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To improve the energy density of lithium-ion batteries, the development of advanced electrolytes with enhanced transport properties is highly important. Here, we show that by confining the conventional electrolyte (1 M LiPF6 in EC-DEC) in a microporous polymer network, the cation transference number increases to 0.79 while maintaining an ionic conductivity on the order of 10−3 S cm−1. By comparison, a non-porous, condensed polymer electrolyte of the same chemistry has a lower transference number and conductivity, of 0.65 and 7.6 × 10−4 S cm−1, respectively. Within Li-metal/LiFePO4 cells, the improved transport properties of the porous polymer electrolyte enable substantial performance enhancements compared to a commercial separator in terms of rate capability, capacity retention, active material utilization, and efficiency. These results highlight the importance of polymer electrolyte structure–performance property relationships and help guide the future engineering of better materials. 

Due to its high theoretical energy density and relative abundancy of active materials, the magnesium–sulfur battery has attracted research attention in recent years. A closely related system, the lithium-sulfur battery, can suffer from serious self-discharge behavior. Until now, the self-discharge of Mg–S has been rarely addressed. Herein, we demonstrate for a wide variety of Mg–S electrolytes and conditions that Mg–S batteries also suffer from serious self-discharge. For a common Mg–S electrolyte, we identify a multi-step self-discharge pathway. Covalent S 8 diffuses to the metal Mg anode and is converted to ionic Mg polysulfide in a non-faradaic reaction. Mg polysulfides in solution are found to be meta-stable, continuing to react and precipitate as solid magnesium polysulfide species during both storage and active use. Mg–S electrolytes from the early, middle, and state-of-the-art stages of the Mg–S literature are all found to enable the self-discharge. The self-discharge behavior is found to decrease first cycle discharge capacity by at least 32%, and in some cases up to 96%, indicating this is a phenomenon of the Mg–S chemistry that deserves focused attention. 

Metal‐sulfur batteries are a promising next‐generation energy storage technology, offering high theoretical energy densities with low cost and good sustainability. An active area of research is the development of electrolytes that address unwanted migration of sulfur and intermediate species known as polysulfides during operation of metal‐sulfur batteries, a phenomenon that leads to low energy efficiency and short life‐spans. A particular class of electrolytes, gel polymer electrolytes, are especially attractive for their ability to repel polysulfides on the basis of structure, electrostatics, and other polymer properties. Herein, within the context of magnesium‐ and lithium‐sulfur batteries, we investigate the impact of gel polymer electrolyte cation solvation capacity, a property related to network dielectric constant and chemistry, on sulfur/polysulfide‐polymer interactions, an understudied property‐performance relationship. Polymers with lower cation solvation capacity are found to permanently absorb less polysulfide active material, which increases sulfur utilization for Li−S batteries and significantly increases charge efficiency and life‐span for Li−S and Mg−S batteries.

 

From the standpoint of material diversification and sustainability, the development of so-called “beyond lithium-ion” battery chemistries is important for the future of energy storage. Na, K, and Ca are promising as the basis for battery chemistries in that these elements are highly abundant. Here, a series of single-ion conducting polymer electrolytes (SIPEs) for Na, K, and Ca batteries are synthesized and investigated. The two classes of metal cation neutralized SIPEs compared are crosslinked poly(ethylene glycol) dimethacrylate-x-styrene sulfonate (PEGDMA-SS) and poly(tetrahydrofuran) diacrylate-x-4-styrenesulfonyl (trifluoromethylsulfonyl)imide (PTHFDA-STFSI); three cation types, three charge densities, and four swelling states are examined. The impact on conductivity of all of these parameters is studied, and in conjunction with small angle X-ray scattering (SAXS), it is found that promoting ion dissociation and preventing the formation of dense ionic aggregates facilitates ion transport. These results indicate many of the lessons learned from the Li SIPE literature can be translated to beyond Li chemistries. At 25 °C, the best performing Na/K and Ca exchanged polymers yield active cation conductivity on the order of 10−4 S/cm and 10−6 S/cm, respectively, for ethylene carbonate:propylene carbonate gelled SIPEs, and 10−5 S/cm and 10−7 S/cm, respectively, for glyme gelled SIPEs.