Safe and Efficient Energy: Game-Changing Battery Materials Discovered

Researchers have discovered a pyrochlore-type oxyfluoride as a stable, lithium-ion conductor with excellent conductivity, suitable for use as solid electrolytes in all-solid-state lithium-ion batteries. Credit: scalespeeder from Openverse

Scientists have identified a stable and highly conductive lithium-ion conductor that can be used as solid electrolytes in solid-state lithium-ion batteries.

Solid-state lithium-ion batteries, which use solid electrolytes, are non-flammable and boast higher energy density and ion transference numbers compared to their liquid electrolyte counterparts. These features position them as potential replacements in markets dominated by traditional liquid electrolyte batteries, including electric vehicles. Despite these benefits, solid electrolytes present drawbacks such as lower lithium-ion conductivity and difficulties in maintaining sufficient contact between the electrodes and the solid electrolyte.

While sulfide-based solid electrolytes are conductive, they react with moisture to form toxic hydrogen disulfide. Therefore, there’s a need for non-sulfide solid electrolytes that are both conductive and stable in air to make safe, high-performance, and fast-charging solid-state Li-ion batteries.

In a recent study published in the journal Chemistry of Materials, a research team led by Professor Kenjiro Fujimoto, Professor Akihisa Aimi from Tokyo University of Science, and Dr. Shuhei Yoshida from DENSO CORPORATION, discovered a stable and highly conductive Li-ion conductor in the form of a pyrochlore-type oxyfluoride.

According to Prof. Fujimoto, “Making all-solid-state lithium-ion secondary batteries has been a long-held dream of many battery researchers. We have discovered an oxide solid electrolyte that is a key component of all-solid-state lithium-ion batteries, which have both high energy density and safety. In addition to being stable in air, the material exhibits higher ionic conductivity than previously reported oxide solid electrolytes.”

Detailed Analysis and Performance

The pyrochlore-type oxyfluoride studied in this work can be denoted as Li_2-xLa_(1+x)/3M₂O₆F (M = Nb, Ta). It underwent structural and compositional analysis using various techniques, including X-ray diffraction, Rietveld analysis, inductively coupled plasma optical emission spectrometry, and selected-area electron diffraction. Specifically, Li_1.25La_0.58Nb₂O₆F was developed, demonstrating a bulk ionic conductivity of 7.0 mS cm⁻¹ and a total ionic conductivity of 3.9 mS cm⁻¹ at room temperature. It was found to be higher than the lithium-ion conductivity of known oxide solid electrolytes. The activation energy of ionic conduction of this material is extremely low, and the ionic conductivity of this material at low temperatures is one of the highest among known solid electrolytes, including sulfide-based materials.

Exactly, even at –10°C, the new material has the same conductivity as conventional oxide-based solid electrolytes at room temperature. Furthermore, since conductivity above 100 °C has also been verified, the operating range of this solid electrolyte is –10 °C to 100 °C. Conventional lithium-ion batteries cannot be used at temperatures below freezing. Therefore, the operating conditions of lithium-ion batteries for commonly used mobile phones are 0 °C to 45 °C.

The Li-ion conduction mechanism in this material was investigated. The conduction path of pyrochlore-type structure covers the F ions located in the tunnels created by MO₆ octahedra. The conduction mechanism is the sequential movement of Li-ions while changing bonds with F ions. Li ions move to the nearest Li position always passing through metastable positions. Immobile La³⁺ bonded to F ion inhibits the Li-ion conduction by blocking the conduction path and vanishing the surrounding metastable positions.

Unlike existing lithium-ion secondary batteries, oxide-based all solid-state batteries have no risk of electrolyte leakage due to damage and no risk of toxic gas generation as with sulfide-based batteries. Therefore, this new innovation is anticipated to lead future research. “The newly discovered material is safe and exhibits higher ionic conductivity than previously reported oxide-based solid electrolytes. The application of this material is promising for the development of revolutionary batteries that can operate in a wide range of temperatures, from low to high,” envisions Prof. Fujimoto. “We believe that the performance required for the application of solid electrolytes for electric vehicles is satisfied.”

Notably, the new material is highly stable and will not ignite if damaged. It is suitable for airplanes and other places where safety is critical. It is also suitable for high-capacity applications, such as electric vehicles, because it can be used under high temperatures and supports rapid recharging. Moreover, it is also a promising material for the miniaturization of batteries, home appliances, and medical devices.

In summary, researchers have not only discovered a Li-ion conductor with high conductivity and air stability but also introduced a new type of superionic conductor with a pyrochlore-type oxyfluoride. Exploring the local structure around lithium, their dynamic changes during conduction, and their potential as solid electrolytes for all-solid-state batteries are important areas for future research!

Reference: “High Li-Ion Conductivity in Pyrochlore-Type Solid Electrolyte Li2–xLa(1+x)/3M2O6F (M = Nb, Ta)” by Akihisa Aimi, Hitoshi Onodera, Yuta Shimonishi, Kenjiro Fujimoto and Shuhei Yoshida, 28 March 2024, Chemistry of Materials.
DOI: 10.1021/acs.chemmater.3c03288