Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2018 Mixed glass former effect in borate and thioborate sodium-ion conducting glass systems Brittany Curtis Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Materials Science and Engineering Commons, and the Mechanics of Materials Commons Recommended Citation Curtis, Brittany, "Mixed glass former effect in borate and thioborate sodium-ion conducting glass systems" (2018). Graduate Theses and Dissertations. 16337. https://lib.dr.iastate.edu/etd/16337 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Mixed glass former effect in borate and thioborate sodium-ion conducting glass systems by Brittany Curtis A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Materials Science and Engineering Program of Study Committee: Steve Martin, Major Professor Nicola Bowler Gordon Miller Aaron Rossini Xiaoli Tan The student author, whose presentation of the scholarship herein was approved by the program of study committee, is solely responsible for the content of this dissertation. The Graduate College will ensure this dissertation is globally accessible and will not permit alterations after a degree is conferred. Iowa State University Ames, Iowa 2018 Copyright © Brittany Curtis, 2018. All rights reserved. ii DEDICATION To my parents Dwight Curtis and Judy Baker along with my sister Stephanie. To all the families that encouraged, inspired, and supported me in my endeavors: Donna Stitt, The Wikanders, The Mendons, and The Ahlvers/Wilkinsons. iii TABLE OF CONTENTS Page NOMENCLATURE .......................................................................................................... vi ABSTRACT ...................................................................................................................... vii CHAPTER 1. INTRODUCTION ....................................................................................... 1 1.1 Dissertation Organization ........................................................................................ 1 1.2 Dissertation Introduction ......................................................................................... 2 1.2.1 Solid State Batteries ........................................................................................ 3 1.2.2 Benefits of Glassy Electrolytes ....................................................................... 4 1.2.3 Mixed Glass Former Effect ............................................................................. 5 1.2.4 Sulfide-based Glassy Solid State Electrolytes................................................. 6 1.2 Goals of Research ............................................................................................... 7 1.4 References................................................................................................................ 9 CHAPTER 2. COMPOSITION DEPENDENCE OF THE SHORT RANGE ORDER STRUCTURES IN 0.2Na2O + 0.8[xBO3/2 + (1-x)GeO2] MIXED GLASS FORMERS ........................................................................................................................ 15 2.1 Abstract .................................................................................................................. 15 2.2 Introduction ........................................................................................................... 16 2.3 Background ............................................................................................................ 20 2.3.1 Notation of Structural Units .......................................................................... 20 2.3.2 Charge Compensation ................................................................................... 20 2.3.3 Brief Review of the SRO Structures the Binary Systems ............................. 22 2.4 Experimental .......................................................................................................... 25 2.4.1 Sample Preparation........................................................................................ 25 2.4.2 Raman Spectroscopy ..................................................................................... 26 2.4.3 Infrared Spectroscopy .................................................................................... 26 2.4.4 Solid State MAS-NMR ................................................................................. 27 2.5 Results ................................................................................................................... 27 2.5.1 Raman Spectra of the Glasses ....................................................................... 27 2.5.2 IR Spectra of the Glasses............................................................................... 29 2.5.3 11B MAS-NMR Spectra ................................................................................ 30 2.6 Discussion .............................................................................................................. 32 2.6.1 Quantification of the fractions of the SRO units ........................................... 34 2.7 Conclusions ........................................................................................................... 38 2.8 Acknowledgements ............................................................................................... 38 2.9 References.............................................................................................................. 39 CHAPTER 3. GLASS FORMABILITY AND WORKING RANGE OF SODIUM THIOBOROGERMANATE GLASS SYSTEMS ............................................................ 53 3.1 Abstract .................................................................................................................. 53 3.2 Introduction ........................................................................................................... 54 iv 3.3 Background ............................................................................................................ 55 3.3.1 Sodium Thioborate Binary yNa2S + (1-y)B2S3 ............................................. 56 3.3.2 Sodium Thiogermanate Binary yNa2S + (1-y)GeS2 ...................................... 56 3.4 Experimental .......................................................................................................... 56 3.4.1 Synthesis of Raw Materials: Sodium Sulfide, Boron Sulfide, and Germanium (IV) Sulfide ........................................................................................ 56 3.4.2 Synthesis of Glasses ...................................................................................... 57 3.4.3 Determining Glass Transition Temperature .................................................. 58 3.5 Results ................................................................................................................... 58 3.5.1 0.2Na2S + 0.8[xBS3/2 + (1-x)GeS2] ............................................................... 58 3.5.2 0.5Na2S + 0.5[xBS3/2 + (1-x)GeS2] ............................................................... 58 3.5.3 0.6Na2S + 0.4[xBS3/2 + (1-x)GeS2] ............................................................... 59 3.6 Discussion and Conclusion .................................................................................... 59 3.7 References.............................................................................................................. 60 CHAPTER 4. STRUCTURAL INVESTIGATION OF THE SODIUM THIOBOROSILICATE MIXED GLASS FORMER SYSTEM 0.6Na2S + 0.4[xBS3/2 + (1-x)SiS2] ....................................................................................................................... 68 4.1 Abstract .................................................................................................................. 68 4.2 Introduction .......................................................................................................... 69 4.3 Background ............................................................................................................ 70 4.3.1 Notation of SRO Units .................................................................................. 70 4.3.2 yNa2S + (1-y)B2S3 Binary System ................................................................ 71 4.3.3 yNa2S + (1-y)SiS2 Binary System ................................................................. 71 4.3.4 Mixed Glass Former System 0.6Na2S + 0.4[xBS3/2 + (1-x)SiS2].................. 72 4.4 Experiment ............................................................................................................. 73 4.4.1 Preparation of Precursors .............................................................................. 73 4.4.2 Preparation of Glass Samples ........................................................................ 73 4.4.3 Raman Spectroscopy ..................................................................................... 74 4.4.4 Infrared Spectroscopy .................................................................................... 74 4.4.5 11B MASS-NMR ...........................................................................................