Application of Al-Doped LLTO Solid Electrolyte Prepared By Sol-Gel Method in Lithium-Oxygen Batteries

Wednesday, 8 October 2014
Expo Center, 1st Floor, Center and Right Foyers (Moon Palace Resort)
H. T. T. Le, H. S. Jadhav, R. S. Kalubarme, S. Y. Jang, and C. J. Park (Chonnam National University)
To date, lithium lanthanum titanate (LLTO) of the nominal formula Li3xLa2/3-x 1/3-2xTiO3 with perovskite structure have been considered to be promising solid electrolyte materials for lithium-oxygen battery due to a numerous outstanding advantages such as: (i) a high lithium conductivity at room temperature, (ii) a high lithium diffusion coefficient, (iii) a low electronic conductivity, and (iv) an electrochemical window larger than 4 V. However, the LLTO materials have also suffered from a few disadvantages such as insufficient total conductivity due to the large grain boundary resistance and difficulty in controlling Li+ content and Li+ conductivity of the materials especially after exposure to high annealing temperature. In addition, when the LLTO contacts directly with Li metal, Ti4+ in LLTO can be reduced into Ti3+ by metallic Li leading to increase in the electron conductivity of LLTO.

In this study, we investigated the feasibility of application of Al-doped LLTO ceramics with nominal formula of (Li1/3La5/9)1.005Ti0.99Al0.01O3 (denoted as A-LLTO) in Li–O2 batteries. A-LLTO was synthesized using sol-gel modified Pechini method in the aim of (i) reducing the synthesis temperature (up to 300-400 oC compared to the conventional solid state reaction method); (ii) lessening loss of lithium and gaining homogeneous mixture easily. As referred above, since LLTO cannot contacts directly with Li metal, prior to being assembled in organic- type Li-O2 battery as an electrolyte separator On the A-LLTO ceramics with 16 mm diameter and 200 m thickness, a thin protective layer of LiPON of 200 nm in thickness was sputtered for separation of A-LLTO from the Li metal anode. The perovskite material was used as catalyst for cathode material of the batteries.

The XRD patterns of A-LLTO ceramics obtained after annealing were compared and matched with Li0.33La0.56TiO3 (Code: 01-087-0935; Tetragonal) confirming purely the tetragonal crystalline structure P4/mmm space group of perovskite phase without secondary phases. After polished and heat etched at, the surface of the ceramics was observed using SEM. T ceramics was composed of grains of typical rectangle shape connected together closely. The largest grain size reached 100 m.

Ionic conductivity of A-LLTO measured using electrochemical impedance spectroscopy (EIS) exhibited the relatively high conductivity of 3.17 10-4 S/cm. This is attributed to the low total activation energy of 0.358 eV and the somewhat large crystal grain size compared with ceramics prepared at the same temperature.

The Li-O2 cells employing the A-LLTO ceramic electrolytes were tested in galvanostatic and constant capacity mode. Effect of current density and operating temperature on the charge-discharge behavior of Li-O2 cell was investigated. The Li-O2 cell employing A-LLTO electrolyte layer exhibited the satisfactory performance.