Thio-oxynitride phosphate glass electrolytes prepared by mechanical milling
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José Luis G. Fierro Group of Sustainable Energy and Chemistry, Instituto de Catálisis y Petroquímica (CSIC), Cantoblanco, Madrid 28049, Spain
Francisco Muñoz and Alicia Durán Glasses Department, Instituto de Cerámica y Vidrio (CSIC), Cantoblanco, Madrid 28049, Spain
Yusuke Ito, Yoshiaki Hibi, Ryo Harada, Atsutaka Kato, Akitoshi Hayashi, and Masahiro Tatsumisago Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan (Received 11 February 2015; accepted 21 April 2015)
Lithium thio-phosphorus oxynitride glasses, LiPOSN, have been prepared by mechanical milling process from the mixture of Li2S and LiPON glass. The anionic substitution of oxygen by sulphur and nitrogen in the phosphate glass structure has been confirmed by 1D 31P solid state nuclear magnetic resonance and x-ray photoelectron spectroscopy. The study of thermal and electrical properties reveals a decrease in the glass transition temperature, likely due to the depolymerization of glass network by the decrease of bridging oxygens and sulphurs, along with a sharp increase in the ionic conductivity when lithium sulphide is incorporated into the oxynitride glasses. The improvement of chemical durability by the introduction of nitrogen, together with the increase in ionic conductivity up to values closed to the value of commercial LiPON thin film electrolyte, suggests that these LiPOSN glasses could be good candidates as solid electrolytes for lithium microbatteries.
I. INTRODUCTION
Contributing Editor: Zoltan Lences a) Address all correspondence to this author. e-mail: [email protected] DOI: 10.1557/jmr.2015.128
leads to an increase of nonbridging oxygens (NBO) contents, along with an increase in the connectivity of the glass network by the formation of P–N bonds, which have higher covalent character than P–O bonds. These structural changes can explain the increase in the thermal and chemical stability, together with the ionic conductivity. Besides, the increase of ionic conductivity by the effect of nitrogen also depends on the addition of lithium content, as observed by Mascaraque et al.19 Thus, it is expected that the introduction of lithium sulphide in nitrided phosphate glasses results in a simultaneous improvement of electrical and chemical properties that allows their application as solid electrolytes. Nowadays, the study on Li2S–P2S5 glasses has been basically focused on electrical and electrochemical properties, without emphasizing their structure. In a preliminary study on Li2O–Li2S–P2O5–PON glass prepared for the first time by melting,20 it has been demonstrated that the introduction of Li2S and nitrogen produces a notable increase in the ionic conductivity. This process consists of two-step melting from the mixture of Li2S and LiPON glass, which was previously obtained by ammonolysis.18,21 In this work, mechanical milling (MM) was used for the preparation of LiPOSN glasses from the starting
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Ó Materials Research Society 2015
In the last few decades, solid electrolytes
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