High Ionic Conductivity Lithium Garnet Oxides of Li7−xLa3Zr2−xTaxO12 Compositions

Wang, Yuxing; Lai, Wei

doi:10.1149/2.024205esl

Cited by 146 publications

(137 citation statements)

References 27 publications

Supporting

Mentioning

127

Contrasting

Order By: Relevance

“…The 12 (0.2¯x¯0.5) samples showed both tetragonal and cubic phases. Additionally, some unknown peaks were detected in the samples with x = 0.2 and 0.3, as shown in Fig.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li7−xLa3Zr2−xTaxO12 (0 ≤ x ≤ 0.6)

Hamao

Kataoka

Kijima

et al. 2016

J. Ceram. Soc. Japan

View full text Add to dashboard Cite

We investigated the phase formation and the conductive properties of the Al-free Li 7¹x La 3 Zr 2¹x Ta x O 12 (0¯x¯0.6) samples. The X-ray diffraction patterns of the Li 7 La 3 Zr 2 O 12 (x = 0) and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (x = 0.6) samples were assigned to be single phases of tetragonal (space group: I4 1 /acd) and cubic (space group: Ia-3d) structures, respectively. On the other hand, the intermediate compositional samples of Li 7¹x La 3 Zr 2¹x Ta x O 12 (0.2¯x¯0.5) showed a coexistence of both the tetragonal and cubic phases. To investigate the conductive property of the prepared samples, the Li-ion conductivity was measured in a temperature range from 253 to 313 K by AC impedance method. All of the Al-free Li 7¹x La 3 Zr 2¹x Ta x O 12 (0¯x¯0.6) samples exhibited relatively high conductivity of ³10 ¹4 S cm ¹1 at room temperature, and the Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (x = 0.5) sample showed the highest Li-ion conductivity of 8.4 © 10 ¹4 S cm ¹1 at room temperature. In order to clarify the relationship between the Li-ion conductivity and the Li-ion arrangement, the crystal structure analysis of Li 7¹x La 3 Zr 2¹x Ta x O 12 (0¯x¯0.6) was performed by Rietveld analysis using powder X-ray diffraction data. The Li(2) atom at 96h site was gradually shifted together with increasing Ta-content from x = 0.2 to 0.5 resulting the shorter LiLi distance in the loop structure of the cubic garnet-type framework structure.

show abstract

“…The 12 (0.2¯x¯0.5) samples showed both tetragonal and cubic phases. Additionally, some unknown peaks were detected in the samples with x = 0.2 and 0.3, as shown in Fig.…”

Section: Methodsmentioning

confidence: 99%

“…9)12) For this reason, the chemical and structural properties of Li 7¹x La 3 Zr 2¹x Ta x O 12 were widely investigated in the literature. However, it is difficult to prepare the high-quality Li 7¹x La 3 Zr 2¹x Ta x O 12 samples because aluminum is easily contaminated from the crucible material during the hightemperature heating.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li7−xLa3Zr2−xTaxO12 (0 ≤ x ≤ 0.6)

Hamao

Kataoka

Kijima

et al. 2016

J. Ceram. Soc. Japan

View full text Add to dashboard Cite

show abstract

“…16 However the Li 7 lower sintering temperature around 950 • C. 16 The synthesis, structural and electrical conductivity of Ta, Nb, Al, Ga, Si, Y substituted cubic phase LLZ have also been reported. [17][18][19][20][21][22][23][24][25][26] Although there are several reports on synthesis, structure and ionic conductivity a detailed investigation on understanding the Li + dynamics through impedance spectroscopy is scarce. For further understanding of the Li + dynamics in lithium garnets and the effect of tungsten (W) substitution on Li + transport properties of LLZ a detailed impedance spectroscopic investigation has been carried out in the present work on Li 7 3 (Sigma -Aldrich, 99 %).…”

Section: Introductionmentioning

confidence: 99%

Li+ transport properties of W substituted Li7La3Zr2O12 cubic lithium garnets

Dhivya

Janani²,

Palanivel³

et al. 2013

AIP Advances

View full text Add to dashboard Cite

Lithium garnet Li7La3Zr2O12 (LLZ) sintered at 1230 °C has received considerable importance in recent times as result of its high total (bulk + grain boundary) ionic conductivity of 5 × 10−4 S cm−1 at room temperature. In this work we report Li+ transport process of Li7−2xLa3Zr2−xWxO12 (x = 0.3, 0.5) cubic lithium garnets. Among the investigated compounds, Li6.4La3Zr1.7W0.3O12 sintered relatively at lower temperature 1100 °C exhibits highest room temperature (30 °C) total (bulk + grain boundary) ionic conductivity of 7.89 × 10−4 S cm−1. The temperature dependencies of the bulk conductivity and relaxation frequency in the bulk are governed by the same activation energy. Scaling the conductivity spectra for both Li6.4La3Zr1.7W0.3O12 and Li6La3Zr1.5W0.5O12 sample at different temperatures merges on a single curve, which implies that the relaxation dynamics of charge carriers is independent of temperature. The shape of the imaginary part of the modulus spectra suggests that the relaxation processes are non-Debye in nature. The present studies supports the prediction of optimum Li+ concentration required for the highest room temperature Li+ conductivity in LixLa3M2O12 is around x = 6.4 ± 0.1

show abstract

“…Partial substitution of the Zr 4+ site in LLZ by other higher valence cations, such as Nb 5+ (Ohta et al, 2011;Kihira et al, 2013), Ta 5+ (Buschmann et al, 2012;Li et al, 2012b;Logéat et al, 2012;Wang and Wei, 2012;Inada et al, 2014a;Thompson et al, 2014Thompson et al, , 2015 Ren et al, 2015a,b), W 6+ (Dhivya et al, 2013;Li et al, 2015), and Mo 6+ (Bottke et al, 2015) is also reported to be effective in stabilizing the cubic garnet phase, and their conductivity at room temperature is greatly enhanced up to ~1 × 10 −3 S cm −1 by controlling the contents of dopants and optimizing Li + concentration in the garnet framework. Although a demonstration of a solidstate battery with Nb-doped LLZ as SE has been already reported (Ohta et al, 2012(Ohta et al, , 2014, it has also been reported that the chemical stability against a Li metal electrode of Ta-doped LLZ is much superior to a Nb-doped one (Nemori et al, 2015 (Thangadurai and Weppner, 2005;Murugan et al, 2007b;Awaka et al, 2009b;Kihira et al, 2013;Thangadurai et al, 2014Thangadurai et al, , 2015.…”

mentioning

confidence: 99%

Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

et al. 2016

View full text Add to dashboard Cite

All-solid-state lithium-ion batteries are expected to be one of the next generations of energy storage devices because of their high energy density, high safety, and excellent cycle stability. Although oxide-based solid electrolyte (SE) materials have rather lower conductivity and poor deformability than sulfide-based ones, they have other advantages, such as their chemical stability and ease of handling. Among the various oxide-based SEs, lithium-stuffed garnet-type oxide, with the formula of Li7La3Zr2O12 (LLZ), has been widely studied because of its high conductivity above 10 −4 S cm −1 at room temperature, excellent thermal performance, and stability against Li metal anode. Here, we present our recent progress for the development of garnet-type SEs with high conductivity by simultaneous substitution of Ta 5+ into the Zr 4+ site and Ba 2+ into the La 3+ site in LLZ. Li + concentration was fixed to 6.5 per chemical formulae, so that the formula of our Li garnet-type oxide is expressed as Li6.5La3−xBaxZr1.5−xTa0.5+xO12 (LLBZT) and Ba contents x are changed from 0 to 0.3. As a result, all LLBZT samples have a cubic garnet structure without containing any secondary phases. The lattice parameters of LLBZT decrease with increasing Ba 2+ contents x ≤ 0.10 while increase with x from 0.10 to 0.30, possibly due to the simultaneous change of Ba 2+ and Ta 5+ substitution levels. The relative densities of LLBZT are in a range between 89 and 93% and are not influenced in any significant way by the compositions. From the AC impedance spectroscopy measurements, the total (bulk + grain) conductivity at 27°C of LLBZT shows its maximum value of 8.34 × 10 −4 S cm −1 at x = 0.10, which is slightly higher than the conductivity (= 7.94 × 10 −4 S cm ) of LLZT without substituting Ba (x = 0). The activation energy of the conductivity tends to become lower by Ba substation, while excess Ba substitution degrades the conductivity in LLBZT. LLBZT has a wide electrochemical potential window of 0-6 V vs. Li + /Li, and Li + insertion and extraction reactions of TiNb2O7 film electrode formed on LLBZT by aerosol deposition are demonstrated at 60°C. The results indicate that LLBZT can potentially be used as a SE in all-solid-state batteries.Keywords: garnet-type oxide, solid electrolyte, ionic conductivity, all-solid-state battery, aerosol deposition inTrODUcTiOn Lithium-ion batteries (LIBs) consist of a graphite negative electrode, organic liquid electrolyte, and lithium transition-metal oxide. They were first commercialized in 1991, and since then such batteries have been widely distributed globally as a power source for mobile electronic devices, such as cell phones and laptop computers. Nowadays, large-scale LIBs have been developed for application to automotive propulsion and stationary loadleveling for intermittent power generation from solar or wind energy (Tarascon and Armand, 2001;Armand and Tarascon, 2008;Scrosati and Garche, 2010;Goodenough and Kim, 2011). However, increasing battery size creates more serious safety issues for LIBs;...

show abstract

High Ionic Conductivity Lithium Garnet Oxides of Li7−xLa3Zr2−xTaxO12 Compositions

Cited by 146 publications

References 27 publications

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7−</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2−</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 0.6)

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7−</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2−</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 0.6)

Li+ transport properties of W substituted Li7La3Zr2O12 cubic lithium garnets

Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

Contact Info

Product

Resources

About

High Ionic Conductivity Lithium Garnet Oxides of Li7−xLa3Zr2−xTaxO12 Compositions

Cited by 146 publications

References 27 publications

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7&minus;</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2&minus;</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 &le; <i>x</i> &le; 0.6)

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7&minus;</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2&minus;</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 &le; <i>x</i> &le; 0.6)

Li+ transport properties of W substituted Li7La3Zr2O12 cubic lithium garnets

Development of Lithium-Stuffed Garnet-Type Oxide Solid Electrolytes with High Ionic Conductivity for Application to All-Solid-State Batteries

Contact Info

Product

Resources

About

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7−</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2−</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 0.6)

Synthesis, crystal structure and conductive properties of garnet-type lithium ion conductor Al-free Li<sub>7−</sub><i><sub>x</sub></i>La<sub>3</sub>Zr<sub>2−</sub><i><sub>x</sub></i>Ta<i><sub>x</sub></i>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 0.6)