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.
more »
« less
Operando Synchrotron Studies of Inhomogeneity during Anode-Free Plating of Li Metal in Pouch Cell Batteries
Operando synchrotron X-ray diffraction (XRD) studies have not previously been used to directly characterize Li metal in standard batteries due to the extremely weak scattering from Li atoms. In this work, it is demonstrated the stripping and plating of Li metal can be effectively quantified during battery cycling in appropriately designed synchrotron XRD experiments that utilize an anode-free battery configuration in which a Li-containing cathode material of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) is paired with a bare anode current collector consisting of either Cu metal (Cu/NMC) or Mo metal (Mo/NMC). In this configuration, it is possible to probe local variations in the deposition and stripping of Li metal with sufficient spatial sensitivity to map the inhomogeneity in pouch cells and to follow these processes with sufficient time resolution to track state-of-charge-dependent variations in the rate of Li usage at a single point. For the Cu/NMC and Mo/NMC batteries, it was observed that the initial plating of Li occurred in a very homogeneous manner but that severe macroscopic inhomogeneity arose on a mm-scale during the subsequent stripping of Li, contrasting with the conventional wisdom that the greatest challenges in Li metal batteries are associated with Li deposition.
more »
« less
- Award ID(s):
- 1922639
- PAR ID:
- 10357992
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 169
- Issue:
- 2
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- 020571
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Lithium metal batteries (LMBs) are considered one of the most promising next-generation rechargeable batteries due to their high specific capacity. However, severe dendrite growth and subsequent formation of dead lithium (Li) during the battery cycling process impede its practical application. Although extensive experimental studies have been conducted to investigate the cycling process, and several theoretical models were developed to simulate the Li dendrite growth, there are limited theoretical studies on the dead Li formation, as well as the entire cycling process. Herein, we developed a phase-field model to simulate both electroplating and stripping process in a bare Li anode and Li anode covered with a protective layer. A step function is introduced in the stripping model to capture the dynamics of dead Li. Our simulation clearly shows the growth of dendrites from a bare Li anode during charging. These dendrites detach from the bulk anode during discharging, forming dead Li. Dendrite growth becomes more severe in subsequent cycles due to enhanced surface roughness of the Li anode, resulting in an increasing amount of dead Li. In addition, it is revealed that dendrites with smaller base diameters detach faster at the base and produce more dead lithium. Meanwhile, the Li anode covered with a protective layer cycles smoothly without forming Li dendrite and dead Li. However, if the protective layer is fractured, Li metal preferentially grows into the crack due to enhanced Li-ion (Li+) flux and forms a dendrite structure after penetration through the protective layer, which accelerates the dead Li formation in the subsequent stripping process. Our work thus provides a fundamental understanding of the mechanism of dead Li formation during the charging/discharging process and sheds light on the importance of the protective layer in the prevention of dead Li in LMBs.more » « less
-
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.more » « less
-
Anode-free lithium-sulfur batteries feature a cell design with a fully-lithiated cathode and a bare current collector as an anode to control the total amount of lithium in the cell. The lithium stripping and deposition is a key factor in designing an anode-free full cell to realize a practical cell configuration. To realize effective anode protection and achieve a good performance of the anode-free full cell, the manipulation of the electrolyte chemistry toward the modification of the solid-electrolyte interphase on the anode is considered a feasible approach. In this study, the use of neodymium triflate, Nd(OTf)3, as a dual-function electrolyte additive is demonstrated to promote homogeneous catalysis on the cathode conversion reactions and the anode stabilization. Nd(OTf)3 not only facilitates the conversion reaction by promoting the polysulfide adsorption, but also effectively protects the lithium-metal anode and stabilizes the lithium stripping and deposition during cycling. With this electrolyte modification, both Li ǁ Li2S half cells and Ni ǁ Li2S anode-free full cells support a high areal capacity of 5.5 – 7.0 mA h cm-2 and maintain a high Coulombic efficiency of 94 – 95% during cycling.more » « less
-
Abstract The development of practical lithium–sulfur (Li–S) batteries with prolonged cycle life and high Coulombic efficiency is limited by both parasitic reactions from dissolved polysulfides and mossy lithium deposition. To address these challenges, here lithium trithiocarbonate (Li2CS3)‐coated lithium sulfide (Li2S) is employed as a dual‐function cathode material to improve the cycling performance of Li–S batteries. Interestingly, at the cathode, Li2CS3forms an oligomer‐structured layer on the surface to suppress polysulfide shuttle. The presence of Li2CS3alters the conventional sulfur reaction pathway, which is supported by material characterization and density functional theory calculation. At the anode, a stable in situ solid electrolyte interphase layer with a lower Li‐ion diffusion barrier is formed on the Li‐metal surface to engender enhanced lithium plating/stripping performance upon cycling. Consequently, the obtained anode‐free full cells with Li2CS3exhibit a superior capacity retention of 51% over 125 cycles, whereas conventional Li2S cells retain only 26%. This study demonstrates that Li2CS3inclusion is an efficient strategy for designing high‐energy‐density Li–S batteries with extended cycle life.more » « less
An official website of the United States government

