Li1.5La1.5MO6 (M = W6+, Te6+) as a new series of lithium-rich double perovskites for all-solid-state lithium-ion batteries

Abstract

Solid-state batteries are a proposed route to safely achieving high energy densities, yet this architecture faces challenges arising from interfacial issues between the electrode and solid electrolyte. Here we develop a novel family of double perovskites, Li1.5La1.5MO6 (M = W6+, Te6+), where an uncommon lithium-ion distribution enables macroscopic ion diffusion and tailored design of the composition allows us to switch functionality to either a negative electrode or a solid electrolyte. Introduction of tungsten allows reversible lithium-ion intercalation below 1 V, enabling application as an anode (initial specific capacity >200 mAh g-1 with remarkably low volume change of ∼0.2%). By contrast, substitution of tungsten with tellurium induces redox stability, directing the functionality of the perovskite towards a solid-state electrolyte with electrochemical stability up to 5 V and a low activation energy barrier (<0.2 eV) for microscopic lithium-ion diffusion. Characterisation across multiple length- and time-scales allows interrogation of the structure-property relationships in these materials and preliminary examination of a solid-state cell employing both compositions suggests lattice-matching avenues show promise for all-solid-state batteries.

Atomic Short‐Range Order in a Cation‐Deficient Perovskite Anode for Fast‐Charging and Long‐Life Lithium‐Ion Batteries

“…[1][2][3][4][5][6][7] Among the various options, perovskite-type oxides have attracted wide attention owing to abundant insertion sites for Li + storage/ migration and the capacity to accommodate a wide range of cation sizes and oxidation states inside the framework. [15][16][17][18][19][20] Generally, the representative perovskite-type structure is composed of an MO 6 (M = Ti, [19] Nb, [20] W, [17] and Te [17] ) octahedral framework stabilized by rare-earth atoms (A-site). Originating from the structural features, high ionic conductivity, which is a prerequisite for the application of fast-charging lithium-ion batteries, can be obtained by variations in the concentration of A-site cation vacancies.…”

“…Currently, a double perovskite structure with long-range cationic order has been applied to reduce the symmetry and consequently suppress the phase transition. [17,23] However, the use of perovskite oxides in fast-charging lithium-ion batteries is limited to only a few reports, and there remain great challenges in exploiting suitable perovskite oxides for high-rate lithium-ion batteries. In addition, the mechanism to increase the rate performance and cycling stability needs to be further investigated, as this holds the key to exploiting new high-rate and long-life perovskite electrode materials.…”

Pressure Dependence of Structural Behavior and Electronic Properties in Double Perovskite Ba2SmSbO6

“…Double perovskite (A 2 B′B″O 6 ) represents a unique class of materials for electrode materials in batteries, sensors, and fuel cells. − These ternary compounds exhibit a wide range of physical and chemical properties, i.e., intersite charge transfer, disproportionation, and phase transformation. − When the difference of charge or ionic radii between B′ and B″ cations are greater, double perovskites have ordered structures. , A 2 B′B″O 6 with rare-earth B′ and B″ cations attracts widespread attention, due to geometric magnetic frustration and high-quality superconducting thick films . Recently, reports of double perovskites continue to exhibit significant progress in magnetic order , and photoluminescence properties. , For example, the antiferromagnetic order of Ni 2+ ion moments is determined by Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb in double perovskite NaLnNiWO 6 in the range of 23–30 K .…”

Effect of Li concentration on the ionic conductivity of Li<i>_x</i>La₍₁₋<i>_x</i>_)/3Nb_0.80Ta_0.20O₃ solid solutions

“…Based on crystal structure, oxide electrolytes can be classified into several types including lithium superionic conductor, 5) sodium superionic conductor, 6) garnet, 7) and perovskite. 8), 9) Among them, double perovskites such as La 2/3¹x Li 3x TiO 3 , 8),10), 11) Li x La (1¹x)/3 -NbO 3 , 12), 13) Li x La (1¹x)/3 TaO 3 , 14), 15) and Li 1.5 La 1.5 MO 6 (M = W 6+ , Te 6+ ) 16) have relatively high ionic conductivities (•). Specifically, La 2/3¹x Li 3x TiO 3 with x = 0.117 exhibits • = 10 ¹3 S cm ¹1 at room temperature.…”