Battery_Part I - Lecture Series on Solid State...

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Unformatted text preview: Lecture Series on Solid State Electrochemistry in Rechargeable Batteries By Y. Shirley Meng Crystal Structures and Their Relevance to Lithium Ion Battery 1 EMA 6446 Solid State Ionics - Rechargeable Batteries 2 EMA 6446 Solid State Ionics - Rechargeable Batteries 3 EMA 6446 Solid State Ionics - Rechargeable Batteries 4 EMA 6446 Solid State Ionics - Rechargeable Batteries 5 EMA 6446 Solid State Ionics - Rechargeable Batteries 6 EMA 6446 Solid State Ionics - Rechargeable Batteries 7 EMA 6446 Solid State Ionics - Rechargeable Batteries 8 EMA 6446 Solid State Ionics - Rechargeable Batteries 9 EMA 6446 Solid State Ionics - Rechargeable Batteries 10 EMA 6446 Solid State Ionics - Rechargeable Batteries 11 EMA 6446 Solid State Ionics - Rechargeable Batteries Outline: 1. Different types of layered stacking 2. Competing structures 3. Several important structures and their voltage curves a. Layered O3 b. Spinel c. Olivine 5. Less open structures - conversion vs. intercalation 6. Connect structures with a. Diffusion of ion b. Electronic conductivity c. Phase transformation 12 EMA 6446 Solid State Ionics - Rechargeable Batteries Structural Classification of Layered Oxides General formula AxMO2 A - alkali ion and M - one or several ions with various oxidation states MO6 edge-sharing octahedrons form MO2 sheet A is inserted in environments of octahedral (O) tetrahedral (T) prismatic (P) 13 EMA 6446 Solid State Ionics - Rechargeable Batteries Stacking sequence determines local environments (T) (O) (P) 14 EMA 6446 Solid State Ionics - Rechargeable Batteries Layered transition metal oxides MO2 slab M= Co, Ni, Mn 15 EMA 6446 Solid State Ionics - Rechargeable Batteries Transition Metal in Other Coordination Prismatic-form -19.558eV/formula -21.706eV/formula -23.575eV/formula TiS2 MoS2 WS2 Octahedral-form -19.983eV/formula -20.854eV/formula -22.770eV/formula 16 EMA 6446 Solid State Ionics - Rechargeable Batteries Layered transition metal oxides made of stacked slabs 17 EMA 6446 Solid State Ionics - Rechargeable Batteries Li intercalation compounds (for Li-batteries) 18 EMA 6446 Solid State Ionics - Rechargeable Batteries O3 Li : M ratio = 1 : 1 both Li and Co are in octahedral sites 19 EMA 6446 Solid State Ionics - Rechargeable Batteries Projection along c axis B A 20 EMA 6446 Solid State Ionics - Rechargeable Batteries Other types of stacking possible CoO2 O2 -LiCoO2 LiCoO2 B A C B A C B A B B A B A A B C B A O3 stacking Rombohedral symmetry O1 stacking Hexagonal symmetry O2 stacking 21 EMA 6446 Solid State Ionics - Rechargeable Batteries Available tetrahedral site Projection along c axis AB stacking - tetrahedral site 22 EMA 6446 Solid State Ionics - Rechargeable Batteries Features of tetrahedral site in layered oxides Tetrahedron is face sharing with octahedron strong electrostatic repulsion! Octahedron and octahedron are edge sharing 23 EMA 6446 Solid State Ionics - Rechargeable Batteries Stacking for trigonal prismatic occupancy A A B B A A B (P) (O) AABB P2 stacking 24 EMA 6446 Solid State Ionics - Rechargeable Batteries NaxCoO2 P2 - Na0.7CoO2 Thermoelectric compound! Co O Na(1) Na(2) 25 EMA 6446 Solid State Ionics - Rechargeable Batteries ...
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This note was uploaded on 04/24/2008 for the course EMA 6446 taught by Professor Wachsman during the Fall '08 term at University of Florida.

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