped hollow carbon shells as a high-performance electrode for asymmetric supercapacitors,Chem.Eur.J.21(2015)7119-7126;(b)M.Yang,B.G.Choi,Rapid one-step synthesis of conductive and porous MnO_2/graphene nanocomposite for high performance supercapacitors,J.Electroanal.Chem.776(2016)134-138;(c)Y.Liu,X.Cai,B.Luo,et al.,MnO_2 decorated on carbon sphere intercalated graphene film for high-performance supercapacitor electrodes,Carbon 107(2016)426-432.
[16](a)H.Xu,Z.Qu,C.Zong,et al.,MnOx/graphene for the catalytic oxidation and adsorption of elemental mercury,Environ.Sci.Technol.49(2015)6823-6830;(b)Y.Zhao,Y.Meng,J.Peng,Carbon@MnO_2 core-shell nanospheres for flexible high-performance supercapacitor electrode materials,J.Power Sources 259(2014)219-226.
[17]X.Feng,Z.Yan,N.Chen,et al.,The synthesis of shape-controlled MnO_2/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors,J.Mater.Chem.A 1(2013)12818-12825.
[18](a)S.Chen,J.Zhu,X.Wu,et al.,Graphene oxide-MnO_2 nanocomposites for supercapacitors,ACS Nano 4(2010)2822-2830;(b)D.Portehault,S.Cassaignon,E.Baudrin,et al.,Morphology control of cryptomelane type MnO_2 nanowires by soft chemistry,growth mechanisms in aqueous medium,Chem.Mater.19(2007)5410-5417.
[19]Y.Li,G.Wang,T.Wei,et al.,Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors,Nano Energy 19(2015)165-175.
[20]D.Zhu,K.Cheng,Y.Wang,et al.,Nitrogen-doped porous carbons with nanofiber-like structure derived from poly(aniline-co-p-phenylenediamine)for supercapacitors,Electrochim.Acta 224(2017)17-24.
[21](a)Y.He,W.Chen,J.Zhou,et al.,Constructed uninterrupted charge-transfer pathways in three-dimensional micro/nanointerconnected carbon-based electrodes for high energy-density ultralight flexible supercapacitors,ACS Appl.Mater.Interfaces 6(2013)210-218;(b)M.Liu,W.W.Tjiu,J.Pan,et al.,One-step synthesis of graphene nanoribbonMnO_2 hybrids and their all-solid-state asymmetric supercapacitors,Nanoscale6(2014)4233-4242.
[22](a)J.H.Kim,D.Bhattacharjya,J.S.Yu,Synthesis of hollow TiO_2@N-doped carbon with enhanced electrochemical capacitance by an in situ hydrothermal process using hexamethylenetetramine,J.Mater.Chem.A 2(2014)11472-11479;(b)W.Lu,M.Liu,L Miao,et al.,Nitrogen-containing ultramicroporous carbon nanospheres for high performance supercapacitor electrodes,Electrochim.Acta 205(2016)132-141;(c)Z.Xu,Q,Guo,A simple method to prepare monodisperse and size-tunable carbon nanospheres from phenolic resin,Carbon 52(2013)464-467.
[2](a)L Zhang,X.Zhao,Carbon-based materials as supercapacitor electrodes,Chem.Soc.Rev.38(2009)2520-2531;(b)X.Wang,G.Shi,Flexible graphene devices related to energy conversion and storage,Energy Environ.Sci.8(2015)790-823;(c)Y.Dai,H.Jiang,Y.Hu,et al.,Controlled synthesis of ultrathin hollow mesoporous carbon nanospheres for supercapacitor applications,Ind.Eng.Chem.Res.53(2014)3125-3130;(d)M.Liu,L.Chen,D.Zhu,et al.,Zinc tartrate oriented hydrothermal synthesis of microporous carbons for high performance supercapacitor electrodes,Chin.Chem.Lett.27(2016)399-404;(e)Z.Xu,J.Wang,Z.Hu,et al.,Structure evolutions and high electrochemical performances of carbon aerogels prepared from the pyrolysis of phenolic resin gels containing ZnCl_2,Electrochim.Acta 231(2017)601-608.
[3](a)H.Chang,H.Wu,Graphene-based nanocomposites:preparation,functionalization,and energy and environmental applications,Energy Environ.Sci.6(2013)3483-3507;(b)K.Pinkert,L.Giebeler,M.Herklotz,et al.,Functionalised porous nanocomposites:a multidisciplinary approach to investigate designed structures for supercapacitor applications,J.Mater.Chem.A 1(2013)4904-4910.
[4](a)M.Liu,L.Can,W.Xiong,et al.,Development of MnO_2/porous carbon microspheres with a partially graphitic structure for high performance supercapacitor electrodes,J.Mater.Chem.A 2(2014)2555-2562;(b)H.Yu,J.Wu,L.Fan,et al.,An efficient redox-mediated organic electrolyte for high-energy supercapacitor,J.Power Sources 248(2014)1123-1126;(c)M.Liu,M.Shi,D.Zhu,et al.,Core-shell reduced graphene oxide/MnOx@carbon hollow nanospheres for high performance supercapacitor electrodes,Chem.Eng.J.313(2017)518-526.
[5]G.Wang,L.Zhang.J.Zhang,A review of electrode materials for electrochemical supercapacitors,Chemlnform 41(2012)797-828.
[6](a)L.Zhang,X.Zhao,Carbon-based materials as supercapacitor electrodes,Chem.Soc.Rev.38(2009)2520-2531;(b)W.Qu,Y.Xu,A.Lu,et al.,Converting biowaste corncob residue into high value added porous carbon for supercapacitor electrodes,Bioresour.Technol.189(2015)285-291.
[7](a)D.Qu,S.Hang,Studies of activated carbons used in double-layer capacitors,J.Power Sources 74(1998)99-107;(b)M.Liu,J.Qian,Y.Zhao,et al.,Core-shell ultramicroporous@microporous carbon nanospheres as advanced supercapacitor electrodes,J.Mater.Chem.A3(2015)11517-11526;(c)D.Zhu,Y.Wang,W.Lu,et al.,A novel synthesis of hierarchical porous carbons from interpenetrating polymer networks for high performance supercapacitor electrodes,Carbon 111(2016)667-674.
[8]E.Frackowiak,F.Beguin,Carbon materials for the electrochemical storage of energy in capacitors Carbon 39(2001)937-950.
[9](a)J.Chmiola,G.Yushin,Y.Gogotsi,et al.,Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer,Science 313(2006)1760-1763;(b)C.Vix-Guterl,E.Frackowiak,K.Jurewicz,et al.,Electrochemical energy storage in ordered porous carbon materials,Carbon 43(2005)1293-1302.
[10]U.Jeong,Y.L.Wang,M.Ibisate,et al.,Some new developments in the synthesis,functionalization,and utilization of monodisperse colloidal spheres,Chemlnform 15(2006)1907-1921.
[11](a)H.K.Jeong,M.Jin,E.J.Ra,et al.,Enhanced electric double layer capacitance of graphite oxide intercalated by poly(sodium 4-styrensulfonate)with high cycle stability,ACS Nano 4(2010)1162-1166;(b)D.Wang,F.Li,2.Chen,et al.,Synthesis and electrochemical property of boron-doped mesoporous carbon in supercapacitor,Chem.Mater.20(2008)7195-7200;(c)Q,Shi,R.Zhang,Y.Lv,et al.,Nitrogen-doped ordered mesoporous carbons based on cyanamide as the dopant for supercapacitor.Carbon 84(2015)335-346;(d)L.Miao,H.Duan,M.Liu,et al.,Poly(ionic liquid)-derived,N,S-codoped ultramicroporous carbon nanoparticles for supercapacitors,Chem.Eng.J.317(2017)651-659;(e)L.Wang,C.Yang,S.Dou,et al.,Nitrogen-doped hierarchically porous carbon networks:synthesis and applications in lithium-ion battery,sodium-ion battery and zinc-air battery,Electrochim.Acta 219(2016)592-603.
[12](a)CD.Lokhande,D.P.Dubai,O.S.Joo,Metal oxide thin film based supercapacitors,Curr.Appl.Phys.11(2011)255-270;(b)R.Bi,X.Wu,F.Cao,et al.,Highly dispersed RuO_2 nanoparticles on carbon nanotubes:facile synthesis and enhanced supercapacitance performance,J.Phys.Chem.C 114(2010)2448-2451.
[13](a)J.Ge,H.Yao,W.Hu,et al.,Facile dip coating processed graphene/MnO_2,nanostructured sponges as high performance supercapacitor electrodes Nano Energy 2(2013)505-513;(b)P.Wang,Y.Zhao,L.Wen,et al.,Ultrasound-microwave-assisted synthesis of MnO_2 supercapacitor electrode materials,Ind.Eng.Chem.Res.53(2014)20116-20123.
[14](a)S.Li,C.Wang,Design and synthesis of hierarchically porous MnO_2/carbon hybrids for high performance electrochemical capacitors,J.Colloid Interface Sci.438(2015)61-67;(b)Z.Lei,J.Zhang,X.Zhao,Ultrathin MnO_2 nanofibers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes,J.Mater.Chem.22(2011)153-160.
[15](a)L.Li,R.Li,S.Gai,et al.,MnO_2 nanosheets grown on nitrogen-doped hollow carbon shells as a high-performance electrode for asymmetric supercapacitors,Chem.Eur.J.21(2015)7119-7126;(b)M.Yang,B.G.Choi,Rapid one-step synthesis of conductive and porous MnO_2/graphene nanocomposite for high performance supercapacitors,J.Electroanal.Chem.776(2016)134-138;(c)Y.Liu,X.Cai,B.Luo,et al.,MnO_2 decorated on carbon sphere intercalated graphene film for high-performance supercapacitor electrodes,Carbon 107(2016)426-432.
[16](a)H.Xu,Z.Qu,C.Zong,et al.,MnOx/graphene for the catalytic oxidation and adsorption of elemental mercury,Environ.Sci.Technol.49(2015)6823-6830;(b)Y.Zhao,Y.Meng,J.Peng,Carbon@MnO_2 core-shell nanospheres for flexible high-performance supercapacitor electrode materials,J.Power Sources 259(2014)219-226.
[17]X.Feng,Z.Yan,N.Chen,et al.,The synthesis of shape-controlled MnO_2/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors,J.Mater.Chem.A 1(2013)12818-12825.
[18](a)S.Chen,J.Zhu,X.Wu,et al.,Graphene oxide-MnO_2 nanocomposites for supercapacitors,ACS Nano 4(2010)2822-2830;(b)D.Portehault,S.Cassaignon,E.Baudrin,et al.,Morphology control of cryptomelane type MnO_2 nanowires by soft chemistry,growth mechanisms in aqueous medium,Chem.Mater.19(2007)5410-5417.
[19]Y.Li,G.Wang,T.Wei,et al.,Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors,Nano Energy 19(2015)165-175.
[20]D.Zhu,K.Cheng,Y.Wang,et al.,Nitrogen-doped porous carbons with nanofiber-like structure derived from poly(aniline-co-p-phenylenediamine)for supercapacitors,Electrochim.Acta 224(2017)17-24.
[21](a)Y.He,W.Chen,J.Zhou,et al.,Constructed uninterrupted charge-transfer pathways in three-dimensional micro/nanointerconnected carbon-based electrodes for high energy-density ultralight flexible supercapacitors,ACS Appl.Mater.Interfaces 6(2013)210-218;(b)M.Liu,W.W.Tjiu,J.Pan,et al.,One-step synthesis of graphene nanoribbonMnO_2 hybrids and their all-solid-state asymmetric supercapacitors,Nanoscale6(2014)4233-4242.
[22](a)J.H.Kim,D.Bhattacharjya,J.S.Yu,Synthesis of hollow TiO_2@N-doped carbon with enhanced electrochemical capacitance by an in situ hydrothermal process using hexamethylenetetramine,J.Mater.Chem.A 2(2014)11472-11479;(b)W.Lu,M.Liu,L Miao,et al.,Nitrogen-containing ultramicroporous carbon nanospheres for high performance supercapacitor electrodes,Electrochim.Acta 205(2016)132-141;(c)Z.Xu,Q,Guo,A simple method to prepare monodisperse and size-tunable carbon nanospheres from phenolic resin,Carbon 52(2013)464-467.