High Ion Conductivity in Garnet-type F-doped Li7La3Zr2O12

doi:10.15541/jim20150163

Abstract

Abstract:

A novel garnet-type solid electrolyte, F-doped Li₇La₃Zr₂O₁₂ (LLZO), was prepared via conventional solid-state reaction. Certain fluoride compounds were known to form the pure cubic garnet structure after continuous calcination at 900℃ and 1125℃, seperately. Fluorine ions doped in LLZO contributed to the stabilization of high ion conductivity garnet phase as well as the enhancement of sintering activity. The effects of fluorine ions were studied using the dopants LiF and CaF₂. The 1.0wt% LiF-LLZO samples exhibited a total conductivity of 5×10^-4 S/cm close to the bulk conductivity value of un-doped LLZO, while its activation energy was 0.26 eV, lower than that of other cation-doped LLZO samples. The strong intensity of the peaks indexed to (321), (400), (642), and (800) in XRD patterns indicated the growth of ceramic grains of F-doped LLZO in certain favorable crystallographic orientations during sintering process. In addition, a unique microstructure was revealed in the novel garnet-type oxide pellets, showing the grain boundary almost removed and closed pores formed, which resulted in the negligible grain boundary and the high total ion conductivity.

Key words: solid electrolyte, garnet-type, fluorine ion doping, microstructure

LIU Cai, WEN Zhao-Yin, RUI Kun. High Ion Conductivity in Garnet-type F-doped Li₇La₃Zr₂O₁₂[J]. Journal of Inorganic Materials, 2015, 30(9): 995-1001.

Figures/Tables 7

Fig. 1 Crystal structure for the cubic LLZO (a) Three-dimensional migration structure of lithium ion viewed in (111) orientation; (b) F substitution in oxide polyhedral structure model

Fig. 2 XRD patterns of synthesized LLZO powder doped with different amounts of LiF after two-step calcinations

Fig. 3 XRD patterns of synthesized LLZO powder with different fluorides after two-step calcination

Fig. 4 XRD patterns of 1.0F-LLZO sintered pellet and powder The typical peaks of cubic garnet phase were indexed for illustration

Fig. 5 AC impedance plots at room temperature (a) 0.5F-LLZO and 1.0LLZO; (b) 2Al-LLZO; (c) 1.5CF-LLZO

Fig. 6 Temperature dependence of the lithium conductivity of 1.0F-LLZO and the Arrhenius plot linear-fitting results

Fig. 7 The SEM images of cross-section microstructure for LLZO doped with different fluoride compounds (a) 0.5F-LLZO; (b) 1.0F-LLZO; (c) 1.5CF-LLZO; (d) 2Al-LLZO

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High Ion Conductivity in Garnet-type F-doped Li₇La₃Zr₂O₁₂

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