Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl–Li2S All-Solid-State Li-Ion Battery

Yu, Chuang; Ganapathy, Swapna; Klerk, Niek J. J. de; Rosłoń, Irek; Eck, Ernst R. H. van; Kentgens, A.P.M.; Wagemaker, Marnix

doi:10.1021/jacs.6b05066

Cited by 211 publications

(240 citation statements)

References 56 publications

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“…9), which probes the lithium-ion hopping through the bulk lattice, resulted in a conductivity of 0.013(1) S cm −1 at 78 °C with an activation energy of 0.10(5) eV, indicating mobility comparable with recently reported NMR results 51 , and a larger bulk conductivity than that resulting from impedance spectroscopy. This may indicate that, like for the analogous Li 6 PS 5 Cl, grain boundaries may be responsible for the lower bulk conductivity measured by impedance spectroscopy 24 .…”

Section: Resultsmentioning

confidence: 89%

“…In addition to the 2D exchange measurements, faster 1D 7 Li– 7 Li exchange experiments under static conditions were performed to quantify the exchange as a function of t mix and temperature 24, 47, 49 . The much larger static spectral width of 7 Li in Li 2 S compared to that of Li 6 PS 5 Br, see Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

“…An additional opportunity provided by solid-state NMR in multi-phase battery materials, either consisting of multiple electrode phases or a mixture of electrode and electrolyte phases, is the possibility to measure the spontaneous lithium-ion exchange between different lithium-containing phases. This provides unique selectivity for charge transfer over phase boundaries 24, 47, 49 , as recently shown to be feasible for the Li 6 PS 5 Cl–Li 2 S solid electrolyte–electrode combination 24 .…”

Section: Introductionmentioning

confidence: 92%

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Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

et al. 2017

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Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode–electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode–electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte–electrode interface design for future all-solid-state batteries.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

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Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

et al. 2017

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“…24,25 To compare the intrinsic Li-ion mobility, temperature-dependent 7 Li spin–lattice relaxation rate (1/ T 1 ) measurements were performed for both BMA-Li 6 PS 5 Cl and SSM-Li 6 PS 5 Cl, the results of which are shown in Figure 5b. The temperature dependence of the 7 Li spin–lattice relaxation (SLR) rates in the laboratory frame can be used to quantify the Li-ion jump frequency and the corresponding energy barrier.…”

Section: Resultsmentioning

confidence: 99%

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Ganapathy

Hageman

et al. 2018

ACS Appl. Mater. Interfaces

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The high Li-ion conductivity of the argyrodite Li6PS5Cl makes it a promising solid electrolyte candidate for all-solid-state Li-ion batteries. For future application, it is essential to identify facile synthesis procedures and to relate the synthesis conditions to the solid electrolyte material performance. Here, a simple optimized synthesis route is investigated that avoids intensive ball milling by direct annealing of the mixed precursors at 550 °C for 10 h, resulting in argyrodite Li6PS5Cl with a high Li-ion conductivity of up to 4.96 × 10–3 S cm–1 at 26.2 °C. Both the temperature-dependent alternating current impedance conductivities and solid-state NMR spin–lattice relaxation rates demonstrate that the Li6PS5Cl prepared under these conditions results in a higher conductivity and Li-ion mobility compared to materials prepared by the traditional mechanical milling route. The origin of the improved conductivity appears to be a combination of the optimal local Cl structure and its homogeneous distribution in the material. All-solid-state cells consisting of an 80Li2S–20LiI cathode, the optimized Li6PS5Cl electrolyte, and an In anode showed a relatively good electrochemical performance with an initial discharge capacity of 662.6 mAh g–1 when a current density of 0.13 mA cm–2 was used, corresponding to a C-rate of approximately C/20. On direct comparison with a solid-state battery using a solid electrolyte prepared by the mechanical milling route, the battery made with the new material exhibits a higher initial discharge capacity and Coulombic efficiency at a higher current density with better cycling stability. Nevertheless, the cycling stability is limited by the electrolyte stability, which is a major concern for these types of solid-state batteries.

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“…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 reduced by controlling surface chemistry, which contributes to good cycling performance. 15 A mechanically robust and stable interface is also of great importance to all-solid-state Li-ion batteries.…”

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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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Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li₆PS₅Cl–Li₂S All-Solid-State Li-Ion Battery

Cited by 211 publications

References 56 publications

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

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

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Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl–Li2S All-Solid-State Li-Ion Battery

Cited by 211 publications

References 56 publications

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li6PS5Cl Solid-State Electrolyte

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

Contact Info

Product

Resources

About

Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li₆PS₅Cl–Li₂S All-Solid-State Li-Ion Battery

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte