Li Ion Dynamics in Al-Doped Garnet-Type Li7La3Zr2O12 Crystallizing with Cubic Symmetry

Kuhn, Alexander; Choi, Joon-Yong; Robben, Lars; Tietz, Frank; Wilkening, Martin; Heitjans, Paul

doi:10.1524/zpch.2012.0250

Cited by 35 publications

(30 citation statements)

References 31 publications

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“…By reducing the Li content, Li vacancies are created and together with the introduction of the Al substituent, these two chemical modifications play a major role in the Li-ion conduction mechanism, and not only the crystalline structure. A purely cubic LLZ is not necessary for achieving high total Li-ion conductivity as shown here and as there exist also examples of poorly conductive cubic LLZ [31]. Nevertheless, from the ICP-OES results, there is definitely more Li in the samples than what is needed for stoichiometric LLZ:Al if we assume Al 3+ only replacing Li + sites.…”

Section: Resultsmentioning

confidence: 72%

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

et al. 2015

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Al-substituted Li 7 La 3 Zr 2 O 12 (LLZ:Al) was synthesized via conventional solid state reaction. Different dwell times at sintering temperature of 1200°C led to a varying Li content in LLZ:Al which significantly affected the Li-ion conductivity. Electrochemical impedance spectroscopy and X-ray diffraction were used to characterize the sintered pellets which showed a maximum total ionic conductivity of~3 × 10 −4 S cm −1 at room temperature although the samples were composed of cubic and tetragonal LLZ:Al, with the tetragonal phase as its major phase. Inductively coupled plasma optical emission spectroscopy revealed that the Li content steadily decreased from 7.5 to 6.5 Li per formula unit with increasing sintering time. The highest conductivity was observed from the sample with the lowest Li concentration at 6.5 per formula unit. Scanning electron microscopy images revealed the formation of large grains, about 500 μm in diameter, which additionally could be the reason for achieving high total Li-ion conductivity. Electrochemical tests showed that mixed phase LLZ:Al is stable against metallic Li up to 8 V.

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Section: Resultsmentioning

confidence: 72%

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

et al. 2015

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“…In the laboratory frame, an absolute lithium jump rate can be deduced from the maximum condition τ·ω o ≈ 1 which is valid at the maximum relaxation rate. 28 From Figure 5b, it is observed that the maximum SLR rate is reached at 333 K for SSM-Li 6 PS 5 Cl and at 345 K for BMA-Li 6 PS 5 Cl. This corresponds to the same lithium jump frequency (9.80 × 10 8 s –1 ) calculated based on the above-described maximum 1/ T 1 relaxation condition.…”

Section: Resultsmentioning

confidence: 84%

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Ganapathy

Hageman

et al. 2018

ACS Appl. Mater. Interfaces

188

167

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The high Li-ion conductivity of the argyrodite Li6PS5Cl makes it a promising solid electrolyte candidate for all-solid-state Li-ion batteries. For future application, it is essential to identify facile synthesis procedures and to relate the synthesis conditions to the solid electrolyte material performance. Here, a simple optimized synthesis route is investigated that avoids intensive ball milling by direct annealing of the mixed precursors at 550 °C for 10 h, resulting in argyrodite Li6PS5Cl with a high Li-ion conductivity of up to 4.96 × 10–3 S cm–1 at 26.2 °C. Both the temperature-dependent alternating current impedance conductivities and solid-state NMR spin–lattice relaxation rates demonstrate that the Li6PS5Cl prepared under these conditions results in a higher conductivity and Li-ion mobility compared to materials prepared by the traditional mechanical milling route. The origin of the improved conductivity appears to be a combination of the optimal local Cl structure and its homogeneous distribution in the material. All-solid-state cells consisting of an 80Li2S–20LiI cathode, the optimized Li6PS5Cl electrolyte, and an In anode showed a relatively good electrochemical performance with an initial discharge capacity of 662.6 mAh g–1 when a current density of 0.13 mA cm–2 was used, corresponding to a C-rate of approximately C/20. On direct comparison with a solid-state battery using a solid electrolyte prepared by the mechanical milling route, the battery made with the new material exhibits a higher initial discharge capacity and Coulombic efficiency at a higher current density with better cycling stability. Nevertheless, the cycling stability is limited by the electrolyte stability, which is a major concern for these types of solid-state batteries.

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“…7 Li NMR spin-lattice relaxation (SLR) rates R 1 in the laboratory frame of reference were acquired by means of the classical saturation recovery pulse sequence 10 Â p/2 À t d À p/2 À acquisition (acq.) [38][39][40][41][42] The initial ten p/2 pulses in rapid succession are used to destroy any longitudinal magnetization M z . Immediately aer this saturation comb, the recovery of M z is recorded as a function of delay time t d at different temperatures.…”

Section: B Characterization Of Ion Transport and LI Diffusivitymentioning

confidence: 99%

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries

Dunst

Epp

Hanzu

et al. 2014

Energy Environ. Sci.

112

111

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Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Cited by 35 publications

References 31 publications

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries

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Li Ion Dynamics in Al-Doped Garnet-Type Li7La3Zr2O12 Crystallizing with Cubic Symmetry

Cited by 35 publications

References 31 publications

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

High conductivity of mixed phase Al-substituted Li7La3Zr2O12

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li6PS5Cl Solid-State Electrolyte

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li2O2—the discharge product in lithium-air batteries

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Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries