超细Ce_2Sn_2O_7纳米立方晶体的水热合成与储能性能（英文）
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摘要
采用简单水热法合成了尺寸为10 nm左右的纯烧绿石相超细Ce_2Sn_2O_7立方晶体。通过优化温度、pH、反应时间、前驱体类型等参数获得最佳实验条件。通过X射线衍射仪、拉曼光谱、透射电子显微镜、高分辨透射电子显微镜和BET等表征技术对样品的晶体结构、形貌、尺寸和比表面积进行表征。将制备的Ce_2Sn_2O_7超细纳米立方晶体用作电极材料,并通过超级电容器和锂离子电池对其性能进行评估。将其应用于超级电容器,在0.1 A/g下具有222 F/g的高比电容,并且在5000次循环后仍具有良好的循环稳定性,电容保持率高于86%。将其用于锂离子电池负极材料时,在0.05C倍率下具有超过900 mA?h/g的高电池容量。与传统的石墨阳极相比,其倍率性能和循环性能呈现出较好的应用前景。
Ultrafine cube-shape Ce_2Sn_2O_7 nanoparticles crystallized in pure pyrochlore phase with a size of about 10 nm have been successfully synthesized by a facile hydrothermal method. Conditional experiments have been conducted to optimize the processing parameters including temperature, pH, reaction duration, precipitator types to obtain phase-pure Ce_2Sn_2O_7. The crystal structure, morphology and sizes and specific surface area have been characterized by X-ray diffractometer(XRD), Raman spectrum, transmission electron microscope(TEM), high resolution transmission electron microscope(HRTEM), and Brunauer-Emmett-Teller(BET). The as-synthesized Ce_2Sn_2O_7 ultrafine nanocubes have been evaluated as electrode materials for pseudo-capacitors and lithium ion batteries. When testing as supercapacitors, a high specific capacitance of 222F/g at 0.1 A/g and a good cycling stability with a capacitance retention of higher than 86% after 5000 cycle have been achieved. When targeted for anode material for lithium ion batteries, the nanocubes deliver a high specific reversible capacity of more than 900 mA?h/g at 0.05 C rate. The rate capability and cycling performance is also very promising as compared with the traditional graphite anode.
Ultrafine cube-shape Ce_2Sn_2O_7 nanoparticles crystallized in pure pyrochlore phase with a size of about 10 nm have been successfully synthesized by a facile hydrothermal method. Conditional experiments have been conducted to optimize the processing parameters including temperature, pH, reaction duration, precipitator types to obtain phase-pure Ce_2Sn_2O_7. The crystal structure, morphology and sizes and specific surface area have been characterized by X-ray diffractometer(XRD), Raman spectrum, transmission electron microscope(TEM), high resolution transmission electron microscope(HRTEM), and Brunauer-Emmett-Teller(BET). The as-synthesized Ce_2Sn_2O_7 ultrafine nanocubes have been evaluated as electrode materials for pseudo-capacitors and lithium ion batteries. When testing as supercapacitors, a high specific capacitance of 222F/g at 0.1 A/g and a good cycling stability with a capacitance retention of higher than 86% after 5000 cycle have been achieved. When targeted for anode material for lithium ion batteries, the nanocubes deliver a high specific reversible capacity of more than 900 mA?h/g at 0.05 C rate. The rate capability and cycling performance is also very promising as compared with the traditional graphite anode.
引文
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[37]LEE H Y,GOODENOUGH J B.Supercapacitor behavior with KCl electrolyte[J].Journal of Solid State Chemistry,1999,144:220-223.
[2]HU J,LI M C,LV F C,YANY M Y,TAO P P,TANG Y G,LIU H T,LU Z G.Heterogeneous NiCo2O4@polypyrrole core/sheath nanowire arrays on Ni foam for high performance supercapacitors[J].Journal of Power Sources,2015,294:120-127.
[3]SIMON P,GOGOTSI Y.Materials for electrochemical capacitors[J].Nature Materials,2008,7:845-854.
[4]CHENG H,LU Z G,DENG J Q,CHUNG C Y,ZHANG K L,LI Y Y.A facile method to improve the high rate capability of Co3O4 nanowire array electrodes[J].Nano Research,2010,3:895-901.
[5]LIAN J,WANG L M,WANG S X,CHEN J,BOATNER L A,EWING R C.Nanoscale manipulation of pyrochlore:New nanocomposite ionic conductors[J].Physical Review Letters,2001,87:145901.
[6]ZHAO J H,KUNKEL H P,ZHOU X Z,WILLIAMS G W,SUBRAMANIAN M A.Critical behavior of the magnetoresistive pyrochlore Tl2Mn2O7[J].Physical Review Letters,1999,83:219-222.
[7]LUTIQUE S,KONINGS R J M,RONDINELLA V V,SOMERS J,WISS T.The thermal conductivity of Nd2Zr2O7pyrochlore and the thermal behaviour of pyrochlore-based inert matrix fuel[J].Journal of Alloys and Compounds,2003,352:1-5.
[8]NAG A,DASGUPTA P,JANA Y M,GHOSH D.A study on crystal field effect and single ion anisotropy in pyrochlore europium titanate(Eu2Ti2O7)[J].Journal of Alloys and Compounds,2004,384:6-11.
[9]SOHN J M,KIM M R,WOO S I.The catalytic activity and surface characterization of Ln2B2O7(Ln=Sm,Eu,Gd and Tb;B=Ti or Zr)with pyrochlore structure as novel CH4combustion catalyst[J].Catalysis Today,2003,83:289-297.
[10]ALI N,HILL P,ZHANG X,WILLIS F.Magnetization and thermoremanent magnetization of Tb2Mo2O7 and Y2Mo2O7spin glasses[J].Journal of Alloys and Compounds,1992,181:281-285.
[11]YANG M Y,CHENG H,GU Y Y,SUN Z F,HU J,CAO L J,LV F C,LI M C,WANG W X,WANG Z Y,WU S F,LIU HT,LU Z G.Facile electro-deposition of 3D concentrationgradient Ni-Co hydroxide nanostructures on nickel foam as high performance electrodes for asymmetric supercapacitors[J].Nano Research,2015,8(8):2744-2754.
[12]SHARMA N,SUBBA R G V,CHOWDARI B V R.Anodic properties of tin oxides with pyrochlore structure for lithium ion batteries[J].Journal of Power Sources,2006,159:340-344.
[13]MIMS C A,JACOBSON A J,HALL R B,LEWANDOSKI JT.Methane oxidative coupling over nonstoichiometric bismuth-tin pyrochlore catalysts[J].Journal of Catalysis,1995,153:197-207.
[14]CHENG H,WANG L P,LU Z G.A general aqueous sol-gel route to Ln2Sn2O7 nanocrystals[J].Nanotechnology,2008,19:025706.
[15]YU T H,TULLER H L.Ionic conduction and disorder in the Gd2Sn2O7 pyrochlore system[J].Solid State Ionics,1996,86-88:177-182.
[16]PORAT O,HEREMANS C,TULLER H L.Stability and mixed ionic electronic conduction in Gd2(Ti1-xMox)2O7 under anodic conditions[J].Solid State Ionics,1997,94:75-83.
[17]SICKAFUS K E,MINERVINI L,GRIMES R W,VALDEZ JA,ISHIMARU M,LI F,MCCLELLAN K J,HARTMANNT.Radiation tolerance of complex oxides[J].Science,2000,289:748-751.
[18]LI K W,WANG H,HUI Y.Hydrothermal preparation and photocatalytic properties of Y2Sn2O7 nanocrystals[J].Journal of Molecular Catalysis A:Chemical,2006,249:65-70.
[19]TOLLA B,DEMOURGUES A,POUCHARD M,RABARAEL L,FOURNES L,WATTIAUX A.Oxygen exchange properties in the new pyrochlore solid solution Ce2Sn2O7-Ce2Sn2O8[J].Comptes Rendus de l'Academie des Sciences Serie IIc:Chemie,1999,2:139-146.
[20]ISMUMANDAR KENNEDY B J,HUNTER B A,VOGT T.Bonding and structural variations in doped Bi2Sn2O7[J].Journal of Solid State Chemistry,1997,131:317-325.
[21]WANG S W,LU M K,ZHOU G J,ZHOU Y Y,ZHANG H P,WANG S F,YANG Z S.Synthesis and luminescence properties of La2-xREx Sn2O7(RE=Eu and Dy)Phosphor nanoparticles[J].Materials Science and Engineering:B,2006,133:231-234.
[22]MOON J,AWANO M,MAEDA K.Hydrothermal synthesis and formation mechanisms of lanthanum tin pyrochlore oxide[J].Journal of the American Ceramic Society,2001,84:2531-2536.
[23]LU Z G,WANG J W,TANG Y G,LI Y D.Synthesis and photoluminescence of Eu3+-doped Y2Sn2O7 nanocrystals[J].Journal of Solid State Chemistry,2004,177:3075-3079.
[24]ZHU H L,JIN D L,ZHU L M,YANG H,YAO K H,XI Z Q.A General hydrothermal route to synthesis of nanocrystalline lanthanide stannates:Ln2Sn2O7(Ln=Y,La-Yb)[J].Journal of Alloys and Compounds,2008,464:508-513.
[25]ZENG J,WANG H,ZHANG Y C,ZHU M K,YAN H.Hydrothermal synthesis and photocatalytic properties of pyrochlore La2Sn2O7 nanocubes[J].Journal of Physical Chemistry C,2007,111:11879-11887.
[26]HUANG H,MIAO X,LIAO N,WANG L C,JIN D L.Study on the oxygen exchange capacities of Ce2Sn2O7 pyrochlore[J].Russian Journal of Inorganic Chemistry,2011,56:1621-1624.
[27]YANG J Y,SU Y C,LIU X Y.Hydrothermal synthesis,characterization and optical properties of La2Sn2O7:Eu3+micro-octahedra[J].Transactions of Nonferrous Metals Society of China,2011,21:535-543.
[28]GLERUP M,NIDLSEN O F,POULSEN F W.The structural transformation from the pyrochlore structure,A2B2O7,to the fluorite structure,AO2,studied by Raman spectroscopy and defect chemistry modeling[J].Journal of Solid State Chemistry,2001,160:25-32.
[29]WU S F,WANG W X,Li M C,CAO L J,LV F C,YANG MY,WANG Z Y,SHI Y,NAN B,YU S C,SUN Z F,LIU Y,LU Z G.Highly durable organic electrode for sodium-ion batteries via a stabilizedα-C radical intermediate[J].Nature Communications,2016,7:13318.
[30]GUPTA H C,BROWN S,RANI N,GOHEL V B.A lattice dynamical investigation of the Raman and the infrared frequencies of the cubic A2Sn2O7 pyrochlores[J].International Journal of Inorganic Materials,2001,3:983-986.
[31]VANDENBORRE M T,HUSSON E,CHATRY J P,MICHEL D.Rare-earth titanates and stannates of pyrochlore structure;vibrational spectra and force fields[J].Journal of Raman Spectroscopy,1983,14:63-71.
[32]XU M W,KONG L B,ZHOU W J,LI H L.Hydrothermal synthesis and pseudocapacitance properties ofα-Mn O2hollow spheres and hollow urchins[J].The Journal of Physical Chemistry C,2007,111:19141-19147.
[33]TOUPIN M,BROUSSE T,BELANGER D.Charge storage mechanism of Mn O2 electrode used in aqueous electrochemical capacitor[J].Chemistry of Materials,2004,16:3184-3190.
[34]LI F H,SONG J F,YANG H F,GAN S Y,ZHANG Q X,HAN D X,ARILVASKA LI N.One-step synthesis of Graphene/Sn O2 nanocomposites and its application in electrochemical supercapacitors[J].Nanotechnology,2009,20:455602.
[35]PANG S C,ANDERSON M A,CHAPMAN T W.Novel electrode materials for thin‐film ultracapacitors:Comparison of electrochemical properties of sol-gel-derived and electrodeposited manganese dioxide[J].Journal of the Electrochemical Society,2000,147:444-450.
[36]SUBRAMANIAN V,ZHU H W,VAJTAI R,AJAYAN P M,WEI B Q.Hydrothermal synthesis and pseudocapacitance properties of Mn O2 nanostructures[J].The Journal of Physical Chemistry B,2005,109:20207-20214.
[37]LEE H Y,GOODENOUGH J B.Supercapacitor behavior with KCl electrolyte[J].Journal of Solid State Chemistry,1999,144:220-223.