Page 19 - Handbook of Battery Materials

XVIII Contents

17.3.2 Ion-Pair Association Constants 551
17.3.3 Triple-Ion Association Constants 554
17.3.3.1 Bilateral Triple-Ion Formation 554
17.3.3.2 Unilateral Triple Ion Formation 555
17.3.3.3 Selective Solvation of Ions and Competition between Solvation and
Ion Association 558
17.4 Bulk Properties 560
17.4.1 Electrochemical Stability Range 560
17.4.2 Computational Determination of Electrochemical Stability 565
17.4.3 Passivation and Corrosion Abilities of Lithium Salt Electrolytes 569
17.4.4 Chemical Stability of Electrolytes with Lithium and Lithiated
Carbon 573
17.4.5 Conductivity of Concentrated Solutions 579
17.4.5.1 Introduction 579
17.4.5.2 Conductivity-Determining Parameters 586
17.4.5.3 The Walden Rule and the Haven Ratio 588
17.4.5.4 The Role of Solvent Viscosity, Ionic Radii, and Solvation 589
17.4.5.5 The Role of Ion Association 591
17.4.5.6 Application of the Effects of Selective Solvation and Competition
between Solvation and Ion Association 592
17.4.5.7 Conductivity Optimization of Electrolytes by Use of Simplex
Algorithm 595
17.4.6 Transference Numbers 598
17.4.6.1 Introduction 598
17.4.6.2 Hittorf Method 600
17.4.6.3 Electromotive Force (emf) Method 601
17.4.6.4 Potentiostatic Polarization Method 602
17.4.6.5 Conductivity Measurement 603
17.4.6.6 Galvanostatic Polarization Method 603
17.4.6.7 Transference numbers from NMR-diffusion coefficients 605
17.4.6.8 Impedance Measurements 605
17.4.7 Diffusion Coefficients in Liquids 606
17.4.7.1 Introduction 606
17.4.7.2 Pfg-NMR 607
17.4.7.3 Moir´ e Pattern 608
17.4.7.4 Microelectrodes 608
17.4.7.5 Restricted Diffusion 608
17.5 Additives 609
References 611

18 Polymer Electrolytes 627
Fiona Gray and Michel Armand
18.1 Introduction 627
18.2 Solvent-Free Polymer Electrolytes 629
18.2.1 Technology 629