Ionic Conductivity and Air Stability of Al-Doped Li7La3Zr2O12 Sintered in Alumina and Pt Crucibles

Xia, Wenhao; Xu, Biyi; Duan, Huanan; Guo, Yiping; Kang, Hongzhang; Li, Hua; Liu, Hezhou

doi:10.1021/acsami.5b12186

Cited by 249 publications

(210 citation statements)

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“…Garnet-like solid electrolytes are chemically stable with Li metal and have a high electrochemical window of up to 6 V. [36][37][38][39][40][41][42][43][44][45]67] However, many studies demonstrated that LLZO is unstable in air [68][69][70][71][72] mainly because of water vapor and carbon dioxide, and thus its body integrity and ionic conductivity are considerably affected. A small amount of Li 2 CO 3 forms on the surface of www.advenergymat.de LLZO ceramics and greatly increases interfacial resistance.…”

Section: Chemical Stability Of the Solid Electrolytesmentioning

confidence: 99%

“…[70] As a result, LLZO ceramic with small grain size is often preferred. However, Xia et al [71] refuted the opinion that LLZO pellets sintered in Pt crucible with large grains and reduced grain boundaries improves air stability. Consequently, the particle size should be controlled for air stability and surface treated before using LLZO pellets.…”

Section: Chemical Stability Of the Solid Electrolytesmentioning

confidence: 99%

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Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

Liu

Zhou

2017

Advanced Energy Materials

259

190

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batteries based on intercalation materials cannot meet the demands of long-distance transport (i.e., >300 km).Recently, interest in Li-air [4][5][6] (or Li-O 2 as oxygen is the cathode active component) and Li-S batteries [7][8][9] has increased because of their high theoretical capacities and energy densities, which are suitable for remote transportation. Abraham and Jiang introduced the first rechargeable Li-O 2 battery in 1996, [10] although it drew little interest until Bruce and co-workers proved the rechargeability of Li 2 O 2 . [11] Li-O 2 cells possess significant strength because oxygen gas can be obtained from ambient air. Li-ions react with oxygen according to Equation (1), and Li 2 O 2 is the discharge product with an equilibrium potential of 2.96 V, delivering a large specific energy of 3600 W h kg −1 . Investigations on Li-S cell date back to the 1940s. The insulating nature of sulfur, Li 2 S 2 , and Li 2 S and the solubility of polysulfide intermediates greatly hinder its development. Fortunately, recent studies on new electrolytes and nanostructured material design provide merits and opportunities in developing Li-S batteries. Similar to Li-O 2 batteries, Li-S batteries, which contain inexpensive and abundant sulfur as positive electrode material, produce an average voltage of 2.15 V and possess a theoretical energy density of up to 2600 W h kg −1 , as further indicated by Equation (2). Many studies showed that intermediate polysulfide is produced during the discharge process where Li 2 S is formed as the final product. Typically, Li-O 2 and Li-S batteries both adopt Li metal as anode. The reason is that Li possesses the largest capacity (3860 mA h g −1 ) and the lowest negative electrochemical potential (−3.04 V) versus standard hydrogen electrodes. Thus, Li-O 2 and Li-S batteries are considered to be promising next-generation energy storage systems for PEVs and HEVs However, despite the advantages of Li-O 2 and Li-S batteries, they exhibit ignitability, toxicity, liquid leakage, and volatilization because of their organic liquid electrolyte components. Moreover, Li dendrites form during cycling, resulting in internal short circuit that leads to combustion and even cell explosion. [12,13] More seriously, the charging process in Li-air

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Section: Chemical Stability Of the Solid Electrolytesmentioning

confidence: 99%

Section: Chemical Stability Of the Solid Electrolytesmentioning

confidence: 99%

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

Liu

Zhou

2017

Advanced Energy Materials

259

190

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“…Estimated lattice parameters are in agreement with the literature. 32 To understand the phase purity of the calcined LLZO polycrystalline powders (750 o C for 3 h) and the corresponding sintered LLZO pellet, unpolarized micro-Raman spectroscopic studies were conducted in the wavenumber range from 100 to 550 cm −1 . The results are plotted in Fig.…”

Section: Crystallographic Properties Related To Garnet Phase Puritymentioning

confidence: 99%

“…32 For comparison, the relative density of the pellet was also examined by the conventional Archimedes method and is almost identical to the projected value. Morphological features at fractured surface of the sintered pellet are shown in Fig.…”

Section: Crystallographic Properties Related To Garnet Phase Puritymentioning

confidence: 99%

A novel low-temperature solid-state route for nanostructured cubic garnet Li₇La₃Zr₂O₁₂ and its application to Li-ion battery

et al. 2016

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We present a novel approach to the solid-state synthesis of garnet-type cubic Li7La3Zr2O12 (c-LLZO) nanostructured particles with 1.0 mass% Al at 750 o C within 3 h. In contrast to conventional solid-state processes, a highly reactive precursor was prepared in two steps: (i) by homogenizing the stoichiometric mixture without Li, and (ii) subsequent addition of Li in the form of an ethanolic solution of lithium acetate. The actual composition determined by ICP analysis was Li6.61La3Zr2Al0.13O11.98. Sintering these nanoparticles at 1100 o C for 3 h in air after cold isostatic pressing brought a dense ceramic pellet with a relative density of 90.5%. The corresponding ionic conductivity with Au electrodes was 1.6 × 10 −4 S cm −1 at room temperature. To study its electrochemical behavior as an electrolyte, a model cell of Li//(1M LiPF6 + c-LLZO)//LiCoO2 configuration was constructed. Cyclic voltammetry of the cell delivered one set of redox couple with narrow voltage separation (15 mV) with a Li + diffusion coefficient at room temperature of about 2 × 10 −11 cm 2 s −1 at the interface between LiCoO2 and 1M LiPF6 + c-LLZO. The cell received an average discharge capacity of 64.4, 60.3, 56.1, 51.9 and 46.9µAh cm −2 µm −1 at discharge rates 0.5C, 1C, 2C, 4C and 6C, respectively. The cell exhibited complete oxidation and reduction reactions with an average initial discharge capacity of about 64 µAh cm −2 µm −1 , which is 92.7 % of LiCoO2 theoretical value.These observations indicate the applicability of the present c-LLZO as an electrolyte for a solid-state Li-ion battery. IntroductionA lithium ion battery (LIB) with higher safety and affordability is of utmost importance for better utilization of renewable energy and high-energy electric vehicles. 1,2 Stringent requirements are highenergy density, long cycle life with improved safety, reliability and leakage-free properties in wider operating temperature regimes, enabling a cost-effective process. In current battery technology, we have relatively promising electrode materials in terms of higher energy density and structural stability. On the other hand, we still use flammable, volatile and unstable organic solvents based electrolytes containing Li-salts with polymer separator in all types of conventional Li-ion batteries. These electrolytes not only cause irreversible capacity losses due to the formation of solid-electrolyte interphases (SEI), but also limit the safety of the batteries. Solidstate electrolytes (SSE) with fast Li-ion diffusion were recognized as promising alternative, addressing better thermal and chemical stabilities and opening a wider operational temperature window. 3 For the high-performance SSE, however, great challenges remain, such as: (i) increase in the ionic conductivity and (ii) optimization of fabrication processes. 4 Within the variety of SSE including lithium superionic conductor (LISICON), thio-LISICON or sodium superionic conductor (NASICON), garnet-type c-LLZO is regarded as one of the most promising SSE due to its high ionic conductivity...

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“…48,49 Similarly, reaction with the solvent may produce ionically insulating surface layers, such as carbonates, on particles in solution, complicating subsequent sintering. [50][51][52] The successful sintering of metal oxides to high density requires control of multiple process parameters, and processes must typically be tuned to the specific compound being sintered. 53 Here, factors of importance based on LLZO are highlighted.…”

mentioning

confidence: 99%

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

Kerman

Luntz

Viswanathan

et al. 2017

J. Electrochem. Soc.

586

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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Ionic Conductivity and Air Stability of Al-Doped Li₇La₃Zr₂O₁₂ Sintered in Alumina and Pt Crucibles

Cited by 249 publications

References 43 publications

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

A novel low-temperature solid-state route for nanostructured cubic garnet Li₇La₃Zr₂O₁₂ and its application to Li-ion battery

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

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Ionic Conductivity and Air Stability of Al-Doped Li7La3Zr2O12 Sintered in Alumina and Pt Crucibles

Cited by 249 publications

References 43 publications

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials, Construction, and Challenges

A novel low-temperature solid-state route for nanostructured cubic garnet Li7La3Zr2O12 and its application to Li-ion battery

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

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Product

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Ionic Conductivity and Air Stability of Al-Doped Li₇La₃Zr₂O₁₂ Sintered in Alumina and Pt Crucibles

A novel low-temperature solid-state route for nanostructured cubic garnet Li₇La₃Zr₂O₁₂ and its application to Li-ion battery