High-Energy Secondary Metal-Sulfur Batteries Cathode and Anode Solutions

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1 High-Energy Secondary Metal-Sulfur Batteries Cathode and Anode Solutions Lynden A. Archer October 20, 2016 Acknowledgements: NSF-DMR , ARPAE-DE-AR & DOE-BESC

2 Pros Lithium-Sulfur Batteries Excellent specific energy (2580 Wh/kg) Potential for new types of rechargeable batteries with 5-10 times the energy density of Li-ion Sulfur is cheap and abundant! Li & S 8 react readily and reversibly (no need for expensive catalysts) The Good Cons Low cell discharge voltage (2.2 V) Poor conductivity (5 x S/cm at 25 C) The Bad Part 1: Lithium Metal Anode - Unstable (dendritic) electrodeposition - potential for premature & catastrophic cell failure Part 2: Polysulfide dissolution & shuttling parasitic reactions consume anode and cathode materials The Ugly!

3 The Lithium Metal Battery Cathode TiS 2 ; MnO 2 Whittingham, M.S., Electrical Energy-Storage and Intercalation Chemistry. Science, Na, Al, Zn, Cu; Mg!

4 Dendrite Formation Mechanism?

5 Dendrite Propagation with Transport C c t N c ; C a,m t N a,m M. Tikekar - + z N c RT c C c F c C c c c C c p s N a,m R c T a,m C a,m F a,m C a,m a,m a,m C a,m p s C c C a,m C 0 C a, f ; C a, f C a, f 0 (1 u s ) Cathode Anode s s = 2n s G s È ( ³u s )I + G s Í u s + ( u s ) Ý 1-2n s Î Þ p s = tr(s s ) = - K s ³u s Solve the transport problem for Growth Rate σ ŽH m sf e n ³J c H % = - v c Žt m ; F Žt σ determines the stability of deposition σ > 0 means unstable deposition σ < 0 means stable deposition ŽH s sf = - v c e n ³J c % H c F ; J c = F(N c - N a,m ) Tikekar, Archer & Koch Science Adv, 2016

6 σ / J Perturbation growth rate 2 L / J F L P 1 Concentration of current on tips 2 Deposition kinetics slowed by pressure 2 L 2 P 2 2L / 25 Mobile anions migrate in response to gradient unstable σ mu 2 L / CR stable

7 λ (dendrite nucleqte size) convergence of electrical flux (unstable) Concentration of current on tips l = l cr : P 2-1/2 l : P 1-1 elasticity-induced reaction retardation pressure-driven stabilization a << λ c G S = G Li G S (separator / electrolyte modulus) P 1 JFL t Li G S P 2 JFL2 t Li S Tikekar, Archer et. al. Nature Energy, 2016

8 Nanoporous Membrane Electrolytes Z. Tu Infuse liquid electrolytes (1M LiTFSI in DOL/DME) into Al 2 O 3 nanoproes Ionic conductivity of electrolyte-infused Al 2 O 3 Membranes

9 High Current densities a_al 2 O 3 = 20 nm 1 ma/cm 2 Li Li Al 2 O 3 Electrolyte Lithium Foil 2 ma/cm 2 3 ma/cm 2 Elapsed Time [h]

10 A Plethora of Solutions! Stone, Balsara, et al. JES 2012 Kurana, et al JACS, 2014 Lu, et al. Angew. Chem, 2013 Choudhury, et al. Nat. Comms., 2015 Lu, et al. Adv. Energy Mater., 2015 d p Electrolyte in a variety of configurations have been designed that enable LMBs

11 Joint-Density Functional Analysis D. Gunceler Gunceler, Arias and co-workers, 16 th International Workshop on Computation Physics and Materials Science 2012, arxiv

12 Galvanostatic Cycling Studies Y. Lu LiF 30 mol % LiF LiF Lu, Tu & Archer, Nature Materials (2014); Accts of Chem. Res. (2015)

13 A Plethora of Solutions Kurana, et al JACS, 2014 Lu, et al. Angew. Chem, 2013 Choudhury, et al. Nat. Comms., M[0.7 LiTFSI+0.3 LiF] Lu, Tu, Archer Nat. Mater.,2014 Lu, et al. Adv. Energy Mater., 2015 d p Electrolyte modulus alone does not determine lifetime of lithium metal batteries

14 Summary & Perspective Advanced batteries based on metallic Li anode and sulfur cathodes limited by stability of both electrodes Theoretical analysis shows that most unstable mode for electrodeposition of metals is a strong function of membrane structure, anion mobility and mechanical modulus of the membrane LMBs based on Nanoporous ceramic membranes infused with liquid electrolyte do not fail by dendrite-induced short circuits Polymer-inorganic hybrids yield electrolytes with tunable mechanical properties, reasonable ionic conductivity and promising ability to prevent cell failure by dendrite short circuits Liquid electrolytes based on metal halide salts (e.g. LiF and LiBr) exhibit exceptional effectiveness in stabilizing lithium metal anodes

15 P. Agarwal Dow S. Choudhury Cornell Y. Lu Zhejiang U S. Moganty NOHMS J. Schaefer U. Notre Dame M. Tikekar Cornell Z. Tu Cornell Acknowledgements NSF-Division of Materials Research Polymers Program (DMR ) ARPAE-IDEAS (DE-AR ) DOE-Basic Energy Sciences (BESC & BES ) KAUST-Cornell Center for Energy and Sustainability (KUSC ) NSF-Partnerships for Innovation Building Innovation Capacity (IIP )

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