Solid Electrolytes

Perovskite Lithium Conductors

A-site-deficient perovskites in the (Li,La)TiO3 (LLTO) family with bulk ionic conductivities above 1 mS/cm. Grain-boundary resistance and Ti4+ reduction against lithium metal define their engineering limits.

At a glance

Class Statistics

Compounds Tracked
13
Multi-Source DFT
2
With Synthesis Routes
0
Avg. Agreement
Overview

What are Perovskite Lithium Conductors?

Perovskite lithium conductors, primarily represented by the lithium lanthanum titanate (LLTO) family, are a class of solid-state electrolyte materials characterized by an ABO3 perovskite crystal structure. These materials are typically engineered to be A-site deficient, which facilitates the migration of lithium ions through the lattice via a vacancy-hopping mechanism. Chemically, they consist of a rigid framework of corner-sharing TiO6 octahedra, with lithium and lanthanum cations occupying the A-sites. The high bulk ionic conductivity of these materials makes them significant candidates for next-generation solid-state batteries, as they offer the potential for high power density and improved safety compared to traditional liquid electrolytes. However, their practical application is constrained by several engineering hurdles. Notably, the high grain-boundary resistance significantly limits total ionic transport across polycrystalline samples. Furthermore, the thermodynamic instability of the Ti4+ species when in direct contact with lithium metal leads to reduction, causing electronic conductivity that can result in short-circuiting. Despite these challenges, LLTO remains a cornerstone of solid-state ionics research. Notable members include various compositions within the Li(3x)La(2/3-x)TiO3 series, where the precise stoichiometry of lithium and lanthanum is tuned to optimize the vacancy concentration and lattice parameters. Ongoing research focuses on grain-boundary engineering and protective coating strategies to mitigate reactivity, aiming to harness the exceptional bulk transport properties of these perovskites for stable, high-performance energy storage devices.

Members

Top Perovskite Lithium Conductors

Ranked by data richness — literature synthesis coverage, multi-source DFT corroboration, and patent activity.

FormulaBand GapBest EAH (eV/atom)StabilityDFT SourcesRecipes
LiLaTi2O61.76–1.86 eV0.0623Metastable20
LiLaTiO42.26 eV0.0288Metastable20
La5Li1O24Ti82.00–2.20 eV0.0279Metastable10
La5LiO24Ti82.00–2.20 eV0.0279Metastable10
La2Li2O8Ti22.26 eV0.0288Metastable10
La2LiNaO12Ti41.90–2.16 eV0.0309Metastable10
La2Li2O10Ti31.77 eV0.0204Near hull (likely stable)10
LiLa3Ti4O12Metallic / not reported0.0287Metastable10
LiLa2TiO6Metallic / not reported0.0628Metastable10
LiLa4Ti3O12Metallic / not reported0.0306Metastable10
La2LiO6TiMetallic / not reported0.0628Metastable10
La5Li4Nb2O26Ti6Metallic / not reported0.0490Metastable10
LaLi2O7Ti2Metallic / not reportedNot assessed10
Reference

Frequently Asked Questions

How many perovskite lithium conductors are in the database?
13 perovskite lithium conductors are tracked, of which 2 have multi-source DFT validation and 0 have documented synthesis routes.
What is the most data-rich perovskite lithium conductor?
LiLaTi2O6 is the most thoroughly characterized, with 9 reported structures.
Which perovskite lithium conductor has the widest band gap?
Among the top compounds, LiLaTiO4 has the widest reported DFT band gap (2.26 eV).
What is the primary mechanism of lithium-ion transport in LLTO?
Lithium ions move through the perovskite lattice primarily via a vacancy-hopping mechanism, where ions migrate between available A-site vacancies within the rigid titanium-oxygen framework.
Why is the grain boundary a major limitation for these materials?
In polycrystalline samples, the grain boundaries often exhibit significantly higher resistance than the bulk material, which severely restricts the overall ionic conductivity of the electrolyte.
Can perovskite lithium conductors be used directly with lithium metal anodes?
Generally, no. The Ti4+ ions in the perovskite structure are prone to reduction when in contact with lithium metal, which increases electronic conductivity and can lead to internal short-circuiting.
How does A-site deficiency affect the performance of these conductors?
A-site deficiency is crucial because it introduces the necessary vacancies in the crystal lattice that allow lithium ions to move; without these vacancies, the ionic conductivity would be negligible.
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