Abstract A vertically aligned carbon nanofiber (VACNF) array with unique conically stacked graphitic structure directly grown on a planar Cu current collector (denoted as VACNF/Cu) is used as a high‐porosity 3D host to overcome the commonly encountered issues of Li metal anodes. The excellent electrical conductivity and highly active lithiophilic graphitic edge sites facilitate homogenous coaxial Li plating/stripping around each VACNF and forming a uniform solid electrolyte interphase. The high specific surface area effectively reduces the local current density and suppresses dendrite growth during the charging/discharging processes. Meanwhile, this open nanoscale vertical 3D structure eliminates the volume changes during Li plating/stripping. As a result, highly reversible Li plating/stripping with high coulombic efficiency is achieved at various current densities. A low voltage hysteresis of 35 mV over 500 h in symmetric cells is achieved at 1 mA cm−2with an areal Li plating capacity of 2 mAh cm−2, which is far superior to the planar Cu current collector. Furthermore, a Li–S battery using a S@PAN cathode and a lithium‐plated VACNF/Cu (VACNF/Cu@Li) anode with slightly higher capacity (2 mAh cm−2) exhibits an excellent rate capability and high cycling stability with no capacity fading over 600 cycles.
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Deciphering the effect of nucleation/growth kinetics on the morphology of Li plating/stripping on vertically aligned carbon nanofibers - A low-tortuosity 3-D nanostructured carbon host
Reversible lithium metal anodes (LMAs) are the holy grail for future rechargeable lithium metal batteries. Threedimensional (3-D) conductive hosts have been extensively explored as an effective approach to suppressing dendrite formation and enabling reversible Li plating/stripping. However, the microscopic morphologies of Li plating and their correlation with the cell performance are not clear. Herein we unravel these issues using the vertically aligned carbon nanofiber (VACNF) array as a model 3-D conductive carbon host which has a welldefined vertical low-tortuosity structure allowing observation of the intrinsic Li morphologies infiltrated into the 3-D host. The VACNF array indeed provides much higher stability and reversibility for Li plating/stripping due to its high surface area and lithiophilic properties. We found that Li plating on both VACNF array and planar Cu electrodes follows the classical nucleation and growth model. Though the low plating current density (≤0.10 mA/cm2) provides better cycling stability consistent with the Sand’s equation, it forms sparse irregular grains stacked with dendrite-like long Li fibers. In contrast, the moderate to high plating current densities (1.0 - 5.0 mA/cm2) produce more uniform Li morphologies consisting of smaller micro-columns or micro-spheres. By decoupling the plating and stripping current densities, we unravel that the more uniform micro-columnar Li infiltrated in the VACNF array obtained at the moderate plating current density (~1.0 mA/cm2) indeed exhibits the highest cycling performance. This provides new insights into the relationship between macroscopic electrochemical tests and microscopic Li morphologies, aiding in optimizing the performance of LMAs based on 3-D conductive hosts.
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- PAR ID:
- 10511123
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Chemical Engineering Journal
- Volume:
- 484
- Issue:
- C
- ISSN:
- 1385-8947
- Page Range / eLocation ID:
- 149515
- Subject(s) / Keyword(s):
- Lithium metal anode 3-D conductive host Microscopic morphology Nucleation-growth theory Vertically aligned carbon nanofibers
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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