Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7–2xLa3Zr2–xMoxO12 (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+

Rettenwander, Daniel; Welzl, Andreas; Cheng, Lei; Fleig, Jürgen; Musso, Maurizio; Suard, Emmanuelle; Doeff, Marca M.; Redhammer, Günther J.; Amthauer, Georg

doi:10.1021/acs.inorgchem.5b01895

Cited by 103 publications

(91 citation statements)

References 24 publications

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“…Based on our previous work R e characterizes the bulk response and corresponds to σ bulk of 1.1 mS·cm –1 . 9 The capacitance of the semicircle can be determined via C int = ( R int 1– n CPE int ) 1/ n 1 , where n is a fitting value. The capacitance obtained was in the μF range which is a typical value characterizing charge transfer processes at interfaces; the intermediate arc is, therefore, attributed to the interfacial resistance.…”

Section: Results and Discussionmentioning

confidence: 99%

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

et al. 2018

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The interface stability versus Li represents a major challenge in the development of next-generation all-solid-state batteries (ASSB), which take advantage of the inherently safe ceramic electrolytes. Cubic Li7La3Zr2O12 garnets represent the most promising electrolytes for this technology. The high interfacial impedance versus Li is, however, still a bottleneck toward future devices. Herein, we studied the electrochemical performance of Fe3+-stabilized Li7La3Zr2O12 (LLZO:Fe) versus Li metal and found a very high total conductivity of 1.1 mS cm–1 at room temperature but a very high area specific resistance of ∼1 kΩ cm2. After removing the Li metal electrode we observe a black surface coloration at the interface, which clearly indicates interfacial degradation. Raman- and nanosecond laser-induced breakdown spectroscopy reveals, thereafter, the formation of a 130 μm thick tetragonal LLZO interlayer and a significant Li deficiency of about 1–2 formula units toward the interface. This shows that cubic LLZO:Fe is not stable versus Li metal by forming a thick tetragonal LLZO interlayer causing high interfacial impedance.

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Section: Results and Discussionmentioning

confidence: 99%

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

et al. 2018

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“…Regarding Li 7 La 3 Zr 2 O 12 , its tetragonal modification is a moderate Li ion conductor [119]. The replacement of La and Zr ions with isovalent or aliovalent cations greatly affects, however, (i) the defect chemistry, (ii) the crystal structure parameters and (iii) also the Li content of the garnets [40,[120][121][122]. These variations lead to a series of oxides that may largely differ in ionic conductivities [19].…”

Section: Garnet-type Oxides: Cation-stabilized Cubic Llzo and Llzmomentioning

confidence: 99%

Ion dynamics in solid electrolytes for lithium batteries

et al. 2017

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All-solid-state batteries with ceramic electrolytes and lithium metal anodes represent an attractive alternative to conventional ion battery systems. Conventional batteries still rely on flammable liquids as electronic insulators. Despite the great efforts reported over the last years, the optimum solid electrolyte has, however, not been found yet. One of the most important properties which decides whether a ceramic is useful to work as electrolyte is ionic transport. The various time-domain nuclear magnetic resonance (NMR) techniques might help characterize and select the most suitable candidates. Together with conductivity measurements it is possible to analyze ion dynamics on different length-scales, i.e., to differentiate between local, within-site hopping processes from long-range ion transport. The latter needs to be sufficiently fast in the ceramic, in the best case competing with that of liquid electrolytes. In addition to conductivity spectroscopy, NMR can help understand the relationship between local structure and dynamic parameters. Besides information on activation energies and jump rates the data also contain suggestions about the relevant elementary steps of ion hopping and, thus, Support by the Deutsche Forschungsgemeinschaft (DFG) is highly appreciated (FOR 1277 diffusion pathways through the crystal lattice. Recent progress in characterizing ion dynamics in ceramic electrolytes by NMR relaxometry will be briefly reviewed. Focus is put on presently discussed solid electrolytes such as garnets, phosphates and sulfides, which have so far been studied in our lab.

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“…For a capacitance of 5 nF a relative permittivity of 152 is calculated, which is about 3 times the value previously reported for bulk transport of Li-ions in Mo-doped LLZO bulk ceramics. 35 It is known that the calculation of ε r on the basis of a simple parallel-plate capacitor (Eq. 4) leads to values higher than expected, if bulk and grain boundary conduction are of similar order of magnitude.…”

Section: Assignment Of the R1-cpe1 Element To The LI 7 La 3 Zr 2 O 12mentioning

confidence: 99%

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

111

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The detailed characterization of garnet-type Li-ion conducting Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte thin films grown by novel CO 2 -laser assisted chemical vapor deposition (LA-CVD) is reported. A deposition process parameter study reveals that an optimal combination of deposition temperature and oxygen partial pressure is essential to obtain high quality tetragonal LLZO thin films. The polycrystalline tetragonal LLZO films grown on platinum have a dense and homogeneous microstructure and are free of cracks. A total lithium ion conductivity of 4.2 · 10 −6 S · cm −1 at room temperature, with an activation energy of 0.50 eV, is achieved. This is the highest total lithium ion conductivity value reported for tetragonal LLZO thin films so far, being about one order of magnitude higher than previously reported values for tetragonal LLZO thin films prepared by sputtering and pulsed laser deposition. The results of this study suggest that the tetragonal LLZO thin films grown by LA-CVD are applicable for the use in all-solid-state thin film lithium ion batteries. Over the last decades a progressive miniaturization of electronic components took place. As a result there is an increasing demand for micro-sized power sources that drives the current research on thin film batteries. Possible applications range from sensors and radiofrequency identification tags to implantable medical devices. For these applications an all-solid-state thin film Li-ion battery is desirable due to considerable advantages such as excellent safety properties and easy integration in microelectronics. Furthermore, the energy density of such an all-solid-state cell can be increased compared to a cell with conventional liquid electrolyte, if the chosen solid electrolyte material is stable toward high voltage cathode materials as well as toward a lithium metal anode. The garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO), first reported in 2007 by Murugan et al., 1 is a material that combines those properties with reasonably high lithium ion conductivity of up to 2.3 · 10 −5 S · cm −1 in its tetragonal 2 and up to 1.2 · 10 −3S · cm −1 in its cubic 3 modification. However, these high conductivity values have so far only been achieved for bulk ceramics, but not for thin films. Apparently, over the last years researchers have focused on the optimization of the lithium ion conductivity in bulk ceramics, e.g. by stabilization of the cubic LLZO phase via doping, 4,5 while only a few publications have addressed LLZO thin film deposition at all. 6-12The advantage of thin films is that their lithium ion conductivity for the use in an all-solid-state battery does not need to be as high as compared to bulk solid electrolytes, taking into account the electrolyte resistance R:where A is the contact area, l is the thickness and σ is the Li-ion conductivity of the solid electrolyte, respectively. For example, in their recent study Liu et al. 13 report on a functioning bulk all-solid-state battery using cubic LLZO as solid electrolyte with ∼ 1 mm thickn...

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Synthesis, Crystal Chemistry, and Electrochemical Properties of Li_7–2xLa₃Zr_2–xMo_xO₁₂ (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr⁴⁺ by Mo⁶⁺

Cited by 103 publications

References 24 publications

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

Ion dynamics in solid electrolytes for lithium batteries

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

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Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7–2xLa3Zr2–xMoxO12 (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+

Cited by 103 publications

References 24 publications

Interface Instability of Fe-Stabilized Li7La3Zr2O12 versus Li Metal

Interface Instability of Fe-Stabilized Li7La3Zr2O12 versus Li Metal

Ion dynamics in solid electrolytes for lithium batteries

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State Batteries

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Synthesis, Crystal Chemistry, and Electrochemical Properties of Li_7–2xLa₃Zr_2–xMo_xO₁₂ (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr⁴⁺ by Mo⁶⁺

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

Interface Instability of Fe-Stabilized Li₇La₃Zr₂O₁₂ versus Li Metal

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries