A reversible oxygen redox reaction in bulk-type all-solid-state batteries

Abstract

An all-solid-state lithium battery using inorganic solid electrolytes requires safety assurance and improved energy density, both of which are issues in large-scale applications of lithium-ion batteries. Utilization of high-capacity lithium-excess electrode materials is effective for the further increase in energy density. However, they have never been applied to all-solid-state batteries. Operational difficulty of all-solid-state batteries using them generally lies in the construction of the electrode-electrolyte interface. By the amorphization of Li2RuO3 as a lithium-excess model material with Li2SO4, here, we have first demonstrated a reversible oxygen redox reaction in all-solid-state batteries. Amorphous nature of the Li2RuO3-Li2SO4 matrix enables inclusion of active material with high conductivity and ductility for achieving favorable interfaces with charge transfer capabilities, leading to the stable operation of all-solid-state batteries.

Multiscale understanding of high-energy cathodes in solid-state batteries: from atomic scale to macroscopic scale

“…LiCoO 2 , Nirich layered oxides, LRLO, and Li-free cathodes) are enabling the construction of high-energy-dense SSBs [33]. Figure 3 schematically presents their properties in terms of volume change, specific capacity, rate capability, working voltage, cost, and cycle performance (in ascending order of specific capacity) [27,28,[39][40][41][42][43][44]. The upper cutoff voltage of commercial cathode material LiCoO 2 (LCO) was only 4.2 V vs. Li + /Li, which possesses only a specific capacity of 137 mAh g −1 [45].…”

“…By matching S 8 -Mo 6 S 8 -AEA cathode with the Li metal, the SSBs can deliver the capacity of 483 mAh g −1 , with volumetric and gravimetric energy densities of 2778 W h l −1 and 905.5 W h kg −1 , respectively. Nagao et al also designed a novel Li-rich cathode materials Li 2 Ru 0.8 S 0.2 O 3.2 [80Li 2 RuO 3 • 20Li 2 SO 4 ] through the amorphization of Li 2 RuO 3 with Li 2 SO 4 , which enables the CAMs to have high ductility and conductivity for obtaining favorable interfaces, resulting in the stable operation of SSBs [27].…”

Bidirectionally Compatible Buffering Layer Enables Highly Stable and Conductive Interface for 4.5 V Sulfide‐Based All‐Solid‐State Lithium Batteries

“…[14] As a result, the upper cutoff voltage of sulfide-based ASSLBs has rarely broken through 4.3 V (Table S1, Supporting Information). Although some pioneers have tried to match ≥4.5 V high-voltage cathodes (e.g., 4.5 V LiCoO 2 , [15] 4.6 V LiNi 1/3 Mn 1/3 Co 1/3 O 2 , [17] Li 2 RuO 3 , [3] LiNi 0.5 Mn 1.5 O 4 [11,19] ) with sulfide SEs, the corresponding discharge capacity and long cycle performance are still very limited (Table S1, Supporting Information). Therefore, scientifically informed design of thermodynamically stable and highly conductive interphase is still a key challenge in realization of sulfide-based high-voltage ASSLBs (HVASSLBs).…”

“…[2] By replacing organic liquid electrolytes with nonflammable solid electrolytes (SEs), ASSLBs are expected to address safety concerns associated with flammable organic electrolytes, and achieve wide-temperature-range applications. [3] Moreover, a higher volumetric energy density (>50%) can be achieved at the pack and system level, while the energy density of ASSLBs is virtually identical to that of conventional lithium-ion batteries at the materials level. [1a] Among various types of SEs, sulfide is viewed as one of the most promising High-voltage all-solid-state lithium batteries (HVASSLBs) are considered attractive systems for portable electronics and electric vehicles, due to their theoretically high energy density and safety.…”

Transitioning solid-state batteries from lab to market: Linking electro-chemo-mechanics with practical considerations

“…Nevertheless, recent efforts have proposed promising solutions to circumvent several of these interfacial and manufacturing challenges in the cathode component. These efforts include the usage of alternative cathode-active materials that are engineered to have more favorable ductility, 70,71 conductivity, 70 sintering temperatures, 71 and lithiation/delithiation strains. 72 For continued development of all-SSBs, there is a need for more directed efforts to understanding the many challenges-from manufacturing to cell failure-of cathode integration.…”