High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X=0–2)

Ohta, Shingo; Kobayashi, Tetsuro; Asaoka, Takahiko

doi:10.1016/j.jpowsour.2010.11.089

Cited by 583 publications

(458 citation statements)

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“…Optimization efforts have focused on obtaining the cubic phase by promoting disorder across the Li sublattice; dopant incorporation is typically employed, targeting the framework cation sites (i.e., La and Zr). Some notable improvements were reported for Te-doped LLZrO (1.02 × 10 −3 S/cm), 15 Tadoped LLZrO (1.0 × 10 −3 S/cm), 16−19 Nb-doped LLZrO (8.0 × 10 −4 S/cm), 20 Sb-doped LLZrO (7.7 × 10 −4 S/cm), 21 and Sr-doped LLZrO (5.0 × 10 −4 S/cm). 22 Simultaneous substitution was also explored in the series Li 7+x−y (La 3−x A x )-(Zr 2−y Nb y )O 12 (where A is an alkali earth metal) and has shown that an optimum lattice parameter at a constant lithium content of 6.5 per formula unit (p.f.u.)…”

Section: ■ Introductionmentioning

confidence: 91%

“…The Ga−Li g(r) plots confirm the presence of inaccessible Li sites around Ga 3+ (see Figure S5a in the Supporting Information); a radius enclosing up to the second NN sites tends to be occupied only with an average of ∼1. 20 Li + ions at any time (cutoff radius: 4.4 Å). For a classical ionic conductor, a conductivity maximum is usually observed, based on eq 4, when vacancies are progressively added.…”

Section: Chemistry Of Materialsmentioning

confidence: 99%

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Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations

et al. 2015

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Garnet-type Li 7 La 3 Zr 2 O 12 (LLZrO) is a candidate solid electrolyte material that is now being intensively optimized for application in commercially competitive solid state Li + ion batteries. In this study we investigate, by forcefield-based simulations, the effects of Ga 3+ doping in LLZrO. We confirm the stabilizing effect of Ga 3+ on the cubic phase. We also determine that Ga 3+ addition does not lead to any appreciable structural distortion. Li site connectivity is not significantly deteriorated by the Ga 3+ addition (>90% connectivity retained up to x = 0.30 in Li 7−3x Ga x La 3 Zr 2 O 12 ). Interestingly, two compositional regions are predicted for bulk Li + ion conductivity in the cubic phase: (i) a decreasing trend for 0 ≤ x ≤ 0.10 and (ii) a relatively flat trend for 0.10 < x ≤ 0.30. This conductivity behavior is explained by combining analyses using percolation theory, van Hove space time correlation, the radial distribution function, and trajectory density. ■ INTRODUCTIONSolid electrolytes with high lithium ionic conductivity are now being actively investigated for application in commercially competitive all-solid-state rechargeable lithium-ion batteries. Among them, Li-based garnet oxides have shown promise for meeting the much needed safety and reliability requirements of today's commercial lithium ion batteries.1−7 One of the garnet compositions being considered is the cubic Li 7 La 3 Zr 2 O 12 (LLZrO), this is due to its stability with elemental lithium and a total conductivity on the order of 10 −4 S/cm. 2 Its structure is usually defined in the Ia3̅ d space group with Li cations partiallly occupying 24d tetrahedral (Td) and 48g/96h octahedral (Oh) sites, La cations fully occupying 24c dodecahedral sites, Zr cations fully occupying 16a octahedral sites, and O anions fully occupying the 96h sites (see Figure 1). However, a more stable tetragonal symmetry (I4 1 /acd) has also been reported to exist at room temperature, with Li ordering in three crystallographic sites: one at the 8a site, which forms a subset of the cubic garnet 24d site, and the other two highly distorted 16f and 32g sites which, when combined, are equivalent to the cubic garnet 48g/96h sites. 8,9 This ordering is responsible for the low bulk Li + ion conductivity measured for tetragonal LLZrO, a value on the order of 1 × 10 −6 S/cm at room tempertaure.

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Section: ■ Introductionmentioning

confidence: 91%

Section: Chemistry Of Materialsmentioning

confidence: 99%

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations

et al. 2015

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“…208 Therefore, substitution of Zr IV by Ta V or Nb V has been used to increase the number of empty interstitial sites and to realize a Li + conductivity of 10 À3 S cm À1 at 25 1C. 207,209 However, samples were commonly fired in an alumina boat, and incorporation of …”

Section: Garnetsmentioning

confidence: 99%

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

et al. 2015

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Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/ opportunities are comprehensively discussed.

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“…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.…”

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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

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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;...

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High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X=0–2)

Cited by 583 publications

References 16 publications

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

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

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High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X=0–2)

Cited by 583 publications

References 16 publications

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li5La3Ta2O12 by ab-Initio Calculations

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li5La3Ta2O12 by ab-Initio Calculations

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

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

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Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations

Insights into the Lithium-Ion Conduction Mechanism of Garnet-Type Cubic Li₅La₃Ta₂O₁₂ by ab-Initio Calculations