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4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.00 20 40 60 80 100 120 140 Capacity (mAh g-1) Figure 3.5.2. Discharge curves at various discharge rates from slow (0.125C) to fast (10C) for all solid-state bulk-scale Li battery based on sulfide- based electrolyte. From Ref. 23. Reproduced with permission of Nature Publishing Group. Polymeric Solid Electrolytes: In polymer electrolytes – another class of solid electrolytes – lithium salts are dissolved in high molecular weight polymer solvents. Electron donor groups on the polymer chains solvate the Li cations, leading to salt dissolution and the generation of mobile charge carriers. The archetypical formula for a polymer electrolyte is PEOn:LiX, where PEO stands for polyethylene oxide, n denotes the ratio of ethylene oxide functionalities to Li cations, and X is a soft anion with delocalized negative charge to aid dissolution in the polymer matrix.27 As lithium mobility in these systems is correlated to segmental motion and, consequently, lower stiffness, the tradeoff between conductivity and mechanical stiffness is a fundamental challenge. Material design strategies have been developed over the past 30+ years to address this trade-off and identify optimized materials for integration into practical cells. Examples include the fabrication of polymer electrolyte composites, where stiff inorganic fillers are dispersed into the polymer matrix,28 and the design of block copolymers such as poly(styrene-b-ethylene oxide), where the styrene microphase-separated block provides mechanical reinforcement, and the ethylene oxide block conducts lithium.29 Comparing the entire class of polymer electrolytes to the sulfides and oxides (see radar plots in Figure 3.5.1), polymers have inferior transport properties (lower ionic conductivities and lithium transport numbers), but have advantages in low-cost processability and integration into cells. Since the early 1980s, there have been several demonstrations of full lithium-ion battery cells with good capacity retention over several hundred cycles. Typically, elevated temperatures (80-100°C) are required to achieve full electrode utilization due to the modest ambient ionic conductivities of the polymers.30,31 Comparison with Current Technology: Conventional Li-ion technology (i.e., based on liquid electrolytes) is widely used in portable electronics and is slowly making inroads into low-volume electric vehicles (plug-in hybrid and battery electric) and niche high performance vehicles. Large-scale adoption of electrified powertrains would, however, strongly benefit from lower cost, higher performance, and safer batteries. The opportunity to realize these improvements has created the impetus to pursue bulk-scale all-solid-state batteries employing an alkali metal as the negative electrode. Owing to their low mass, low electronegativity, and high volumetric and specific capacity, alkali metals are highly attractive negative electrodes. However, short-circuit failures caused by the formation of dendrites have limited the widespread use of rechargeable batteries using alkali metal negative electrodes coupled with liquid electrolytes. Consequently, one of the most appealing features offered by solid- state batteries is the prospect of stabilizing the alkali metal electrode (i.e., suppressing dendrites), which would enable cell-level energy densities substantially higher than current technology ( ≥ 1,000 Wh/l). NEXT GENERATION ELECTRICAL ENERGY STORAGE 10C 1.5C 0.125C LiNbO3-coated LiCoO2 Solid electrolyte Acetylene black 10μm PANEL 5 REPORT 131 Voltage (V)PDF Image | Next Generation Electrical Energy Storage
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