A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries

Kim, Sangryun; Oguchi, Hiroyuki; Toyama, Naoki; Sato, Toyoto; Takagi, Shigeyuki; Otomo, Toshiya; Dorai, Arunkumar; Kuwata, Naoaki; Kawamura, Junichi; Orimo, Shin Ichi

doi:10.1038/s41467-019-09061-9

Cited by 272 publications

(286 citation statements)

References 46 publications

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“…Among the various materials reported to date, complex borohydrides are considered outstanding potential candidates for the solid electrolyte in SSBs because of the high Li-or Na-ion conductivity (exceeding 10 −1 S cm −1 ) [12][13][14][15][16][17][18][19][20], which enables a wide range of chemical substitutions and opens up the possibility of searching for even better ion-conductive materials. The general form of metal borohydrides is written as M x (M y H z ), where M can be replaced by alkali or alkaline-earth atoms.…”

Section: Introductionmentioning

confidence: 99%

Reorientational motion and Li+ -ion transport in Li2B12H12 system: M

Ikeshoji

Kim

et al. 2019

Phys. Rev. Materials

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Li 2 B 12 H 12 and its derivatives are promising solid electrolytes for solid-state batteries. In this work, a potential model is proposed, and an extensive classical molecular dynamics study is performed to understand the origin of the fast ion conduction in Li 2 B 12 H 12 . The proposed potential model reveals structural and dynamical properties of Li 2 B 12 H 12 that are consistent with first-principles molecular dynamics simulation and experimental results. The mechanism of Li + -ion transport is studied systematically. The low-temperature α phase exhibits negligible diffusivity within a timescale of a few nanoseconds, whereas the high-temperature β phase with a similar crystal structure and larger lattice parameter exhibits entropy-driven high Li + -ion diffusion assisted by anionic reorientation. We explicitly demonstrate the role of closo-borane anionic reorientational motion in the Li + -ion diffusion and explain how the cell parameter facilitates the anionic reorientational motion. In addition, enhancing the degree of H freedom (by changing the B-B-H angular force parameters) results in significantly high cationic diffusivity at low temperature. Further insight into Li + -ion transport is obtained by constructing a three-dimensional density map and determining the free-energy barrier, and the factors affecting cationic diffusion are thoroughly investigated with high precision using long simulations (5 ns).

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Section: Introductionmentioning

confidence: 99%

Reorientational motion and Li+ -ion transport in Li2B12H12 system: M

Ikeshoji

Kim

et al. 2019

Phys. Rev. Materials

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“…Tremendous attempts have been tried to mitigate uncontrolled lithium dendrites, mainly including: (i) improving the interface properties between electrode and electrolyte; (ii) constructing lithium‐based composites with 3D hosts. To improve the interface properties, various strategies are proposed and explored, including prefabricating artificial SEI films, precoating chemically inert protective layers, inducing additives in the electrolyte to amend SEI films, and even developing solid‐state electrolyte . Meanwhile, comparing to these attempts on stabilizing lithium anode surface, efforts on constructing lithium‐based composites with 3D hosts are superior on the reduction of local current density and bulk effect during cycling.…”

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confidence: 99%

Gradient‐Distributed Nucleation Seeds on Conductive Host for a Dendrite‐Free and High‐Rate Lithium Metal Anode

Yang

Shi

et al. 2019

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Much attention is paid to metal lithium as a hopeful negative material for reversible batteries with a high specific capacity. Although applying 3D hosts can relieve the dendrite growth to some extent, gradient‐distributed lithium ion in 3D uniform hosts still induces uncontrolled lithium dendrites growth, especially at high lithium capacity and high current density. Herein, a 3D conductive carbon nanofiber framework with gradient‐distributed ZnO particles as nucleation seeds (G‐CNF) to regulate lithium deposition is proposed. Based on such a unique structure, the G‐CNF electrode exhibits a high average Coulombic efficiency (CE) of 98.1% for 700 cycles at 0.5 mA cm−2. Even at 5 mA cm−2, the G‐CNF electrode performs a stable cycling process and high CE of 96.0% for over 200 cycles. When the lithium‐deposited G‐CNF (G‐CNF‐Li) anode is applied in a full cell with a commercial LiFePO4 cathode, it exhibits a stable capacity of 115 mAh g−1 and high retention of 95.7% after 300 cycles. Through inducing the gradient‐distributed nucleation seeds to counter the existing Li‐ion concentration polarization, a uniform and stable lithium deposition process in the 3D host is achieved even under the condition of high current density.

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“…We also believe that the overall electrochemical performance of the solid‐state full cell can be further improved by i) using highly Li‐ion conductive Li‐B‐H based electrolyte to enable the stable cycling at room temperature; [ 35–41 ] ii) modifications on the cathode/electrolyte interface to avoid the formation of thick cathode electrolyte interphase film. [ 42–45 ] The above results prove that the SSPP Li‐Al‐H anode is very promising for future practical applications.…”

Section: Resultsmentioning

confidence: 99%

Solid‐State Prelithiation Enables High‐Performance Li‐Al‐H Anode for Solid‐State Batteries

Pang

Wang

Shi

et al. 2020

Advanced Energy Materials

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Lithium alanates exhibit high theoretical specific capacities and appropriate lithiation/delithiation potentials, but suffer from poor reversibility, cycling stability, and rate capability due to their sluggish kinetics and extensive side reactions. Herein, a novel and facile solid‐state prelithiation approach is proposed to in situ prepare a Li3AlH6‐Al nanocomposite from a short‐circuited electrochemical reaction between LiAlH4 and Li with the help of fast electron and Li‐ion conductors (C and P63mc LiBH4). This nanocomposite consists of dispersive Al nanograins and an amorphous Li3AlH6 matrix, which enables superior electrochemical performance in solid‐state cells, as much higher specific capacity (2266 mAh g−1), Coulombic efficiency (88%), cycling stability (71% retention in the 100th cycle), and rate capability (1429 mAh g−1 at 1 A g−1) are achieved. In addition, this nanocomposite works well in the solid‐state full cell with LiCoO2 cathode, demonstrating its promising application prospects. Mechanism analysis reveals that the dispersive Al nanograins and amorphous Li3AlH6 matrix can dramatically enhance the lithiation and delithiation kinetics without side reactions, which is mainly responsible for the excellent overall performance. Moreover, this solid‐state prelithiation approach is general and can also be applied to other Li‐poor electrode materials for further modification of their electrochemical behavior.

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A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries

Cited by 272 publications

References 46 publications

Reorientational motion and Li+ -ion transport in Li2B12H12 system: M

Reorientational motion and Li+ -ion transport in Li2B12H12 system: M

Gradient‐Distributed Nucleation Seeds on Conductive Host for a Dendrite‐Free and High‐Rate Lithium Metal Anode

Solid‐State Prelithiation Enables High‐Performance Li‐Al‐H Anode for Solid‐State Batteries

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