October 2007 New Process and Larger Molecules Overturn Conventional Wisdom about Lithium–Polymer Electrolyte Batteries Principal Investigator: Nitash P. Balsara (Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, and Department of Chemical Engineering, UC Berkeley) Accomplishment This work presents a new approach to preparing polymer electrolytes for lithium–polymer electrolyte batteries. Instead of using pure polyethylene oxide, the new method introduces two new twists. Key difference #1: Soft, conductive polyethylene oxide is combined with stiff, nonconductive polystyrene (the main component of motorcycle and bicycle helmets) to form a diblock copolymer—a composite of two polymers that segregate into discrete regions. Key difference #2: The copolymer is blended with a lithium salt so that the electrolyte is already doped with lithium ions before being paired with its lithium electrode in a battery. The electrical and mechanical properties were tested extensively, and the results were surprising in several ways. Surprise #1: The stiffer the polystyrene “framework,” the better the conductivity of the overall membrane. (Conventional wisdom said the opposite.) Surprise #2: Bigger polyethylene oxide molecules provided better conductivity. (Conventional wisdom predicted a plateau at high molecular weights.) Surprise #3: The copolymer did not have a structured network of channels (as confirmed by X-ray and electron microscopy measurements), yet conductivity was still high. (Conventional wisdom held that networks were necessary to ion transport.) Viccaro, CHE (ChemMatCARS) Polystyrene/poly- ethylene oxide copolymer: dark areas show the conductive PEO composition SEO(36–25): polystyrene molecular weight 36.4 kg/mol; PEO molecular weight 24.8 kg/mol Secondary peaks are missing in small angle x-ray scattering data, showing copolymer did not form network structures Park M.J. et al.Nano Lett. 2007, 7(11), Singh M. et al., Macromolecules 2007, 40,

October 2007 New Process and Larger Molecules Overturn Conventional Wisdom about Lithium-Polymer Electrolyte Batteries Principal Investigator: Nitash P. Balsara (Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, and Department of Chemical Engineering, UC Berkeley) Impact The new synthesis approach may overcome performance barriers that have, so far, made lighweight lithium– polymer electrolyte batteries impractical for use in electric vehicles. In these batteries, the lithium anode is separated from the cathode by a film of pure polyethylene oxide. In the past, such batteries developed shorts after repeated charging and discharging, as “dendrites” grew from the anode out into the film and eventually reached the cathode. Without this limitation, such batteries could exceed the U.S. Department of Energy’s targets for electric vehicle range and acceleration. Because the new electrolyte does not require special processing to align the polymer domains, a wide range of possible compositions and structures can be explored to achieve optimal conductivities. The method is also important because it confirms theoretical studies that predicted that increasing the shear modulus (rigidity) of the electrolyte would stop the formation of dendrites. The results also show that the mechanical and electrical properties of polymer electrolytes can be manipulated separately. Viccaro, CHE (ChemMatCARS) In earlier technology, dendrites from lithium anode penetrated the polyethylene oxide electrolyte, shorting the battery Li/PE/Li cell assembly, one of 20 cells tested Li PEO Cells charged and discharged for 3 weeks without change in performance [SEO (36-25), ratio lithium ion– to–ethylene oxide moiety = 0.02, 85 °C, i applied = 5 µA]