Extending the Frontiers of Lithium-Ion Conducting Oxides: Development of Multicomponent Materials with γ-Li<sub>3</sub>PO<sub>4</sub>-Type Structures

Zhao, Guowei; Suzuki, Kota; Okumura, Toyoki; Takeuchi, Tomonari; Hirayama, Masaaki; Kanno, Ryoji

doi:10.1021/acs.chemmater.1c04335

Cited by 21 publications

(16 citation statements)

References 52 publications

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“…Specifically, the 24 g site occupancy was much increased, thereby decreasing the intercage jump distances. A low activation energy seems to be one of the key features of high-entropy Li-ion conductors. , Taken together, the unique charge-transport characteristics of Li 6.5 [P 0.25 Si 0.25 Ge 0.25 Sb 0.25 ]S 5 I result from a combination of favorable (local) structural changes to the Li sublattice and lattice softening because of the presence of various different elements. The material was also tested as a potential SE for use in bulk-type SSBs with a Ni-rich NCM cathode and LTO anode.…”

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confidence: 99%

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

Lin

Cherkashinin

Schäfer

et al. 2022

ACS Materials Lett.

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Bulk-type solid-state batteries (SSBs) constitute a promising next-generation technology for electrochemical energy storage. However, in order for SSBs to become competitive with mature battery technologies, (electro)chemically stable, superionic solid electrolytes are much needed. Multicomponent or high-entropy lithium argyrodites have recently attracted attention for their favorable material characteristics. In the present work, we report on increasing the configurational entropy of the Li 6+a P 1−x M x S 5 I solid electrolyte system and examine how this affects the structureconductivity/stability relationships. Using electrochemical impedance spectroscopy and 7 Li pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy, multicationic substitution is demonstrated to result in a very low activation energy for Li diffusion of ∼0.2 eV and a high room-temperature ionic conductivity of ∼13 mS cm −1 (for Li 6.5 [P 0.25 Si 0.25 Ge 0.25 Sb 0.25 ]S 5 I). The transport properties are rationalized from a structural perspective by means of complementary neutron powder diffraction and magic-angle spinning NMR spectroscopy measurements. The Li 6.5 [P 0.25 Si 0.25 Ge 0.25 Sb 0.25 ]S 5 I solid electrolyte was also tested in high-loading SSB cells with a Ni-rich layered oxide cathode and found by X-ray photoelectron spectroscopy to suffer from interfacial side reactions during cycling. Overall, the results of this study indicate that optimization of conductivity is equally important to optimization of stability, and compositionally complex lithium argyrodites represent a new playground for a rational design of (potentially advanced) superionic solid electrolytes.

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confidence: 99%

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

Lin

Cherkashinin

Schäfer

et al. 2022

ACS Materials Lett.

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“…LISICON-type Li 3.55 (Ge 0.45 Si 0.10 V 0.45 )O 4 (LGSV) powder synthesized by a solid-state reaction method was used to compare with LiGaBr 4 . The synthesis procedure is the same as reported. − The starting materials were Li 2 O, SiO 2 (99.0%, Energy Chemicals Co., Ltd., Shanghai, China), GeO 2 (99.99%, Adamas-beta Reagent, Shanghai, China), and V 2 O 5 (99.0%, Sinopharm Chemical Reagent Co., Ltd., China). The starting materials were weighed in stoichiometric ratios, ground with a mortar and pestle, and then pelletized to pellets (diameter = 10 mm, thickness = 1 mm) at 20–30 MPa in an Ar-filled glovebox (<1 ppm of O 2 , H 2 O).…”

Section: Methodsmentioning

confidence: 99%

High Formability Bromide Solid Electrolyte with Improved Ionic Conductivity for Bulk-Type All-Solid-State Lithium–Metal Batteries

Gao

Fan

Tong

et al. 2022

ACS Appl. Energy Mater.

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Solid electrolytes with excellent formability and high room-temperature Li-ion conductivities used in bulk-type all-solid-state lithium-metal batteries (ASSLBs) are expected to suppress the formation of Li dendrites that affects the application of metal Li anodes with high energy density. However, voids and cracks within sintered electrolytes lead to short-circuiting of ASSLBs due to the formation of Li dendrites. This work aimed to develop solid electrolytes with high formability and high room-temperature Li-ion conductivities that can suppress Li dendrites’ formation in ASSLBs. Three indicators of bulk moduli, lithium-ion migration energies, and energies above the hull were investigated: formability, ionic conductivity, and thermodynamic stability. The 109 inorganic materials containing elements of Li and Br listed in the open web-based database of the Materials Project were surveyed due to their weak Coulombic interaction with Li ions and high polarizability. LiGaBr4 with monoclinic symmetry (LGB, S.G.: P121/a1) was focused on due to its lower values for all three analyzed indicators. A ball milling mechanochemical synthesis method was adopted to synthesize LGB. It indicated that the obtained LGB possessed a monoclinic structure with a lithium ionic conduction of 2.0 × 10–5 S cm–1 (cold isostatic pressed powder) at 25 °C. The ionic conductivity was nearly three times higher than that of the conventional sintered LGB and comparable to that of a typical oxide-type electrolyte of LISICON-type Li3.55(Ge0.45Si0.10V0.45)O4 (LGSV) at 25 °C, which is appealing for applying the sintered samples for Li-metal anodes. The SEM and the distribution of relaxation times (DRT) analysis demonstrated that LGB contributed minimal grain-boundary resistance due to tight connections between the particles, while the LGSV oxides contributed an extremely large grain-boundary resistance. An ASSLB using LGB powder as an electrolyte, bare LiCoO2 as a cathode, and lithium metal as the anode exhibited the ability to function smoothly, while short-circuiting occurred at the second cycle with LGSV, demonstrating that LGB is a pure ionic conductor and may be suitable for use in ASSLB that can prevent Li dendrites with electrochemical stability.

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“…Solid electrolytes are key enabling materials to address the need for safer high-density energy storage, but so far, only a few classes of materials meet the technological requirement of combining a fast ion mobility with electrochemical and structural stability and favorable mechanical properties. This has inspired significant efforts to identify new and optimize known classes of fast-ion conducting oxide, sulfide, or halide ceramics, but the progress is slow partly due to a lack of understanding of the structural requirements for fast ionic conductivity . While sulfide-based solid electrolytes achieve the fastest room temperature conductivities, − there is strong demand to reach these high room temperature conductivities with oxides.…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Structure and Ionic Conductivity of LiTa₂PO₈ Ceramics

et al. 2022

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LiTa2PO8 has recently been reported as a new fast Li-ion conducting structure type within the series of Li x (MO6/2) m (TO4/2) n polyanion oxides. Here, we demonstrate the preparation of LiTa2PO8 by solid-state syntheses, clarify the temperature dependence of lithium distribution and ionic conductivity, and study the structural stability, densification, and achievable total conductivity as a function of sintering conditions synergizing experimental neutron and X-ray powder diffraction and electrochemical studies with computational energy landscape analyses and molecular dynamics simulations. A total room temperature conductivity of 0.7 mS cm–1 with an activation energy of 0.27 eV is achieved after sintering at 1323 K for 10 h. Spark plasma sintering yields high densification >98%, highly reproducible bulk conductivities of 2.8 mS cm–1, in agreement with our bond valence site energy-based pathway predictions, and total conductivities of 0.6 mS cm–1 within minutes. Powder diffraction studies from 3 to 1273 K reveal a reversible flipping of the monoclinic angle from above to below 90° close to room temperature as a consequence of rearrangements of the mobile ions that change the detailed pathway topology. A consistent model of the temperature-dependent Li redistribution, conductivity anisotropy, and transport mechanism is derived from a synopsis of diffraction experiments, experimental conductivity studies, and simulations. Due to the limited electrochemical window of Li x (TaO6/2)2(PO4/2)1 (LTPO), a direct contact with Li metal or high voltage cathode materials leads to degradation, but as demonstrated in this work, semi-solid-state batteries, where LTPO is protected from direct contact with lithium by organic buffer layers, achieve stable cycling.

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Extending the Frontiers of Lithium-Ion Conducting Oxides: Development of Multicomponent Materials with γ-Li₃PO₄-Type Structures

Cited by 21 publications

References 52 publications

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

High Formability Bromide Solid Electrolyte with Improved Ionic Conductivity for Bulk-Type All-Solid-State Lithium–Metal Batteries

Temperature Dependence of Structure and Ionic Conductivity of LiTa₂PO₈ Ceramics

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Extending the Frontiers of Lithium-Ion Conducting Oxides: Development of Multicomponent Materials with γ-Li3PO4-Type Structures

Cited by 21 publications

References 52 publications

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

High Formability Bromide Solid Electrolyte with Improved Ionic Conductivity for Bulk-Type All-Solid-State Lithium–Metal Batteries

Temperature Dependence of Structure and Ionic Conductivity of LiTa2PO8 Ceramics

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Extending the Frontiers of Lithium-Ion Conducting Oxides: Development of Multicomponent Materials with γ-Li₃PO₄-Type Structures

Temperature Dependence of Structure and Ionic Conductivity of LiTa₂PO₈ Ceramics