采用十六烷基三甲基溴化铵(CTAB)为模板剂,磷酸三甲酯(C3H9O4P)为辅助模板剂,以二水合四氯化锡(SnCl4·2H2O)为锡源,在水溶液中用水热法合成了孔壁为结晶态多孔氧化锡纳米粒子团聚体.通过扫描电子显微镜(SEM),高分辨透射电子显微镜(HRTEM),X射线衍射(XRD),热分析,N2吸附-脱附等对样品的结构和形貌进行了表征分析.结果表明:小分子磷酸三甲酯的加入能够很好地辅助四氯化锡在CTAB胶束附近的堆积,有利于提高材料的比表面积,并改善体系的热稳定性.进一步通过恒电流法研究了材料作为锂离子电池负极材料的电化学性能.经300℃煅烧处理的多孔氧化锡团聚体表现出了高的首次可逆脱锂容量(962.4 mAh/g),经分析原因发现,这是由于体系内残留的不完全燃烧的碳及材料本身的多孔结构引起的.综上可见,加入电负性较大的大体积反离子作为共模板剂可作为一种改善多孔金属氧化物材料性能的有益尝试.
Porous SnO2 agglomerates with crystalline pore walls were obtained by employing CTAB and trimethyl phosphate (TMP) as molecular co-templates via hydrothermal method.Tin (IV) chloride dihydrate was used as the inorganic precursor at high molar ratio of surfactant/Sn4+.The resulting samples were characterized by SEM,(HR)TEM,XRD,thermal analysis and nitrogen adsorption-desorption to examine the structural and morphological characters.The results indicate that the addition of small co-template TMP can facilitate the assembling of tin ions near the CTAB miceUes,which can increase the specific surface area and improve the thermal stability of the resulted sample.The electrochemical properties of porous SnO2 as the anode materials of lithium-ion battery (LIB) are further investigated by using galvanostatic method.The porous SnO2 calcined at 300℃ displays a much higher reversible capacity of 962.4mAb/g,which can be ascribed to the incomplete combustion of the organic materials and the unique nanostructure itself.The addition of bigger counter ions with large electric negativity might give an alternative approach to improve the properties of porous metal oxides synthesized by soft template method.
参考文献
| [1] | Bullis K.Building batteries for electric cars.Technol.Rev.,2011,114:80-82. |
| [2] | Goodenough J B,Kim Y.Challenges for rechatgeable Li batteries.Chem.Mater.,2010,22(3):587-603. |
| [3] | Tarascon J M,Armand M.Issues and challenges facing rechargesble lithium batteries.Nature,2001,414:359-367. |
| [4] | Wang T,Ma Z N,Xu F,et al.The one-step preparation and electrochemical characteristics of tin dioxide nanocrystalline materials.Electrochem.Commun.,2003,5(7):599-602. |
| [5] | Idota Y,Mineo Y,Matsufuji A,et al.Promising anode active materials for the coming lithium secondary batteries.3.Tin based oxide as the negative electrode material of the lithium.Denki Kagaku,1997,65:717-722. |
| [6] | Ng S H,Santos dos D I,Chew S Y,et al.Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage,Electrochem.Commun.,2007,9(5):915-919. |
| [7] | Kim E,Son D,Kim T G,et al.A mesoporous/crystalline composite material containing tin phosphate for use as the anode in lithium-ion batteries.Angew.Chem.Int.Edit.,2004,43(44):5987-5990. |
| [8] | Ulagappan N,Rao C N R.Synthesis and characterization of the mesoporous chromium silicates,Cr-MCM-41.Chem.Commun.,1996(9):1047-1048. |
| [9] | Qi L M,Ma J M,Cheng H M,et al.Synthesis and characterization of mesostructured tin oxide with crystalline walls.Langmuir,1998,14(9):2579-2581. |
| [10] | Wang Y D,Ma C L,Sun X D,et al.Synthesis of mesostructured SnO2 with CTAB and hydrous tin chloride.Mater.Lett.,2001,51(4):285-288. |
| [11] | Severin K G,Abdel-Fattah T M,Pinnavaia T J.Supramolecular assembly of mesostructured tin oxide.Chem.Commun.,1998(13):1471-1472. |
| [12] | Yang P D,Zhao D Y,Margolese D I,et al.Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline framework.Chem..Mater.,1999,11(10):2813-2826. |
| [13] | Scott R W J,Mamak M,Kwong K,et al.Making sense out of sulfated tin dioxide mesostructures.J.Mater.Chem.,2003,13(6):1406-1412. |
| [14] | Wu N L,Tung C Y.Evolution in microstructural properties of cetyltrimethylammonium bromide-templated mesoporous tin oxide upon thermal crystallization.J.Am.Ceram.Soc.,2004,87(9):1741-1746. |
| [15] | Han S H,Che H W,Hou W G,et al.Ordered mesoporous tin oxide with crystalline pore walls:preparation and thermal stability.Micropor.Mesopor.Mat.,2010,130(1/2/3):1-6. |
| [16] | Stucky G D,Yang P D,Zhao D Y,et al.Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline framework.Chem.Mater.,1999,11(10):2813-2826. |
| [17] | Huo Q S,Margolese D I,Ciesla U,et al.Organization of organic-molecules with inorganic molecular-species into nanocomposite biphase arrays.Chem.Mater.,1994,6(8):1176-1191. |
| [18] | Korosi L,Papp S,Beke S,et al.Effects of phosphate modification on the structure and surface properties of ordered mesoporous SnO2.Micropor.Mesopor.Mat.,2010,134(1/2/3):79-86. |
| [19] | Hyodo T,Nishida N,Shimizu Y,et al.Preparation and gas-sensing properties of thermally stable mesoporous SnO2.Sensor Actuat.B-Chem.,2002,83(1/2/3):209-215. |
| [20] | Wang Y D,Ma C L,Sun X D,et al.Synthesis of mesoporous structured material based on tin oxide.Micropor.Mesopor.Mat.,2001,49(1/2/3):171-178. |
| [21] | Gao X P,Bao J L,Pan G L,et al.Preparation and electrochemical performance of polycrystalline and single crystalline CuO nanorods as anode materials for Li ion battery.J.Phys.Chem.B,2004,108(18):5547-5551. |
| [22] | Wang J-H,LI B,Wu H Y,et al.Synthesis of mesoporous SnO2 and its applicat ion in lithium-ion battery.Acta Phys.Chim.Sin.,2008,24(4):681-685. |
| [23] | Yu A S,Frech R.Mesoporous tin oxides as lithium intercalation anode materials.J.Power Sources,2002,104(1):97-100. |
| [24] | Demir-Cakan R,Hu Y S,Antonietti M,et al.Facile one-pot synthesis of mesoporous SnO2 microspheres via nanopatticles assembly and lithium storage properties.Chem.Mater.,2008,20(4):1227-1229. |
| [25] | Li N,Liu G,Zhen C,et al.Battery performance and photocatalytic activity of mesoporous anatase TiO2 nanospheres/graphene composites by template-free self-assembly.Adv.Funct.Mater.,2011,21(9):1717-1722. |
| [26] | Xu G L,Chen S R,Li J T,et al.A composite material of SnO2/ordered mesoporous carbon for the application in lithium-ion battery.J.Electroanal.Chem.2011,656(1/2):185-191. |
| [27] | Wen Z H,Wang Q,Zhang Q,et al.In situ growth of mesoporous SnO2 on multiwalled carbon nanotubes:a novel composite with porous-tube structure as anode for lithium batteries.Adv.Funct.Mater.,2007,17(15):2772-2778. |
| [28] | Xu C H,Sun J,Gao L.Synthesis of multiwalled carbon nanotubes that are both filled and coated by SnO2 nanoparticles and their high performance in lithium-ion batteries.J.Phys.Chem.C,2009,113(47):20509-20513. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%