Conspectus
The energy
density of the ubiquitous lithium-ion batteries is rapidly
approaching its theoretical limit. To go beyond, a promising strategy
is the replacement of conventional intercalation-type materials with
conversion-type materials possessing substantially higher capacities.
Among the conversion-type cathode materials, sulfur constitutes a
cost-effective and earth-abundant element with a high theoretical
capacity that has a potential to be game-changing, especially within
an emerging solid-state battery configuration. Employment of nonflammable
solid electrolytes that improves battery safety and boosts the energy
density, as lithium metal anodes are also viable. The long-standing
inherent problem of conventional lithium–sulfur batteries,
arising from the reaction intermediates dissolved in liquid electrolytes,
can be eliminated with inorganic solid ion conductors. In particular,
the highly conducting and easily processable lithium-thiophosphates
have successfully enabled the lab-scale solid-state lithium–sulfur
cells to achieve close-to-theoretical capacities. For applications
requiring safe, energy-dense, lightweight batteries, solid-state lithium–sulfur
batteries are an ideal choice that could surpass conventional lithium-ion
batteries.
Nevertheless, there are challenges specific to practical
solid-state
lithium–sulfur batteries, beyond the typical challenges inherent
to solid-state batteries in general. While the conversion reaction
of sulfur realizes a large specific capacity, the associated significant
total volume changes of the active material results in contact losses
among the cathode components and, consequently, decreases reversible
capacity. Additionally, the ionically and electronically insulating
active material requires composite formation with solid electrolytes
and electron-conductive additives to secure sufficient ion and electron
supply at a triple-phase boundary. However, the compositing process
itself makes the carrier transport pathways very tortuous and requires
the balancing of carrier transport and optimization of the attainable
energy density. Lastly, the requirement of a high interfacial area
to establish sufficient triple-phase boundaries promotes the degradation
of the solid electrolytes, and the formation of less-conductive interphases
further deteriorates the transport in the composites.
This Account
focuses on the challenges associated with developing
practical solid-state lithium–sulfur batteries and provides
an overview over recently developed concepts to tackle these critical
challenges: (1) Introduction of the conversion efficiency to enable quantitative assessments of the impact of chemo-mechanical
failure. (2) For long-term cycling, the electrolyte degradation at
the interface and the electrochemical activity of the formed interphases
come into play. Practical stability tests with increased interfacial
areas and subsequently altered reversal potentials can quantify the
magnitude of the electrolyte degradation and confirm influences of
reversible redox activity o...