The performance of the rechargeable Li metal battery anode is limited by the poor ionic conductivity and poor mechanical properties of its solid-electrolyte interphase (SEI) layer. To overcome this, a 3 : 1 v/v ethyl methyl carbonate (EMC) : fluoroethylene carbonate (FEC) containing 0.8 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 0.2 M lithium difluoro(oxalate)borate (LiDFOB) dual-salts with 0.05 M lithium hexafluorophosphate (LiPF 6 ) was tested to promote the formation of a multitude of SEI-beneficial species. The resulting SEI layer was rich in LiF, Li 2 CO 3 , oligomeric and glass borates, Li 3 N, and Li 2 S, which enhanced its role as a protective yet Li + conductive film, stabilizing the lithium metal anode and minimizing dead lithium build-up. With a stable SEI, a Li/Li[Ni 0.59 Co 0.2 Mn 0.2 Al 0.01 ]O 2 Li-metal battery (LMB) retains 75% of its 177 mA h g −1 specific discharge capacity for 500 hours at a coulombic efficiency of greater than 99.3% at the fast charge–discharge rate of 1.8 mA cm −2 .
more »
« less
Lithium-based vertically aligned nancomposite films incorporating Li x La 0.32 (Nb 0.7 Ti 0.32 )O 3 electrolyte with high Li + ion conductivity
Vertically aligned nanocomposite (VAN) thin films have shown strong potential in oxide nanoionics but are yet to be explored in detail in solid-state battery systems. Their 3D architectures are attractive because they may allow enhancements in capacity, current, and power densities. In addition, owing to their large interfacial surface areas, the VAN could serve as models to study interfaces and solid-electrolyte interphase formation. Here, we have deposited highly crystalline and epitaxial vertically aligned nanocomposite films composed of a Li x La 0.32±0.05 (Nb 0.7±0.1 Ti 0.32±0.05 )O 3±δ -Ti 0.8±0.1 Nb 0.17±0.03 O 2±δ -anatase [herein referred to as LL(Nb, Ti)O-(Ti, Nb)O 2 ] electrolyte/anode system, the first anode VAN battery system reported. This system has an order of magnitude increased Li + ionic conductivity over that in bulk Li 3x La 1/3−x NbO 3 and is comparable with the best available Li 3x La 2/3−x TiO 3 pulsed laser deposition films. Furthermore, the ionic conducting/electrically insulating LL(Nb, Ti)O and electrically conducting (Ti, Nb)O 2 phases are a prerequisite for an interdigitated electrolyte/anode system. This work opens up the possibility of incorporating VAN films into an all solid-state battery, either as electrodes or electrolytes, by the pairing of suitable materials.
more »
« less
- PAR ID:
- 10341595
- Date Published:
- Journal Name:
- APL Materials
- Volume:
- 10
- Issue:
- 5
- ISSN:
- 2166-532X
- Page Range / eLocation ID:
- 051102
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The performance of all‐solid‐state batteries (ASSBs) relies on the Li+transport and stability characteristics of solid electrolytes (SEs). Li3PS4is notable for its stability against lithium metal, yet its ionic conductivity remains a limiting factor. This study leverages local structural disorder via O substitution to achieve an ionic conductivity of 1.38 mS cm−1with an activation energy of 0.34 eV for Li3PS4−xOx(x = 0.31). Optimal O substitution transforms Li+transport from 2D to 3D pathways with increased ion mobility. Li3PS3.69O0.31exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li3PS4. The practical implementation of Li3PS3.69O0.31in ASSBs half‐cells, particularly when coupled with TiS2as the cathode active material, demonstrates substantially enhanced capacity and rate performance. This work elucidates the utility of introducing local structural disorder to ameliorate SE properties and highlights the benefits of strategically combining the inherent strengths of sulfides and oxides via creating oxysulfide SEs.more » « less
-
Self-assembled vertically aligned metal–oxide (Ni–CeO 2 ) nanocomposite thin films with novel multifunctionalities have been successfully deposited by a one-step growth method. The novel nanocomposite structures presents high-density Ni-nanopillars vertically aligned in a CeO 2 matrix. Strong and anisotropic magnetic properties have been demonstrated, with a saturation magnetization ( M s ) of ∼175 emu cm −3 and ∼135 emu cm −3 for out-of-plane and in-plane directions, respectively. Such unique vertically aligned ferromagnetic Ni nanopillars in the CeO 2 matrix have been successfully incorporated in high temperature superconductor YBa 2 Cu 3 O 7 (YBCO) coated conductors as effective magnetic flux pinning centers. The highly anisotropic nanostructures with high density vertical interfaces between the Ni nanopillars and CeO 2 matrix also promote the mixed electrical and ionic conductivities out-of-plane and thus demonstrate great potential as nanocomposite anode materials for solid oxide fuel cells and other potential applications requiring anisotropic ionic transport properties.more » « less
-
Abstract A dual‐layer interphase that consists of an in‐situ‐formed lithium carboxylate organic layer and a thin BF 3 ‐doped monolayer Ti 3 C 2 MXene on Li metal is reported. The honeycomb‐structured organic layer increases the wetting of electrolyte, leading to a thin solid electrolyte interface (SEI). While the BF 3 ‐doped monolayer MXene provides abundant active sites for lithium homogeneous nucleation and growth, resulting in about 50% reduced thickness of inorganic‐rich components among the SEI layer. A low overpotential of less than 30 mV over 1000 h cycling in symmetric cells is received. The functional BF 3 groups, along with the excellent electronic conductivity and smooth surface of the MXene, greatly reduce the lithium plating/stripping energy barrier, enabling a dendrite‐free lithium‐metal anode. The battery with this dual‐layer coated lithium metal as the anode displays greatly improved electrochemical performance. A high capacity‐retention of 175.4 mAh g −1 at 1.0 C is achieved after 350 cycles. In a pouch cell with a capacity of 475 mAh, the battery still exhibits a high discharge capacity of 165.6 mAh g −1 with a capacity retention of 90.2% after 200 cycles. In contrast to the fast capacity decay of pure Li metal, the battery using NCA as the cathode also displays excellent capacity retention in both coin and pouch cells. The dual‐layer modified surface provides an effective approach in stabilizing the Li‐metal anode.more » « less
An official website of the United States government

