Argyrodite Sulfide Electrolytes with Dry Atmospheric Stability for All-Solid-State Lithium Batteries.
basic_science · Level V
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- Record sourced from PubMed, PMID 42289953.
- Also identified by DOI 10.1002/adma.73671.
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Abstract
The instability of sulfide electrolytes toward air and their incompatibility with solvents remain a great challenge that hampers their scalable manufacturing for all-solid-state lithium batteries. In this work, the effects of major components in air on argyrodite sulfide electrolytes are systematically investigated, including N<sub>2</sub>, O<sub>2</sub>, and CO<sub>2</sub>. Both Li<sub>6</sub>PS<sub>5</sub>Cl and Li<sub>5.4</sub>PS<sub>4.4</sub>Cl<sub>1.6</sub> exhibit chemical inertness toward N<sub>2</sub>, but easily react with O<sub>2</sub> and CO<sub>2</sub>. Notably, Li<sub>5.4</sub>PS<sub>4.4</sub>Cl<sub>1.6</sub> shows inferior stability against O<sub>2</sub> and CO<sub>2</sub> compared to Li<sub>6</sub>PS<sub>5</sub>Cl, attributed to the weakness of P─Cl bond in the PS<sub>3</sub>Cl motif as confirmed by density functional theory calculations. Nevertheless, oxygen doped Li<sub>6.05</sub>PS<sub>4.9</sub>O<sub>0.1</sub>Cl<sub>1.05</sub> and Li<sub>5.3</sub>PS<sub>4.2</sub>O<sub>0.2</sub>Cl<sub>1.5</sub> possess more positive free energy changes towards O<sub>2</sub> and CO<sub>2</sub> oxidation, thereby suppressing the decomposition of PS<sub>4</sub> <sup>3-</sup> units. In addition, Li<sub>5.3</sub>PS<sub>4.2</sub>O<sub>0.2</sub>Cl<sub>1.5</sub> also shows excellent tolerance to sec-butyl acetate, realizing a 12 µm-thick membrane with high ionic conductivity of 2.34 mS cm<sup>-1</sup> by wet-coating process. Moreover, the improved interface compatibility between Li<sub>5.3</sub>PS<sub>4.2</sub>O<sub>0.2</sub>Cl<sub>1.5</sub> and lithium metal enables stable cycling for 10 000 h at 0.1 mA cm<sup>-2</sup>. The resultant LiNbO<sub>3</sub>@LiCoO<sub>2</sub>|Li<sub>5.3</sub>PS<sub>4.2</sub>O<sub>0.2</sub>Cl<sub>1.5</sub>|Li battery retains 81.6% of its initial capacity after 1000 cycles at 1 C, and the LiNbO<sub>3</sub>@LiCoO<sub>2</sub>||Li pouch cell with Li<sub>5.3</sub>PS<sub>4.2</sub>O<sub>0.2</sub>Cl<sub>1.5</sub> membrane delivers 86.6% capacity retention after 250 cycles at 0.1 C.