Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Castillo, A.G. Chavez; Charpentier, Thibault; Rapaud, Olivier; Pradeilles, Nicolas; Yagoubi, S.; Foy, Eddy; Moskura, Mélanie; Khodja, H.

doi:10.1016/j.ceramint.2018.07.119

Cited by 12 publications

(5 citation statements)

References 29 publications

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“…10,[51][52][53][54][55][56] In this work, we concentrated on designing a tri-functioal modification strategy, by employing Li6.4La3Al0.2Zr2O12 (LLAZO) precursor (Li, Al, La, Zr based salts) to coat LNMO precursor powders followed by calcination at 820 o C to form the coating layer and LNMO material simultaneously. [57][58] In this case, LLAZO coating layer restricts the growth of LNMO precursor particles during crystalization process. 59 Moreover, it is expected that alien ions will diffuse into the lattice of LNMO.…”

Section: Introductionmentioning

confidence: 99%

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Zhao

et al. 2020

Journal of Power Sources

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Instable surface structure and low capacity retention hinder the further application of high voltage LiNi0.5Mn1.5O4 (LNMO) cathode in lithium-ion battery. In order to promote its electrochemical performances, Li6.4La3Al0.2Zr2O12 (LLAZO) with the intrinsic property of fast ion conductivity has been employed as a protective layer to modify surface of LNMO. By regulating the LLAZO contents, 1 wt. % LLAZO coated LNMO (LLAZO-1) cathode shows a high capacity of 92.1 mAh g -1 over 600 cycles with a capacity retention of 72.6 % at 1 C and a reversible capacity of 57.9 mAh g -1 at 20 C, much higher than those of pristine LNMO. Further investigation indicates that the greatly improved electrochemical performances of LLAZO-1 can be attributed to the LLAZO modification, which including the LLAZO surface coating 2 and La 3+ and Zr 4+ gradient co-doping. In addition, the LLAZO precursor significantly restricts the growth of LNMO precursor particles during calcination process, shorting Li + migration pathway. Thus, modification strategy effectively improves the structure stability of LNMO, accompanied with the enhancement in lithium-ion diffusion kinetics performances and confinement in particle growth. This optimization approach with tri-functions sheds light on novel electrode design and construction in rechargeable batteries.

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Section: Introductionmentioning

confidence: 99%

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Zhao

et al. 2020

Journal of Power Sources

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“…Lithium-ion conductivity values of Al-doped solid electrolytes are equal to ~10 −4 S/cm at 25 °C [ 20 , 28 ]. Li 7−3x Al x La 3 Zr 2 O 12 solid electrolytes were obtained by various methods (solid-state reaction, sol–gel, spark plasma sintering, self-consolidation method) and under different final heat-treatment conditions, which have a significant effect on the lithium content in the compound, the stabilization of highly conductive cubic modification, the phase composition and density of ceramic membranes, and, as a result, on the total conductivity of the obtained solid electrolytes [ 20 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 ]. Rangasamy et al [ 36 ] studied the effect of the Li and Al ions concentration on the cubic LLZ formation.…”

Section: Resultsmentioning

confidence: 99%

Recent Strategies for Lithium-Ion Conductivity Improvement in Li7La3Zr2O12 Solid Electrolytes

Il’ina

2023

IJMS

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The development of solid electrolytes with high conductivity is one of the key factors in the creation of new power-generation sources. Lithium-ion solid electrolytes based on Li7La3Zr2O12 (LLZ) with a garnet structure are in great demand for all-solid-state battery production. Li7La3Zr2O12 has two structural modifications: tetragonal (I41/acd) and cubic (Ia3d). A doping strategy is proposed for the stabilization of highly conductive cubic Li7La3Zr2O12. The structure features, density, and microstructure of the ceramic membrane are caused by the doping strategy and synthesis method of the solid electrolyte. The influence of different dopants on the stabilization of the cubic phase and conductivity improvement of solid electrolytes based on Li7La3Zr2O12 is discussed in the presented review. For mono-doping, the highest values of lithium-ion conductivity (~10−3 S/cm at room temperature) are achieved for solid electrolytes with the partial substitution of Li+ by Ga3+, and Zr4+ by Te6+. Moreover, the positive effect of double elements doping on the Zr site in Li7La3Zr2O12 is established. There is an increase in the popularity of dual- and multi-doping on several Li7La3Zr2O12 sublattices. Such a strategy leads not only to lithium-ion conductivity improvement but also to the reduction of annealing temperature and the amount of some high-cost dopant. Al and Ga proved to be effective co-doping elements for the simultaneous substitution in Li/Zr and Li/La sublattices of Li7La3Zr2O12 for improving the lithium-ion conductivity of solid electrolytes.

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“…Castillo et al studied Li and Al distribution behaviors and Li mobility in Al-doped LLZO after SPS treatment. [232] The results indicated that SPS treatment caused a redistribution of Al ions into Li sublattice, which resulted in enhancement of Li mobility and consequently higher bulk conductivity. [233] Despite the abovementioned advantages, impurity phase, such as La 2 Zr 2 O 7 , is easily produced if the powder preparation process is not well controlled.…”

Section: Advanced Sintering Techniques and Other Methodsmentioning

confidence: 94%

“…studied Li and Al distribution behaviors and Li mobility in Al‐doped LLZO after SPS treatment. [ 232 ] The results indicated that SPS treatment caused a redistribution of Al ions into Li sublattice, which resulted in enhancement of Li mobility and consequently higher bulk conductivity. [ 233 ]…”

Section: Processing Llzo Ceramicsmentioning

confidence: 99%

Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes

Chen

Wang

et al. 2022

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the limited electrochemical window of liquid organic electrolytes, high-voltage cathode materials and Li metal cannot be incorporated in current battery chemistry, thus making it challenge to further improve the energy density. Moreover, the flammability of liquid electrolytes also poses serious safety concerns of LIBs. Under such context, solid-state battery (SSB) using solid state electrolytes (SSEs) have attracted much attention. SSEs are typically nonflammable with wide electrochemical window and high mechanical strength. These merits allow to employ high-voltage cathodes and the "holy-grail" Li metal anode (≈3860 mAh g −1 ), offering drastic improvements in energy density and safety performance. Owing to these promises, SSB has been intensively studies in recent years.Developing a suitable solid electrolyte is critical to realize SSB technology. Substantial efforts have been made on developing various SSE systems, including NASICON (Na Super Ion Conductor)-type, perovskite-type, Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO), sulfide-based, polymer electrolytes, and composite electrolytes. Among these materials, LLZO possesses high ionic (10 −4 -10 −3 S cm −1 ) and low electronic (σ e < 10 −8 S cm −1 ) conductivities at room temperature, [2,3] good mechanical strength, and good electrochemical stability. As such, it has received tremendous attention since its discovery in 2007. [3] Numerous experimental and computational studies have been conducted over the past decades. LLZO-based SSBs have also been demonstrated through various interface engineering strategies.Various formats of LLZO electrolyte have been studied so far. Based on the properties and processing routes, they can be in general categorized into three types, ceramic bulk/tape-based, thin film-based, and single crystal-based electrolytes (Figure 1 and Table 1). Among them, thin film LLZO processing faces the difficulties of Li loss and impurity phase formation during deposition and annealing (Figure 1a). Successful preparation of dense, uniform, and single phase LLZO films is rarely demonstrated. The reported conductivities of thin film LLZO in most studies are between 10 −8 and 10 −4 S cm −1 , which is far behind its ceramic counterpart. In addition, due to geometric limit (≈µm), the capacity of thin film batteries is low, making them only applicable to microelectronic devices. Single crystal growth also faces many processing-related difficulties (Figure 1b). The LLZO single crystal is mostly for the purposes of mechanistic study in LLZO crystal chemistry, which can be investigated without the interference from microstructural defects. [5] From Garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) is widely considered as one of the most promising candidates for solid state batteries (SSBs) owing to its high ionic conductivity and good electrochemical stability. Since its discovery in 2007, great progress has been made in terms of crystal chemistry, chemical and electrochemical properties, and battery application. Nonetheless, reliable and controll...

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Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Cited by 12 publications

References 29 publications

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Recent Strategies for Lithium-Ion Conductivity Improvement in Li7La3Zr2O12 Solid Electrolytes

Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes

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Bulk Li mobility enhancement in Spark Plasma Sintered Li(7−3x)AlxLa3Zr2O12 garnet

Cited by 12 publications

References 29 publications

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Constructing tri-functional modification for spinel LiNi0.5Mn1.5O4 via fast ion conductor

Recent Strategies for Lithium-Ion Conductivity Improvement in Li7La3Zr2O12 Solid Electrolytes

Processing and Properties of Garnet‐Type Li7La3Zr2O12 Ceramic Electrolytes

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Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes