Laser micro-structuring of magnetron-sputtered SnOx thin films as anode material for lithium ion batteries

SnOx electrode thin films for lithium ion batteries were deposited by reactive and non-reactive rf magnetron sputtering of a SnO2 target in an argon–oxygen atmosphere. Amorphous and nano-crystalline SnOx films could be synthesized, with regard to the O2:Ar volume ratio in the sputter gas which was adjusted to 0, 3.5 or 10%. Laser micro-structuring using a KrF excimer laser operating at a wavelength of λ = 248 nm was applied to create free-standing microstructures. Thus, the active surface of the anode material was significantly increased. Furthermore, it was expected that the large volume changes during electrochemical cycling of SnOx could be better compensated by a microstructured surface. The laser parameters were optimized in a way which leads to structures without any defects and little debris. Depending on the laser fluence and pulse number, free-standing conical structures could be formed with a horizontal spacing of <0.5 μm up to 2 μm. The structured and unstructured thin films were cycled in a battery tester against metallic lithium. The structured SnOx thin films exhibited significantly better battery performance with respect to cycling stability.

[1]  F. H. Potter,et al.  Sb and Bi implanted SnO2 thin films: photoemission studies and application as gas sensors , 1993 .

[2]  David B. Williams,et al.  Transmission Electron Microscopy , 1996 .

[3]  C. C. Chen,et al.  Modification of sputter deposited solid-state electrolyte thin films , 2010 .

[4]  R. Gordon,et al.  Textured tin oxide films produced by atmospheric pressure chemical vapor deposition from tetramethyltin and their usefulness in producing light trapping in thin film amorphous silicon solar cells , 1989 .

[5]  Jong-Wan Park,et al.  Effect of working pressure on the electrochemical performance of thin film SnO2 microbattery anodes deposited by radio frequency magnetron sputtering , 2001 .

[6]  Wei-Jun Zhang A review of the electrochemical performance of alloy anodes for lithium-ion batteries , 2011 .

[7]  F. J. Lamelas,et al.  Thin-film synthesis of the orthorhombic phase of SnO 2 , 1999 .

[8]  Douglas A. Keszler,et al.  Tin oxide transparent thin-film transistors , 2004 .

[9]  Duk-Dong Lee,et al.  Effects of Substrates on Properties of Tin Oxide Gas Sensors , 2004 .

[10]  J. Whitacre,et al.  Fabrication and testing of all solid-state microscale lithium batteries for microspacecraft applications , 2002 .

[11]  Luca Ottaviano,et al.  Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM , 2010 .

[12]  Matsuhiko Nishizawa,et al.  Amorphous tin oxide films: preparation and characterization as an anode active material for lithium ion batteries , 2001 .

[13]  Min-Zhen Cai,et al.  Structural and electrochemical characterization of SnOx thin films for Li-ion microbattery , 2009 .

[14]  Martin Winter,et al.  Electrochemical lithiation of tin and tin-based intermetallics and composites , 1999 .

[15]  Johannes Proell,et al.  Laser-assisted structuring and modification of LiCoO2 thin films , 2009, LASE.

[16]  P. Shen,et al.  Fabrication and transformation of dense SnO2 via laser ablation condensation , 2009 .

[17]  J. Leger,et al.  X-ray diffraction study of the phase transitions and structural evolution of tin dioxide at high pressure:ffRelationships between structure types and implications for other rutile-type dioxides , 1997 .

[18]  K. Chopra,et al.  Transparent conductors—A status review , 1983 .

[19]  R. Kohler,et al.  Laser annealing of textured thin film cathode material for lithium ion batteries , 2010, LASE.

[20]  Sylvio Indris,et al.  Constitution, microstructure, and battery performance of magnetron sputtered Li–Co–O thin film cathodes for lithium-ion batteries as a function of the working gas pressure , 2010 .

[21]  Wilhelm Pfleging,et al.  Development of high power density cathode materials for Li-ion batteries , 2008 .

[22]  Wilhelm Pfleging,et al.  Laser- and UV-assisted modification of polystyrene surfaces for control of protein adsorption and cell adhesion , 2009 .

[23]  Wilhelm Pfleging,et al.  Laser-assisted modification of polystyrene surfaces for cell culture applications , 2007 .

[24]  Hui Xia,et al.  Thin film microbatteries prepared by pulsed laser deposition , 2007 .

[25]  Ram S. Katiyar,et al.  Dynamics of the rutile structure. III. Lattice dynamics, infrared and Raman spectra of SnO2 , 1971 .

[26]  Young Soo Yoon,et al.  Enhancement of thin film tin oxide negative electrodes for lithium batteries , 2001 .

[27]  J. F. Chen,et al.  Characterizations of SnO2 and SnO2:Sb thin films prepared by PECVD , 2004 .

[28]  M. C. Horrillo,et al.  Transmission electron microscopy investigation of SnO2 thin films for sensor devices , 1999 .

[29]  J. Dahn,et al.  Electrochemical and In Situ X‐Ray Diffraction Studies of the Reaction of Lithium with Tin Oxide Composites , 1997 .

[30]  Thierry Brousse,et al.  Metal oxide anodes for Li-ion batteries , 1997 .

[31]  Prashant N. Kumta,et al.  LiCoO2 and SnO2 thin film electrodes for lithium-ion battery applications , 2005 .

[32]  W. Pfleging,et al.  Laser patterning and welding of transparent polymers for microfluidic device fabrication , 2006, SPIE LASE.

[33]  Fred Roozeboom,et al.  High Energy Density All‐Solid‐State Batteries: A Challenging Concept Towards 3D Integration , 2008 .

[34]  Toshiyuki Mihara,et al.  Electrochemical property of tin oxide thin film by photo-CVD process , 2001 .

[35]  Liang-Tang Zhang,et al.  Solid-state microscale lithium batteries prepared with microfabrication processes , 2009 .

[36]  J. Jiang,et al.  Pressure induced phase transformation in nanocrystal SnO2 , 2001 .

[37]  Junichi Kawamura,et al.  Thin film lithium ion batteries prepared only by pulsed laser deposition , 2006 .

[38]  B. Scrosati,et al.  Lithium batteries: Status, prospects and future , 2010 .

[39]  R. Kohler,et al.  Patterning and annealing of nanocrystalline LiCoO2 thin films , 2010 .