Porous Si/Cu Anode with High Initial Coulombic Efficiency and Volumetric Capacity by Comprehensive Utilization of Laser Additive Manufacturing-Chemical Dealloying

Abstract

Si has been extensively investigated as an anode material for lithium-ion batteries because of its superior theoretical capacity. However, a scalable fabrication method for a Si-based anode with high initial coulombic efficiency (ICE) and large volumetric capacity remains a critical challenge. Herein, we proposed a novel porous Si/Cu anode in which planar Si islands were embedded in the porous Cu matrix through combined laser additive manufacturing and chemical dealloying. The compositions and dimensions of the structure were controlled by metallurgical and chemical reactions during comprehensive interaction. Such a structure has the advantages of micro-sized Si and porous architecture. The planar Si islands decreased the surface area and thus increased ICE. The porous Cu matrix, which acted as both an adhesive-free binder and a conductive network, provided enough access for electrolyte and accommodated volume expansion. The anode structure was well maintained without observable mechanical damage after cycling, demonstrating the high structure stability and integrity. The porous Si/Cu anode showed a high ICE of 93.4% and an initial volumetric capacity of 2131 mAh cm–3, which retained 1697 mAh cm–3 after 100 cycles at 0.20 mA cm–2. Furthermore, the full-cell configuration (porous Si/Cu //LiFePO4) exhibited a high energy density of 464.9 Wh kg–1 and a capacity retention of 84.2% after 100 cycles.

Theoretical study on stability and ion transport property with halide doping of Na3SbS4 electrolyte for all-solid-state batteries

“…To address this issue on volume change, porous morphology structures or porous supports have been tested. 89 Meanwhile, to stop dendrite initiation at the Na metal anode surface, the electrodeposition stability map in Fig. 4b suggests two ways to achieve density-driven stability ( i.e.…”

“…To address this issue on volume change, porous morphology structures or porous supports have been tested. 89 Meanwhile, to stop dendrite initiation at the Na metal anode surface, the electrodeposition stability map in Fig. 4b suggests two ways to achieve densitydriven stability (i.e., region (i)): (i) make Na in the SE compound more densely packed than Na in the Na metal anode or (ii) appropriately pair the SE compound with an anode with lower effective molar volume for Na atom (e.g., alloy).…”

Revisiting the Preparation Progress of Nano‐Structured Si Anodes toward Industrial Application from the Perspective of Cost and Scalability

“…The four types of nanostructured Si and their preparation methods are summarized in Figure 1 . [ 71–75 ] The fabrication methods of 0D nanoparticles mainly include: Ball milling method, [ 76–78 ] plasma enhanced chemical vapor deposition (PECVD) technology, laser‐induced chemical vapor deposition (LICVD) technology, [ 79 ] radio frequency thermal plasma (RFTP) technology, [ 80–82 ] and solution synthesis method; [ 83–86 ] the fabrication processes of 1D nanowires and nanotubes mainly include: Vapor deposition method, [ 87–91 ] chemical etching method, [ 92,93 ] molten salt electrolysis (MSE) [ 94–97 ] and template method; [ 98,99 ] 2D thin‐films are mainly prepared by vapor deposition technology, [ 100,101 ] and magnetron sputtering technology; [ 102 ] 3D porous structure is the hot spot of research, and the synthesis routes mainly include: de‐alloying method for Si metal alloy, [ 103–108 ] magnesium thermal reduction method, [ 109 ] chemical etching, [ 110–112 ] magnesium evaporation method, [ 113,114 ] etc. In addition to these main methods above, there are some infrequent methods such as SiHCl 3 reduction method, [ 115,116 ] laser burning method, [ 117 ] electrostatic spinning, [ 118 ] and so on.…”

Silicon‐Based Lithium Ion Battery Systems: State‐of‐the‐Art from Half and Full Cell Viewpoint

“…Specifically, after carefully evaluating the best results of Si‐based materials in half and full cells reported so far in literature, [ 92–95 ] their prospects can be summarized as follows: I) Si materials with bulk, [ 96–99 ] core–shell, [ 100–106 ] porous, [ 107–111 ] sandwich, [ 112–114 ] and nanowire [ 115–118 ] structures are synthesized through a variety of strategies, such as magnesiothermic reduction, solvothermal, chemical vapor deposition (CVD), and polymerization. In addition to superior half cell performance, their full cells with conventional LFP and LCO cathodes, high capacity NCM and LiNi x Co y Al z O 2 (NCA, x + y + z = 1) cathodes, as well as high voltage LiNi 0.5 Mn 1.5 O 4 (LMNO) cathodes have also been developed to balance their cost, energy densities, and lifetime.…”