自支撑氮掺杂石墨烯纸柔性电极的制备及其储锂性能的研究
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摘要
以氧化石墨烯(GO)为原料,尿素为氮掺杂剂,采用固/气界面水热反应的方式,即在反应釜内将GO抽滤得到的氧化石墨烯纸(GOP)与尿素分解产生的氨蒸气相互作用,成功制备出自支撑氮掺杂石墨烯纸(NGP)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、拉曼光谱(RS)、X射线光电子能谱(XPS)和电化学测试对样品进行形貌结构及电化学性能的表征。测试结果表明:水热条件下尿素能有效地实现氧化石墨烯纸的氮掺杂,氮掺杂量为7.89%;氮掺杂石墨烯纸在100mA/g和500mA/g的电流密度下,充放电循环100周之后,放电比容量可分别保持在288mAh/g和190mAh/g。采用改进的固/气界面水热反应法制备的氮掺杂石墨烯纸较未掺杂石墨烯纸可逆比容量提高了近2.5倍,具有良好的循环稳定性,可为制备高性能的柔性锂离子电池负极材料提供新方法。
Free-standing N-doped graphene paper was prepared by solid/vapor interface hydrothermal reduction method using graphene oxide(GO)as the raw material and urea as the nitrogen dopant.Herein,the solid/vapor interface reaction is utilized,in which the graphene oxide paper obtained via vacuum filtration reacts with ammonia vapor generated from the decomposition of urea.X-ray diffraction(XRD),scanning electron microscopy(SEM),Raman spectroscopy(RS),X-ray photoelectron spectroscopy(XPS)and electrochemical measurements are employed to characterize the morphology and electrochemical performance of the prepared products.The results show that nitrogen can be efficiently doped into oxidized graphene paper with a doping content of ca.7.89% under the hydrothermal conditions.The specific discharge capacity of nitrogen-doped graphene paper can be maintained with 288 mAh/g and 190mAh/g after 100 cycles at a current density of 100mA/g and 500mA/g,respectively.Thus prepared nitrogen-doped graphene paper delivers ca.2.5times higher reversible specific capacity than undoped graphene paper,and exhibits excellent cycling performance,which provides new opportunities for the preparation of high performance flexible lithium ion battery anode material.
Free-standing N-doped graphene paper was prepared by solid/vapor interface hydrothermal reduction method using graphene oxide(GO)as the raw material and urea as the nitrogen dopant.Herein,the solid/vapor interface reaction is utilized,in which the graphene oxide paper obtained via vacuum filtration reacts with ammonia vapor generated from the decomposition of urea.X-ray diffraction(XRD),scanning electron microscopy(SEM),Raman spectroscopy(RS),X-ray photoelectron spectroscopy(XPS)and electrochemical measurements are employed to characterize the morphology and electrochemical performance of the prepared products.The results show that nitrogen can be efficiently doped into oxidized graphene paper with a doping content of ca.7.89% under the hydrothermal conditions.The specific discharge capacity of nitrogen-doped graphene paper can be maintained with 288 mAh/g and 190mAh/g after 100 cycles at a current density of 100mA/g and 500mA/g,respectively.Thus prepared nitrogen-doped graphene paper delivers ca.2.5times higher reversible specific capacity than undoped graphene paper,and exhibits excellent cycling performance,which provides new opportunities for the preparation of high performance flexible lithium ion battery anode material.
引文
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2 Raccichini R,Varzi A,Passerini S,et al.The role of graphene for electrochemical energy storage[J].Nat Mater,2015,14(3):271.
3 El-Kady M F,Kaner R B.Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage[J].Nat Commun,2013,4:1475.
4 Abouimrane A,Compton O C,Amine K,et al.Non-annealed graphene paper as a binder-free anode for lithium-ion batteries[J].J Phys Chem C,2010,114(29):12800.
5 Hu Y,Li X,Geng D,et al.Influence of paper thickness on the electrochemical performances of graphene papers as an anode for lithium ion batteries[J].Electrochim Acta,2013,91:227.
6 Bi H,Chen J,Zhao W,et al.Highly conductive,free-standing and flexible graphene papers for energy conversion and storage devices[J].RSC Adv,2013,3(22):8454.
7 Li X L,Wang H L,Robinson J T,et al.Simultaneous nitrogen doping and reduction of graphene oxide[J].J Am Chem Soc,2009,131(43):15939.
8 Jeon I Y,Zhang S,Zhang L P,et al.Edge-selectively sulfurized graphene nanoplatelets as efficient metal-free electrocatalysts for oxygen reduction reaction:The electron spin effect[J].Adv Mater,2013,25(42):6138.
9 Liu Z W,Peng F,Wang H J,et al.Phosphorus-doped graphite layers with high electrocatalytic activity for the O2reduction in an alkaline medium[J].Angewandte Chem,2011,123(14):3315.
10 Paraknowitsch J P,Thomas A.Doping carbons beyond nitrogen:An overview of advanced heteroatom doped carbons with boron,sulphur and phosphorus for energy applications[J].Energy Environ Sci,2013,6(10):2839.
11 Reddy A L M,Srivastava A,Gowda S R,et al.Synthesis of nitrogen-doped graphene films for lithium battery application[J].ACS Nano,2010,4(11):6337.
12 Wu Z S,Ren W,Xu L,et al.Doped graphene sheets as anode materials with super high rate and large capacity for lithium ion batteries[J].ACS Nano,2011,5(7):5463.
13 Chetty R,Kundu S,Xia W,et al.PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation[J].Electrochim Acta,2009,54(17):4208.
14 Lim H N.Fabrication and characterization of graphene hydrogel via hydrothermal approach as a scaffold for preliminary study of cell growth[J].Int J Nanomedicine,2011,2011:1817.
15 Chen H,Song Z Y,Zhao X C,et al.Reduction of free-standing graphene oxide papers by a hydrothermal process at the solid/gas interface[J].RSC Adv,2013,3(9):2971.
16 Cai D,Wang S,Lian P,et al.Superhigh capacity and rate capability of high-level nitrogen-doped graphene sheets as anode materials for lithium-ion batteries[J].Electrochim Acta,2013,90:492.
17 Jeong H M,Lee J W,Shin W H,et al.Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogendoped sites at basal planes[J].Nano Lett,2011,11(6):2472.
18 Wang H B,Zhang C J,Liu Z H,et al.Nitrogen-doped graphene nanosheets with excellent lithium storage properties[J].J Mater Chem,2011,21(14):5430.
19 Suenaga K,Yudasaka M,Colliex C,et al.Radially modulated nitrogen distribution in CNx nanotubular structures prepared by CVD using Ni phthalocyanine[J].Chem Phys Lett,2000,316(5):365.
20 Xue Y,Chen H,Qu J,et al.Nitrogen-doped graphene by ball-milling graphite with melamine for energy conversion and storage[J].2 D Mater,2015,2(4):044001.
21 Li X F,Geng D S,Zhang Y,et al.Superior cycle stability of nitrogen-doped graphene nanosheets as anodes for lithium ion batteries[J].Electrochem Commun,2011,13(8):822.
22 Dahn J R,Zheng T,Liu Y H,et al.Mechanisms for lithium insertion in carbonaceous materials[J].Science,1995,270(5236):590.
23 Li Y F,Zhou Z,Wang L B.CNxnanotubes with pyridinelike structures:p-type semiconductors and Li storage materials[J].J Chem Phys,2008,129(10):104703.