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A principle of suppressing Li dendrite in solid-state electrolytes is proposed and demonstrated using LiF-rich SEI experimentally.

All-ceramic cathode-electrolyte with a low interfacial resistance can be realized by thermally soldering LiCoO 2 and Li 7 La 3 Zr 2 O 12 (LLZO) together with Li 2.3Àx C 0.7+x B 0.3Àx O 3 solid electrolyte interphase through the reaction between the Li 2.3 C 0.7 B 0.3 O 3 solder and the Li 2 CO 3 layers that can be spontaneously coated on both LLZO and LiCoO 2. The all-solid-state Li/LLZO/LiCoO 2 battery with such an all-ceramic cathode/electrolyte exhibits high cycling stability and high rate performance.

All-solid-state lithium-sulfur batteries (ASSLSBs) using highly conductive sulfide-based solid electrolytes suffer from low sulfur utilization, poor cycle life, and low rate performance due to the huge volume change of the electrode and the poor electronic and ionic conductivities of S and Li2S. The most promising approach to mitigate these challenges lies in the fabrication of a sulfur nanocomposite electrode consisting of a homogeneous distribution of nanosized active material, solid electrolyte, and carbon. Here, we reported a novel bottom-up method to synthesize such a nanocomposite by dissolving Li2S as the active material, polyvinylpyrrolidone (PVP) as the carbon precursor, and Li6PS5Cl as the solid electrolyte in ethanol, followed by a coprecipitation and high-temperature carbonization process. Li2S active material and Li6PS5Cl solid electrolyte with a particle size of ∼4 nm were uniformly confined in a nanoscale carbon matrix. The homogeneous nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic and electronic conductivities enabled a mechanical robust and mixed conductive (ionic and electronic conductive) sulfur electrode for ASSLSB. A large reversible capacity of 830 mAh/g (71% utilization of Li2S) at 50 mA/g for 60 cycles with a high rate performance was achieved at room temperature even at a high loading of Li2S (∼3.6 mg/cm(2)). This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance all-solid-state lithium sulfur batteries.