Electrodeposition of Sn/SnO₂ Composite Materials As Anode Material for Lithium Ion Batteries and the Micro-Mechanical Property

Abstract

Sn/SnO2 composite materials are promising anode materials in lithium ion battery. Electrodeposition with supercritical CO2(sc-CO2) emulsified electrolyte (EP-SCE) is an effective method in controlling morphology (Ni [1], Cu[2], and Co[3]) and crystallinity (ZnO [4]and TiO2 [5]) of electrodeposited materials. Sc-CO2 is CO2 at temperature and pressure above its critical point, which is 304.1 K and 7.38 MPa. CO2 is non-polar, therefore, the solubility of metal salts and electrical conductivity are both very low in sc-CO2. In order to conduct electrochemical reactions, surfactants are used to form emulsified electrolyte. Co-deposition of SnO2 along with electrodeposition of metallic Sn can occur at the same time in a SnCl2 based electrolyte containing NO3 - ions [6]. The EP-SCE is expected to be effective in controlling concentration and properties of the SnO2 in metallic Sn film. In this study, Sn/SnO2 composite films are prepared by electrodeposition with supercritical CO2 (sc-CO2) emulsified electrolyte, and the mechanical properties in micro-scale are evaluated by compression test of micro-pilliars fabricated from the Sn/SnO2 composite film for practical applications. Details of the high pressure electrochemical apparatus can be found in a previous study [1]. The electrolyte is composed of 0.22 M SnCl2, 0.015 M HCl and 0.31 M (NH4)3C6H5O7. The current density applied is varied from 2.8 to 17.3 mA/cm2. For the EP-SCE, the surfactant is C12H25(OCH2CH2)15OH. 0.2 vol.% of the surfactant is used to form the sc-CO2 emulsions. 20 vol.% of CO2 at 343 K and 15 MPa under agitation are used to ensure the formation of a stable emulsion. Electrodeposition without the sc-CO2 emulsions at ambient condition (CONV) was also conducted to be used as a comparison. Surface morphology of the films prepared by EP-SCE were very smooth and compact, and the CONV films were porous. On the other hand, there is not much different in the average grain size between the EP-SCE and CONV films, which was about 50 μm for both the EP-SCE and CONV films. The oxygen content in the EP-SCE films can be up to 28.3 at.% by adjusting the electrodeposition parameters. Micro-pillars with a 20×20 μm2 cross-section and a height at 40 μm were fabricated by focus ion beam from the deposited films. The yield stresses were ranged from 10 to 40 MPa when the current density changed. Acknowledgment: This work was supported by JST CREST Grant Number JPMJCR1433. Reference: [1] Electrochim. Acta 55 (2010) 6469-6475 [2] Thin Solid Films 529 (2013) 25-28 [3] J. Electrochem. Soc. 162 (2015) D423-D426 [4] J. Phys. Chem. C 117 (2013) 25596-25603 [5] Electrochem. Commun. 33 (2013) 68-71 [6] J. Alloys Compd. 403 (2005) 335-340