%0 Journal Article
%A Helm, Bianca
%A Strotmann, Kyra
%A Böger, Thorben
%A Samanta, Bibek
%A Banik, Ananya
%A Lange, Martin A.
%A Li, Yuheng
%A Li, Cheng
%A Hansen, Michael Ryan
%A Canepa, Pieremanuele
%A Zeier, Wolfgang G.
%T Reducing the Defect Formation Energy by Aliovalent Sn(+IV) and Isovalent P(+V) Substitution in $Li_3SbS_4$ Promotes Li${^+}$ Transport
%J ACS applied energy materials
%V 7
%N 5
%@ 2574-0962
%C Washington, DC
%I ACS Publications
%M FZJ-2024-02079
%P 1735 - 1747
%D 2024
%X The search for highly conducting Li+ solid electrolytes focuses on sulfide- and halide-based materials, where typically the strongly atomic disordered materials are the most promising. The atomic disorder corresponds to a flattened energy landscape having similar relative site energies for different Li+ positions facilitating motion. In addition, the highly disordered Li+ conductors have negligible defect formation energy as moving charges are readily available. This work investigates the isovalent Li3Sb1–xPxS4 (0 ≤ x ≤ 0.5) and the aliovalent Li3+xSb1–xSnxS4 (0 ≤ x ≤ 0.2) substitution series of thio-LISICON materials by using X-ray diffraction, high-resolution neutron diffraction, impedance spectroscopy, and defect calculations. The starting composition Li3SbS4 has a low ionic conductivity of ∼10–11 S·cm–1 and both substituents improve the ionic conductivity strongly by up to 4 orders of magnitude. On the one hand, in substituted Li3SbS4 structures, only minor structural changes are observed which cannot sufficiently explain the significant impact on the Li+ conductivity. On the other hand, the Li+ carrier density reveals a correlation to the activation energy and first-principles defect calculations, displaying significantly reduced defect formation energy upon substitution. Here, we show within two different substitution series that the defect formation energy plays a major role for ionic motion in this class of thio-LISICON materials.
%F PUB:(DE-HGF)16
%9 Journal Article
%U <Go to ISI:>//WOS:001176923300001
%R 10.1021/acsaem.3c02652
%U https://juser.fz-juelich.de/record/1024272