Effect of lithium ion concentration on the microstructure evolution and its association with the ionic conductivity of cubic garnet-type nominal Li7Al0.25La3Zr2O12 solid electrolytes

Zhang, Yanhua; Fei, Chen; Tu, Rong; Shen, Qiang; Zhang, Xulong; Zhang, Lianmeng

doi:10.1016/j.ssi.2015.11.014

Cited by 66 publications

(56 citation statements)

References 31 publications

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“…One potential explanation for the decrease in LLCZN bulk conductivity was that samples with different porosities experienced different degrees of Li‐loss. A literature review identified multiple studies where deviating from 6.5 Li ions per formula unit of Li 7 La 3 Zr 2 O 12 (LLZO), either increasing or decreasing, resulted in decreased bulk conductivity 59–63. In particular, Thompson et al measured a 1.0 order of magnitude decrease in bulk conductivity when Li content decreased from 6.5 Li ions to 5.5 Li ions per formula unit of LLZO, similar to the decrease in bulk conductivity observed in this study 61.…”

Section: Resultssupporting

confidence: 79%

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

Hamann

Zhang

Gong

et al. 2020

Adv Funct Materials

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3D focused ion beam tomography is used to analyze the microstructures of Li‐ion conducting Li6.75La2.75Ca0.25Zr1.5Nb0.5O12 (LLCZN) garnet porous electrolytes with different levels of porosity and the theoretical effective bulk conductivities of the electrolyte are calculated based on LLCZN volume fraction, constriction factor, geometric tortuosity, and percolation factor. The experimentally measured effective bulk conductivities are consistently lower than the theoretical values when assuming constant bulk conductivity, suggesting the bulk conductivity of the LLCZN decreased with increasing porosity. This work highlights the importance of understanding the full effects of altering the microstructure of solid‐state electrolytes, as this will play a key role in advancing Li‐ion battery technology to higher energy and power densities.

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Section: Resultssupporting

confidence: 79%

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

Hamann

Zhang

Gong

et al. 2020

Adv Funct Materials

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“…Activation energies (E a ) extracted from Arrhenius plots were E a = 0.46 eV and 0.42 eV for S1-SPS and S2-SPS, respectively, slightly higher than reported values [3,12,15]. …”

Section: Ionic Conductivitycontrasting

confidence: 60%

“…7. In the literature [1,14,15], the two peaks at ~70 ppm and ~82 ppm are attributed to Al 3+ located in the 24d sites and 48g/96h sites in the garnet phase respectively, 48g and 96h being unresolved as they are neighbor sites (see Fig. 1) [10].…”

Section: Microscopic LI Dynamicsmentioning

confidence: 97%

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Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Castillo

Charpentier

Rapaud

et al. 2018

Ceramics International

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Li (7−3x) Al x La 3 Zr 2 O 12 (LLAZO) Al-doped garnets display high ionic conductivity in the range of ~10 -4 S.cm -1 at room temperature and are thus envisioned for future solid-state batteries. In this study, LLAZO powders with two doping levels were synthetized using a solid-state route and sintered using Spark Plasma Sintering (SPS). Both pristine and SPS crushed pellet powders were investigated using X-Ray Diffraction (XRD) confirming the formation of the most conducting cubic phase. Ionic conductivity measurements were performed using electrochemical impedance spectroscopy. Li and Al distributions among available sites were identified using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) experiments, and Li mobility was explored using 7 Li static wideline NMR spectroscopy.Results show that SPS treatment, beyond producing highly densified pellets, mainly modifies Al distribution and strongly impacts the bulk Li + mobility.

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“…The semicircle represents the grain‐boundary impedance, and the long curved tail is arising from the Pt electrode. The equivalent circuit of R uncomp ( R gb CPE gb ) ( R el CPE el ) is adopted to fit the Nyquist plot . The R uncomp and R gb stand for the bulk impedance and the impedance of the grain boundary, respectively.…”

Section: Resultsmentioning

confidence: 99%

Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

et al. 2019

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Bottleneck size is the minimum Li+ migration channel of Li7La3Zr2O12 (LLZO) and it greatly influences the Li+ conductivity. Doping different elements on the Zr site of LLZO can adjust the bottleneck size and improve the Li+ conductivity. However, the regulation mechanism is not clear. In this work, Li6.4La3Zr1.4M0.6O12 (M = Sb, Ta, Nb) has been prepared and the bottleneck size has been adjusted by doping different pentavalent ions. The results manifest that the cell parameter and bottleneck size decrease with the rise of the radius of doped pentavalent ions. This is because larger pentavalent ion leads to larger bond length of M–O, and weaker covalent component between M5+ and O2‐, corresponding, the formal charge on the M5+ become larger, and the bond length of La–O slightly decreases due to the coulomb repulsion between La3+ and M5+ increase. While, the activation energy drop firstly and then rise with the rise of bottleneck size because of the migration of Li+ not only relate to the size of the migration channel but also to the strength of M–O covalent bonding. The bottleneck size and bond length of M–O synergistically affect the migration of Li+.

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Effect of lithium ion concentration on the microstructure evolution and its association with the ionic conductivity of cubic garnet-type nominal Li7Al0.25La3Zr2O12 solid electrolytes

Cited by 66 publications

References 31 publications

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

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Effect of lithium ion concentration on the microstructure evolution and its association with the ionic conductivity of cubic garnet-type nominal Li7Al0.25La3Zr2O12 solid electrolytes

Cited by 66 publications

References 31 publications

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

The Effects of Constriction Factor and Geometric Tortuosity on Li‐Ion Transport in Porous Solid‐State Li‐Ion Electrolytes

Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Dual regulation of Li+ migration of Li6.4La3Zr1.4M0.6O12 (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

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Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O