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Xu, Ming; Park, Min; Lee, Jae-Myung; Kim, Tae Young; Park, Young S.; Ma, Evan

doi:10.1103/physrevb.85.052301

Cited by 154 publications

(103 citation statements)

References 28 publications

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“…[ 13,14,51,52 ] Furthermore, as shown in Table 1 , comparison of the Li-Li bond distances from the results of the structural refi nement of this work reveal decreasing 24d-96h and increasing 96h-96h Li-Li separation distances with increasing Li content. Since the previous NMR reports mentioned above show the 24d site is less mobile than the 96h site, a decreased 24d-96h separation distance would lead to increased coulombic repulsion and destabilization of the ions on the 96h site in the Li sublattice.…”

Section: Resultsmentioning

confidence: 85%

“…In the garnet family of materials, as the Li content is increased from Li = 3 mols toward Li = 7 mols, the ionic conductivity increases by several orders of magnitude. [ 13 ] At Li contents near Li = 6.5 mols, the cubic structure undergoes a reduction of symmetry to a tetragonal polymorph and the ionic conductivity again decreases. [ 14,15 ] A maximum in the ionic conductivity at room temperature has been observed for compositions near the critical Li concentration to stabilize the cubic phase.…”

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confidence: 98%

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A Tale of Two Sites: On Defining the Carrier Concentration in Garnet‐Based Ionic Conductors for Advanced Li Batteries

Thompson

Sharafi

Johannes

et al. 2015

Advanced Energy Materials

153

159

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energy storage. While the primary strategy for improving performance has focused on electrode materials, the development of new solid state ionic conducting electrolytes has been overlooked as a potential means to revolutionize electrochemical energy storage. Examples of some of the technologies ( Figure 1 ) could include: (i) dual electrolyte Li-S batteries, (ii) solidstate batteries employing Li metal anodes, and (iii) all oxide, solid-state Li-ion batteries. Indeed, the need for ionic conducting solid-state electrolytes is clear, but relatively few have been identifi ed as promising candidates. The garnet mineral structure represents a family of complex oxides spanning a broad range of natural and synthetic compositions.Initial work identifi ed Li 5 La 3 M 2 O 12 (M = Nb 5+ , Ta 5+ ) as a promising formulation having a total conductivity of 0.04 mS cm −1 at room temperature. [5][6][7] Recently, Weppner and co-workers discovered a formulation exhibiting up to 0.4 mS cm −1 at room temperature: Li 7 La 3 Zr 2 O 12 (also known as LLZO). [ 8 ] For comparison, conventional battery separators soaked in liquid electrolyte have a total conductivity of 0.4 mS cm −1 at room temperature. [ 9 ] In LLZO, edge-sharing ZrO 6 octahedra and LaO 8 dodecahedra form an isotropic skeleton framework through which Li-ions and Li-ion vacancies form a percolative network of tetrahedral and distorted octahedral sites (Figure 1 ). In addition to high conductivity, LLZO has been reported to have the unprecedented combination of stability against metallic Li, and stability in dry air. [ 8,[10][11][12] LLZO is also referred to as a "stuffed" garnet because of its relatively high Li concentration (7 moles) compared to Li 3 La 3 M 2 O 12 . In the garnet family of materials, as the Li content is increased from Li = 3 mols toward Li = 7 mols, the ionic conductivity increases by several orders of magnitude. [ 13 ] At Li contents near Li = 6.5 mols, the cubic structure undergoes a reduction of symmetry to a tetragonal polymorph and the ionic conductivity again decreases. [ 14,15 ] A maximum in the ionic conductivity at room temperature has been observed for compositions near the critical Li concentration to stabilize the cubic phase. [16][17][18][19] As such, the majority of the work in the literature has focused on understanding how the cubic phase is stabilized at high Li concentrations. [14][15][16][17][18][19][20][21] However, the understanding of the fundamental parameters that control the Li conductivity has Solid electrolytes based on the garnet crystal structure have recently been identifi ed as a promising material to enable advance Li battery cell chemistries because of the unprecedented combination of high ionic conductivity and electrochemical stability against metallic Li. To better understand the mechanisms that give rise to high conductivity, the goal of this work is to correlate Li site occupancy with Li-ion transport. Toward this goal, the Li site occupancy is studied in cubic garnet as a function of Li concentration over the com...

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Section: Resultsmentioning

confidence: 85%

mentioning

confidence: 98%

A Tale of Two Sites: On Defining the Carrier Concentration in Garnet‐Based Ionic Conductors for Advanced Li Batteries

Thompson

Sharafi

Johannes

et al. 2015

Advanced Energy Materials

153

159

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show abstract

“…[27][28][29] Li activation barriers range from 0.1 eV to 0.7 eV for argyrodite-related solid electrolytes. 30 For garnet-type electrolytes, Li hopping barrier has a strong dependence on Li distribution, for instance, 0.26 eV and 0.8 eV for Li 7 31 In this study, Li activation energies are assumed to be 0.45 eV and 0.33 eV in the cathode material and electrolyte, respectively. Nevertheless, the Li reduction-and-transport at the electrolyte-electrode interface is the rate-determining step in the overall electrode reactions due to the high interfacial resistance and the large diffusion barrier for Li through the interface.…”

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confidence: 99%

Mesoscale Analysis of the Electrolyte-Electrode Interface in All-Solid-State Li-Ion Batteries

Feng

Mukherjee

2018

J. Electrochem. Soc.

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Electrolyte-electrode interface plays a critical role in the electrochemical performance of all-solid-state Li-ion batteries. In this work, a mesoscale study is presented to investigate lithium transport and stress in the solid electrolyte based positive electrode during discharge. It is found that increasing electrolyte-electrode interface contact facilitates Li intercalation into the electrode and alleviates the stresses in both the electrode and the electrolyte. Using small electrode particles helps to improve rate capability and avoid interfacial failures due to the volume change of electrode particles. Interface stress strongly depends on the mechanical properties of the two components. In addition, this study demonstrates the importance of electrolyte network through the porous active particle backbone. Li-ion batteries have attracted intensive research interest because of the emerging demand for energy storage devices, and energy density has primarily driven the technological advance of lithium-ion batteries.1,2 Recently, increasing efforts are directed to developing allsolid-state Li-ion batteries, which possess prominent advantages over liquid electrolyte based Li-ion batteries.3-5 Replacing the flammable organic electrolyte with solid electrolyte can improve battery safety by reducing the risk of fire and explosion. For all-solid-state batteries, the mitigation of dendritic growth enables the batteries to use Li metal anode over extended cycling, resulting in high specific capacities and operating voltages. In the literature, various solid electrolytes are used as Li-ion conductors. An electronically insulating electrolyte should have high Liion permeability to enhance Li transport kinetics, as well as the high stiffness to resist the dendritic propagation through electrolyte. The widely investigated electrolytes include polymer polyethylene oxide (PEO), NASICON-type electrolytes, garnet-type electrolytes, and sulfides. [7][8][9] In general, the sulfide electrolytes have high ionic conductivities but low chemical stabilities, which are sensitive to moisture. In contrast, garnet-type electrolytes present the most stable interface with Li metal anodes, which are anticipated to be promising electrolytes to achieve high energy densities. 10Despite the remarkable progress, all-solid-state batteries still face key challenges. Among them, the solid electrolyte-electrode interface is the bottleneck for Li transport. 11,12 The high interfacial resistance between the solid electrolyte and electrode render the charge transfer and Li transport very slow, and thus, it limits the electrochemical performance of all-solid-state Li-ion batteries. Using nuclear magnetic resonance spectroscopy, Yu et al. reported that the electrolyteelectrode Li 6 PS 5 Cl-Li 2 S interface is the dominant factor responsible for the restricted power performance. 13 To improve the interfacial transfer, in addition to interlayer coatings, 14 Sharafi et al. found that the interfacial resistance of Li-Li 7 La 3 Zr 2 O 12 can be dramatically re...

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“…1) [1,6]. Due to partial occupancy of identified Li sites, the diffusion of Li + occurs by a concerted migration mechanism [4,7,8], and the Li content and its distribution among 24d and 48g/96h sites affects the activation energy of the diffusion process [9].…”

Section: Introductionmentioning

confidence: 99%

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

Castillo

Charpentier

Rapaud

et al. 2018

Ceramics International

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Li (7−3x) Al x La 3 Zr 2 O 12 (LLAZO) Al-doped garnets display high ionic conductivity in the range of ~10 -4 S.cm -1 at room temperature and are thus envisioned for future solid-state batteries. In this study, LLAZO powders with two doping levels were synthetized using a solid-state route and sintered using Spark Plasma Sintering (SPS). Both pristine and SPS crushed pellet powders were investigated using X-Ray Diffraction (XRD) confirming the formation of the most conducting cubic phase. Ionic conductivity measurements were performed using electrochemical impedance spectroscopy. Li and Al distributions among available sites were identified using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) experiments, and Li mobility was explored using 7 Li static wideline NMR spectroscopy.Results show that SPS treatment, beyond producing highly densified pellets, mainly modifies Al distribution and strongly impacts the bulk Li + mobility.

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Mechanisms of Li+transport in garnet-type cubic Li3+xLa3

Cited by 154 publications

References 28 publications

A Tale of Two Sites: On Defining the Carrier Concentration in Garnet‐Based Ionic Conductors for Advanced Li Batteries

A Tale of Two Sites: On Defining the Carrier Concentration in Garnet‐Based Ionic Conductors for Advanced Li Batteries

Mesoscale Analysis of the Electrolyte-Electrode Interface in All-Solid-State Li-Ion Batteries

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

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