New insights into the mechanism of cation migration induced by cation–anion dynamic coupling in superionic conductors

Abstract

Understanding the ion diffusion mechanism is one of the key preconditions for designing superionic conductors in solid state lithium batteries and many other energy devices. Besides single-cation vacancy/interstitial-assisted and multi-cation...

Review on the lithium transport mechanism in solid‐state battery materials

“…Such a mechanism has been used to explain the fast Li-ion transports at room temperature in glassy Li 7 P 3 S 11 , 184 β-Li 3 PS 4 , 186 Li 3.25 Si 0.25 P 0.75 S 4 , 186 Li 6 PS 5 X (X = Cl, Br, and I), 187 LiBF 4 , 188 and Li 2 BF 5 . 188 The paddle-wheel effect in glassy Li 7 P 3 S 11 is attributed to the similar vibration frequency distributions of Li ions and anions and similar activation energies (0.27 and 0.22 eV) of PS 4 rotation and Li translation. Very recently, Li et al performed a brilliant theoretical investigation to understand the paddlewheel effect.…”

“…Very recently, Li et al performed a brilliant theoretical investigation to understand the paddlewheel effect. 188 The cation-anion interactions in SEs are further divided into vibrational-and rotational-type couplings by the motions of anion frameworks. A new anion framework BF 4…”

“…In the scenario of the paddle–wheel effect, Li‐ion transport is facilitated by the rotation of anionic frameworks (Figure 8), 101 which is somewhat similar to the transport of people through a multi‐people revolving door. Such a mechanism has been used to explain the fast Li‐ion transports at room temperature in glassy Li 7 P 3 S 11 , 184 β ‐Li 3 PS 4 , 186 Li 3.25 Si 0.25 P 0.75 S 4 , 186 Li 6 PS 5 X (X = Cl, Br, and I), 187 LiBF 4 , 188 and Li 2 BF 5 188 . The paddle–wheel effect in glassy Li 7 P 3 S 11 is attributed to the similar vibration frequency distributions of Li ions and anions and similar activation energies (0.27 and 0.22 eV) of PS 4 rotation and Li translation.…”

“…The paddle–wheel effect in glassy Li 7 P 3 S 11 is attributed to the similar vibration frequency distributions of Li ions and anions and similar activation energies (0.27 and 0.22 eV) of PS 4 rotation and Li translation. Very recently, Li et al performed a brilliant theoretical investigation to understand the paddle–wheel effect 188 . The cation–anion interactions in SEs are further divided into vibrational‐ and rotational‐type couplings by the motions of anion frameworks.…”

New Halide-Based Sodium-Ion Conductors Na3Y2Cl9 Inversely Designed by Building Block Construction

“…Thus the concerted migration effect is prohibited and Na + hardly diffuses in the R32-Na 3 Y 2 Cl 9 phase. Although many articles have highlighted the significant role of rotation of polyanionic groups in ion transport, 40,41 particularly in the Na−Y−Zr−Cl system where the rotation of polyanionic groups significantly enhances the transport properties of Na ions, 28 however the MSD versus time plot of every single Cl atoms in P6 3 -Na 3 Y 2 Cl 9 at 950 K (as shown in Figure S10) indicates that there is no rotation effect of polyanionic groups in the Na 3 Y 2 Cl 9 mentioned in this work, which may be due to the restricted lattice space.…”