Enhanced lithium ion transport in garnet-type solid state electrolytes

Abstract

We have replaced the original with a corrected Figure 4, showing proper units. I suggest to mention the room T ionic conducitivity values explicitely on p. 10 and to compare them with literature data. I have the impression that the Ar sample is in line with several data sets found in literature and the air sample is worse than average literature data? We have added several lines on p. 10 giving the room temperature ionic conductivities of the two different samples, along with some extra literature references for Al-substituted LLZO (all highlighted). Reported conductivities vary a great deal depending on processing details, with values ranging from about less than 0.1-0.5 mS/cm 2. The values we report here for LLZO_air are similar to what we reported before for similarly made samples (see reference 25). Response to Reviewer Comments

Atomistic Insight into Ion Transport and Conductivity in Ga/Al-Substituted Li7La3Zr2O12 Solid Electrolytes

“…where c is the concentration of ionic species with ionic charge z, F the Faraday's constant, R The same behavior is found in experimental works based on impedance spectroscopy for 22,23,[58][59][60][61][62] and Ga-substituted 11,24,49,59,63,64 LLZO systems. Although the overall trend in conductivity is independent of the substituent cation, this is not the case for the corresponding slopes which are related to the activation energies.…”

Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition

“…As a rst step we have to avoid chemical analysis of near surface layers on LLZO; they are well-known to exhibit different chemical compositions and may include different phases. 27,29,[33][34][35] Also Li + /H + exchange caused by water from the air has been reported and should be taken into account. 23,[25][26][27]67 In ref.…”

“…in depths of several mm) were already investigated by laser-induced breakdown spectroscopy (LIBS) and even 3D elemental maps of LLZO ceramics became accessible. 29,[33][34][35] However, they were not correlated with local conductivities, rather the focus was on the impact of the composition on the overall interfacial resistances of the samples. 29,33 In our study, bulk compositional variations within Al stabilized LLZO ceramics are investigated as a possible reason behind the scatter of bulk conductivity values.…”

Al-incorporation into Li7La3Zr2O12 solid electrolyte keeping stabilized cubic phase for all-solid-state Li batteries

“…The peak at approximately 55.4 eV is attributed to Li 2 CO 3 , and the peak at 54.2 eV is due to the Li -O bond of LLZO. Signals from the peaks of La 4 d and Zr 3 d were not detected because of the scattering depth limitation of XPS in inorganic materials [13,27] . Comparing with the intensity of Li 2 CO 3 peaks in all samples, Al-LLZO showed less value and it means that Li 2 CO 3 formation was deterred on Al-LLZO.…”