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Title: Scalable Synthesis of Defect Abundant Si Nanorods for High-Performance Li-Ion Battery Anodes

Journal Article · · ACS Nano
 [1];  [1];  [2];  [1];  [1];  [2]
  1. Jiamusi Univ. (China). School of Materials Science and Engineering
  2. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering

Microsized nanostructured silicon–carbon composite is a promising anode material for high energy Li-ion batteries. However, large-scale synthesis of high-performance nano-Si materials at a low cost still remains a significant challenge. Here we report a scalable low cost method to synthesize Al/Na-doped and defect-abundant Si nanorods that have excellent electrochemical performance with high first-cycle Coulombic efficiency (90%). The unique Si nanorods are synthesized by acid etching the refined and rapidly solidified eutectic Al–Si ingot. To maintain the high electronic conductivity, a thin layer of carbon is then coated on the Si nanorods by carbonization of self-polymerized polydopamine (PDA) at 800 °C. The carbon coated Si nanorods (Si@C) electrode at 0.9 mg cm–2 loading (corresponding to area-specific-capacity of ~2.0 mAh cm–2) exhibits a reversible capacity of ~2200 mAh g–1 at 100 mA g–1 current, and maintains ~700 mAh g–1 over 1000 cycles at 1000 mA g–1 with a capacity decay rate of 0.02% per cycle. High Coulombic efficiencies of 87% in the first cycle and ~99.7% after 5 cycles are achieved due to the formation of an artificial Al2O3 solid electrolyte interphase (SEI) on the Si surface, and the low surface area (31 m2 g–1), which has never been reported before for nano-Si anodes. The excellent electrochemical performance results from the massive defects (twins, stacking faults, dislocations) and Al/Na doping in Si nanorods induced by rapid solidification and Na salt modifications; this greatly enhances the robustness of Si from the volume changes and alleviates the mechanical stress/strain of the Si nanorods during the lithium insertion/extraction process. Introducing massive defects and Al/Na doping in eutectic Si nanorods for Li-ion battery anodes is unexplored territory. We venture this uncharted territory to commercialize this nanostructured Si anode for the next generation of Li-ion batteries.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
SC0001160; 31100687
OSTI ID:
1386081
Journal Information:
ACS Nano, Vol. 9, Issue 6; Related Information: NEES partners with University of Maryland (lead); University of California, Irvine; University of Florida; Los Alamos National Laboratory; Sandia National Laboratories; Yale University; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 81 works
Citation information provided by
Web of Science

References (39)

Building better batteries journal February 2008
Mesoporous silicon sponge as an anti-pulverization structure for high-performance lithium-ion battery anodes journal July 2014
Zn4Sb3(C7) powders as a potential anode material for lithium-ion batteries journal February 2001
All-Solid Lithium Electrodes with Mixed-Conductor Matrix journal January 1981
Lithium-ion rechargeable batteries journal August 1994
Failure Modes of Silicon Powder Negative Electrode in Lithium Secondary Batteries journal January 2004
Hydrogen treated, cap-opened Si nanotubes array anode for high power lithium ion battery journal December 2013
A Critical Size of Silicon Nano-Anodes for Lithium Rechargeable Batteries journal March 2010
Surface Binding of Polypyrrole on Porous Silicon Hollow Nanospheres for Li-Ion Battery Anodes with High Structure Stability journal July 2014
Fabrication of Si core/C shell nanofibers and their electrochemical performances as a lithium-ion battery anode journal May 2012
A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes journal February 2014
Micro-sized Si-C Composite with Interconnected Nanoscale Building Blocks as High-Performance Anodes for Practical Application in Lithium-Ion Batteries journal December 2012
Scalable Synthesis of Nano-Silicon from Beach Sand for Long Cycle Life Li-ion Batteries journal July 2014
Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes journal March 2015
Anisotropic Swelling and Fracture of Silicon Nanowires during Lithiation journal August 2011
Reversible Nanopore Formation in Ge Nanowires during Lithiation–Delithiation Cycling: An In Situ Transmission Electron Microscopy Study journal September 2011
Thickness effects on the lithiation of amorphous silicon thin films journal February 2011
In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation journal August 2010
In Situ Measurements of Stress-Potential Coupling in Lithiated Silicon journal January 2010
Strain Anisotropies and Self-Limiting Capacities in Single-Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium-Ion Battery Anodes journal April 2011
Stress Contributions to Solution Thermodynamics in Li-Si Alloys journal January 2012
A high-performance nanoporous Si/Al 2 O 3 foam lithium-ion battery anode fabricated by selective chemical etching of the Al–Si alloy and subsequent thermal oxidation journal January 2015
The nanostructure of the Si–Al eutectic and its use in lithium batteries journal September 2013
An easy way for preparing high performance porous silicon powder by acid etching Al–Si alloy powder for lithium ion battery journal January 2014
Eutectic modification and microstructure development in Al–Si Alloys journal December 2005
Micro-sized nano-porous Si/C anodes for lithium ion batteries journal January 2015
Aluminum doping improves the energetics of lithium, sodium, and magnesium storage in silicon: A first-principles study journal January 2015
Sn–Zr–Ag alloy thin-film anodes journal June 2003
Modification of eutectic silicon in Al–Si alloys journal May 2008
In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures journal May 2012
Dopamine as a Carbon Source: The Controlled Synthesis of Hollow Carbon Spheres and Yolk-Structured Carbon Nanocomposites journal June 2011
Correlation of Raman and photoluminescence spectra of porous silicon journal January 1992
Microporous carbon coated silicon core/shell nanocomposite via in situ polymerization for advanced Li-ion battery anode material journal January 2009
Three-dimensional porous nano-Ni supported silicon composite film for high-performance lithium-ion batteries journal September 2012
Conversion of diatomite to porous Si/C composites as promising anode materials for lithium-ion batteries journal December 2012
Nano-porous Si/C composites for anode material of lithium-ion batteries journal May 2007
Amorphous Carbon-Coated Silicon Nanocomposites:  A Low-Temperature Synthesis via Spray Pyrolysis and Their Application as High-Capacity Anodes for Lithium-Ion Batteries journal July 2007
Electrochemical properties of the carbon-coated LiFePO4 as a cathode material for lithium-ion secondary batteries journal September 2006
Virus-Enabled Silicon Anode for Lithium-Ion Batteries journal August 2010

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A Facile Path to Graphene-Wrapped Polydopamine-Entwined Silicon Nanoparticles with High Electrochemical Performance journal February 2019
Polymer Binders Constructed through Dynamic Noncovalent Bonds for High‐Capacity Silicon‐Based Anodes journal September 2009
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