Transparent cubic garnet-type solid electrolyte of Al2O3-doped Li7La3Zr2O12

Suzuki, Yosuke; Kami, Kenichiro; Watanabe, Kenji; Watanabe, Akiteru; Saito, Noriko; Ohnishi, T.; Takada, Kazunori; Sudo, R.; Imanishi, Nobuyuki

doi:10.1016/j.ssi.2015.06.009

Cited by 162 publications

(106 citation statements)

References 25 publications

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“…24 And the translucent phenomenon of LLZO is similar to the sample prepared by hot isostatic pressing at high pressure of 127 MPa. 25 It is considered that the addition of 0.6 moles Ta 5+ can promote the sintering and purify the grain boundaries which can improve the grain boundary conductivity. Moreover, since the optimum Li + concentration in the LLZO system is found to be 6.35 ± 0.1 moles, 26,27 the ultra-valence of Ta 5+ ions substituting on Zr 4+ site decreases the lithium ion concentration to 6.4 moles which enhances the grain conductivity.…”

Section: Resultsmentioning

confidence: 99%

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Zhang

Chen

Yang

et al. 2017

J. Electrochem. Soc.

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All-solid-state lithium batteries (ASLBs) have been dramatically attracted recently for its ability of solving the safety issues in traditional lithium ion batteries using liquid electrolyte. However the poor Li + transportation between the active material particles in the cathode greatly deteriorate the specific capacity of ASLBs. Herein, we design a composite cathode composed of polyethylene oxide (PEO) and LiCoO 2 (LCO) in which a three-dimensional (3D) continuous Li + conductive network forms. With the decrease of the LCO: PEO ratio, the 3D Li + conductive network gradually becomes continuous, and the corresponding discharge capacity increase from 50 to 136 mAh g −1 . At LCO: PEO = 6:1 and 4:1, the corresponding ASLBs has a very high discharge capacity of 136 and 124 mAh g −1 , respectively, representing approximately 98% and 90% of the theoretical discharge capacity. The capacity retention after 5 cycles is 97%∼98% of the 2 nd cycle, which confirms stable cycle performance of the battery. The FTIR results show that, in the composite cathode, the LCO particles transport Li + cations by coordinating CO functional group in PEO chains. Compared with other optimized ASLBs based on LLZO solid elctrolyte, our battery has higher specific capacity while being tested under the highest current rate. Recently, the all-solid-state lithium batteries (ASLBs) based on solid electrolyte are receiving significant attention for its safety by the displacement of the volatile and flammable liquid electrolyte.1-4 To develop high performance ASLBs, three critical issues must be considered: (1) get a high lithium ionic conductivity solid electrolyte of 10 −2 ∼10 −3 S cm −1 at room temperature and stability against chemical reaction with lithium anode, (2) lower the interfacial resistance between the electrodes and solid electrolyte, (3) solve the problem of poor Li ionic transportation among active material particles in the cathode. However, the third issue is often overlooked.The garnet-type inorganic oxide lithium ion conductor, nominal Li 7 La 3 Zr 2 O 12 (LLZO), is highly expected to be used as the solid electrolyte to accelerate the development of ASLBs.5-8 Recent reports reveal that doping with elements such as Ga 3+ and Ta 5+ can improve its room temperature conductivity to 0.4∼1.0 × 10 −3 S cm −1 . 9,10The LLZO system is reported to be stable with Li metal anode as well as possessing high electrochemical window (vs Li > 5 v). 11 The wide electrochemical window allows the use of high voltage cathode materials which may result in a potential high specific capacity for ASLBs.So far, the interfacial resistance between the electrodes and solid electrolyte has become the main contributor to the internal resistance of ASLBs, especially the resistance between cathode and solid electrolyte. Electrochemical performance of ASLBs based on LLZO solid electrolyte has been constructed by some groups using various methods aimed at reducing the interfacial resistance.12-15 Tan et al.12 reported a proto-type Li/LLZO/LiCoO 2 (LCO) cell whic...

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Section: Resultsmentioning

confidence: 99%

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Zhang

Chen

Yang

et al. 2017

J. Electrochem. Soc.

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“…Some black spots and cracks were clearly confirmed on the pellet surface. Moreover, some of the cracks penetrated along a thickness direction and reached the opposing pellet surface, indicating that the short circuit locally occurred around these cracks due to the propagation of Li dendrite into SE [33,[47][48][49]. We also observed the microstructures of fractured cross sections of LLZT pellets using SEM and the results are shown in Figure 7.…”

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 89%

“…Together with further examination of the propagation mechanism of Li dendrite into garnet-type SE, both the critical current density at which the short circuit occurs and the threshold in the capacity for Li deposition for stable cycling must be enhanced further to realize a solid-state battery with a garnet-type oxide SE and Li metal anode. We believe that this could be achieved by reducing the interfacial charge-transfer resistance further and by structural improvement of the garnet-type SE by decreasing the porosity [34,47,48], controlling grain size [41,44], and modifying the grain boundary [45,50].…”

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 99%

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

et al. 2018

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Garnet-type Li 7-x La 3 Zr 2-x Ta x O 12 (LLZT) is considered a good candidate for the solid electrolyte in all-solid-state lithium batteries because of its reasonably high conductivity around 10 −3 S cm −1 at room temperature and stability against lithium (Li) metal with the lowest redox potential. In this study, we synthesized LLZT with a tantalum (Ta) content of 0.45 via a conventional solid-state reaction process and constructed a Li/LLZT/Li symmetric cell by attaching Li metal foils on the polished top and bottom surfaces of an LLZT pellet. We investigated the influence of heating temperatures and times on the interfacial charge-transfer resistance between LLZT and the Li metal electrode. In addition, the effect of the interface resistance on the stability for Li deposition and dissolution was examined using a galvanostatic cycling test. The lowest interfacial resistance of 25 Ω cm 2 at room temperature was obtained by heating at 175 • C (5 • C lower than the melting point of Li) for three to five hours. We confirmed that the current density at which the short circuit occurs in the Li/LLZT/Li cell via the propagation of Li dendrite into LLZT increases with decreasing interfacial charge transfer resistance.

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“…Typical batching of 20-50% excess have been reported by teams developing highly dense samples. 33,38,56 Like many other ceramics, the gaseous environment; i.e. oxygen partial pressure, must also be optimized for a given stoichiometry.…”

mentioning

confidence: 99%

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

Kerman

Luntz

Viswanathan

et al. 2017

J. Electrochem. Soc.

589

471

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Solid state electrolyte systems boasting Li + conductivity of >10 mS cm −1 at room temperature have opened the potential for developing a solid state battery with power and energy densities that are competitive with conventional liquid electrolyte systems. The primary focus of this review is twofold. First, differences in Li penetration resistance in solid state systems are discussed, and kinetic limitations of the solid state interface are highlighted. Second, technological challenges associated with processing such systems in relevant form factors are elucidated, and architectures needed for cell level devices in the context of product development are reviewed. Specific research vectors that provide high value to advancing solid state batteries are outlined and discussed. Solid state battery systems are of great interest because of potential benefits in gravimetric and volumetric energy density, operable temperature range, and safety in comparison to traditional liquid electrolyte based systems. However, unresolved fundamental issues remain in the quest to fully understand the behavior of all-solid batteries, especially in the area of electrochemical interfaces.1 There are also a number of significant engineering challenges that require methodical effort to enable a tangible product. Some transitions from academic laboratories to entrepreneurial efforts attempting to overcome these challenges remain unsuccessful in efforts to bring a product to the market.2,3 Vital parameters that require robust understanding from a product development standpoint are material cost, cell lifetime and shelf life, cell energy density on a volumetric and gravimetric basis, operable capabilities for given temperature conditions, and safety. The advantage of energy density remains to be realized in solid state electrolytes (SSEs) since most studies to date utilize thick SSEs or cathodes with low active loading compared to liquid counterparts. 4,5 Furthermore, the desire to use SSEs in conjunction with Li metal anodes requires understanding and managing the morphology of Li metal plating, which can impact volumetric energy density. Operation at both higher and lower temperature compared to conventional technologies is a significant potential advantage of SSE systems. However, reports of solid state cells achieving parity with traditional systems at room temperature or any other temperature do not currently exist. The safety, specifically decreased flammability, of SSE systems is another potential advantage but requires ongoing validation and study.6 Unlike current liquid electrolyte systems, 7 the manufacturability and material component costs of SSEs have not been well characterized, and thus the value of these features will need to be weighed accordingly with any added cost. Operating lifetime of SSEs capturing intrinsic materials parameters such as voltage stability, 8 as well as catastrophic failure modes such as shorting, 9 have been briefly investigated, but in the absence of high energy density electrode formulations and appli...

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Transparent cubic garnet-type solid electrolyte of Al2O3-doped Li7La3Zr2O12

Cited by 162 publications

References 25 publications

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

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Transparent cubic garnet-type solid electrolyte of Al2O3-doped Li7La3Zr2O12

Cited by 162 publications

References 25 publications

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li+Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li+Conductive Network

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

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High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network