Recently, tailored synthesis of solid electrolytes satisfy multiple challenges, i.e. high ionic conductivity and wide (electro)chemical stability window is of great interest. Although both oxide- and sulfide-based solid electrolytes have distinguished merits for meeting such concerns separately, a new solid electrolyte having the excellent aspects of both materials is pursued. Herein, we report the synthesis of a sulfur-doped Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) solid electrolyte with a NASICON crystal structure that combines elevated ionic conductivity with intrinsic stability against an ambient atmosphere. Sulfur doping was carried out using sulfur-amine chemistry and the system was characterized by XRD, Raman, XPS, ICP-OES, and EDS analyses. Bader charge analysis was carried out with the aid of density functional theory calculations to characterize charge accumulation in the local environment of the bare and sulfur doped LATP structures. Our results indicate that the partial replacement of oxygen with sulfur yields higher ionic conductivity due to the lower electronegativity of sulfur compared to oxygen, which reduces the attraction of lithium ions. The enhanced ionic conductivity of LATP is attributed to a decreased lithium ion diffusion activation energy barrier upon sulfur doping. Compared to bare LATP, the as-prepared sulfur doped LATP powders were shown to decrease the activation energy barrier by 10.1%. Moreover, an ionic conductivity of 5.21 × 10⁻⁴ S cm⁻¹ was obtained for the sulfur doped LATP powders, whereas bare LATP had an ionic conductivity of 1.02 × 10⁻⁴ S cm⁻¹ at 40 °C.

中文翻译：

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硫掺杂的Li1.3Al0.3Ti1.7（PO4）3固体电解质，具有增强的离子电导率和降低的活化能垒。

近来，固体电解质的定制合成满足了多个挑战，即高离子电导率和宽的（电）化学稳定性窗口是令人关注的。尽管基于氧化物和基于硫化物的固体电解质都具有分别满足这些问题的显着优点，但是仍在寻求一种具有两种材料的优异方面的新型固体电解质。在此，我们报道了硫掺杂的Li _1.3 Al _0.3 Ti _1.7（PO ₄）₃的合成具有NASICON晶体结构的（LATP）固体电解质，结合了提高的离子电导率和对周围大气的固有稳定性。使用硫胺化学方法进行硫掺杂，并通过XRD，拉曼，XPS，ICP-OES和EDS分析对该系统进行了表征。借助密度泛函理论计算进行了有害电荷分析，以表征裸露和硫掺杂的LATP结构在局部环境中的电荷积累。我们的结果表明，与硫相比，由于硫的电负性较低，因此用硫部分替代氧可产生更高的离子电导率，从而降低了锂离子的吸引力。LATP离子电导率的提高归因于硫掺杂后锂离子扩散活化能垒的降低。与裸LATP相比，已制备的硫掺杂LATP粉末显示出将活化能垒降低了10.1％。此外，离子电导率为5.21×10对于硫掺杂的LATP粉末，获得了^-4 S cm ^-1，而在40℃下，裸露的LATP具有1.02×10 ^-4 S cm ^-1的离子电导率。