Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid‐State Lithium Metal Batteries

Abstract

Considerable efforts are devoted to relieve the critical lithium dendritic and volume change problems in the lithium metal anode. Constructing uniform Li + distribution and lithium "host" are shown to be the most promising strategies to drive practical lithium metal anode development. Herein, a uniform Li nucleation/growth behavior in a confined nanospace is verified by constructing vertical graphene on a 3D commercial copper mesh. The difference of solid-electrolyte interphase (SEI) composition and lithium growth behavior in the confined nanospace is further demonstrated by in-depth X-ray photoelectron spectrometer (XPS) and line-scan energy dispersive X-ray spectroscopic (EDS) methods. As a result, a high Columbic efficiency of 97% beyond 250 cycles at a current density of 2 mA cm −2 and a prolonged lifespan of symmetrical cell (500 cycles at 5 mA cm −2 ) can be easily achieved. More meaningfully, the solid-state lithium metal cell paired with the composite lithium anode and LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM) as the cathode also demonstrate reduced polarization and extended cycle. The present confined nanospace-derived hybrid anode can further promote the development of future all solid-state lithium metal batteries.

Advances in the Design of 3D‐Structured Electrode Materials for Lithium‐Metal Anodes

“…Similar but more developed porous 3D GNS structures were incorporated on 3D Ni foam and a 3D Cu mesh using CVD. [128,129] Vertically grown GNS nanowalls on 3D metal substrates provided a more confined nanospace for Li metal and thus significantly improved Li-ion transfer kinetics (Figure 8b), reduced the voltage hysteresis by 30 mV, and allowed for stable cycling during 2000 h in symmetric-cell tests. [128] More importantly, all-solid-state full cells with a 3D GNS-based LMA and a LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode demonstrated significantly reduced polarization and a capacity retention of ≈84% after 50 cycles (Figure 8c).…”

“…[128] More importantly, all-solid-state full cells with a 3D GNS-based LMA and a LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode demonstrated significantly reduced polarization and a capacity retention of ≈84% after 50 cycles (Figure 8c). [129] As a further specific electrode design, Cao et al introduced highly ordered and interconnected mesoporous carbon prepared by a template method, using the Fe 3 O 4 superlattice as a host structure for Li metal storage on a 2D metal substrate. [130] The ordered mesoporous carbon host on metal foil had a high specific surface area of 1198 m 2 g −1 and uniform nanopores (≈9.2 nm in size), which led to homogeneous metal deposition with no dendritic metal growth at a high current density of 3 mA cm −2 and an areal capacity of 3 mAh cm −2 .…”

Hierarchically Nanoporous 3D Assembly Composed of Functionalized Onion‐Like Graphitic Carbon Nanospheres for Anode‐Minimized Li Metal Batteries

“…[13][14][15] Therefore, recent studies revisiting LMAs have focused on mitigating dendritic metal growth and volume expansion through both electrolyte engineering and the state-of-the-art design of catalytic electrode materials using wellknown chemistry. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] Nanoporous carbon materials have attracted considerable attention as a capacitive/pseudocapacitive electrode because of their superior materials properties, such as high specific surface area, good electrical conductivity, and tunable surface properties, as well as nanoscale effects. [24][25][26][27] Along with the characteristics of the unique material, detailed effects on nanopores were recently revealed.…”

Asymmetric Polymer Electrolyte Constructed by Metal–Organic Framework for Solid‐State, Dendrite‐Free Lithium Metal Battery

“…Lithium metal has attracted extensive research attention as a promising anode material for high-performance lithium batteries because of its high theoretical capacity of 3860 mAh g −1 and extremely low redox potential (−3.04 V vs standard hydrogen electrode). [1][2][3][4][5] Meanwhile, lithium metal plays an important role to meet the ever-increasing demands for high energy-density batteries in electronic equipment and electric vehicles. [6] However, the inherent problems of lithium dendrites formation during charging and discharging, and low columbic efficiency of lithium metal seriously impede its application in lithium metal batteries (LMBs).…”