Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery

Ohta, Shingo; Seki, Juntaro; Yagi, Yusuke; Kihira, Yuki; Tani, Takao; Asaoka, Takahiko

doi:10.1016/j.jpowsour.2014.04.065

Cited by 228 publications

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“…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. Since the ionic radii of Ba 2+ (142 pm) is greater than La 3+ (116 pm), the lattice sizes of LLBZT with fixed Li + concentration per chemical formulae will be changed by the Ba substitution level, which will modify the ionic conducting property.…”

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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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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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“…On the other hand, the reduction of Li3BO3 content leads to the decrease, circa of 10%, of relative density. Higher content of Li3BO3 could create an unfavorable effect producing the drop of the Li-ion conductivity since the Li-ion 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 8 conductivity of Li3BO3 is two orders of magnitude lower than that of the LLZ garnet [15,18] [18,14].…”

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confidence: 99%

“…Li-ion conductivity of Li6.625La3Zr1.625Ta0.375O12 sintered at 1000 °C (24 h) with 29 mol% Al [12] reaches 5 × 10 -4 S/cm. Other compounds used as sintering additives include Li2O, Li3BO3, Li3PO4 and Li4SiO4 [13][14][15][16][17][18]. These materials act as binder between the garnet particles during the sintering treatment by the formation of liquid phases at low temperatures, reducing the grain boundary resistance and improving the Li-ion conductivity pathway.…”

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Optimization of Al2O3 and Li3BO3 Content as Sintering Additives of Li7−x La2.95Ca0.05ZrTaO12 at Low Temperature

Rosero-Navarro

Miura

Higuchi

et al. 2016

Journal of Elec Materi

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Simultaneous effect of Al2O3 and Li3BO3 addition on sintering behavior and Li-ion conductivity of Li7-xLa2.95Ca0.05ZrTaO12 (LLCZT) garnet electrolyte sintered at 900 °C (10 h) is evaluated. Crystal phase and microstructure of the different composites were evaluated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electrical properties of the composites with high relative densities (95 %) were examined by impedance spectroscopy (EIS). Cubic phase was formed for LLCZT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64

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Interfaces in Oxide‐Based Li Metal Batteries*

Balaish

Kim

Wadaguchi

et al. 2022

Transition Metal Oxides for Electrochemical Energy Storage

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Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery

Cited by 228 publications

References 20 publications

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

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

Optimization of Al2O3 and Li3BO3 Content as Sintering Additives of Li7−x La2.95Ca0.05ZrTaO12 at Low Temperature

Interfaces in Oxide‐Based Li Metal Batteries*

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