Research Papers

Freestanding Flexible Si Nanoparticles–Multiwalled Carbon Nanotubes Composite Anodes for Li-Ion Batteries and Their Prelithiation by Stabilized Li Metal Powder

[+] Author and Article Information
K. Yao

Materials Science and Engineering,
Florida State University,
Tallahassee, FL 32310;
Aero-Propulsion, Mechatronics and Energy
Center (AME),
Florida State University,
Tallahassee, FL 32310;
High-Performance Materials Institute (HPMI),
Florida State University,
Tallahassee, FL 32310

R. Liang

High-Performance Materials Institute (HPMI),
Florida State University,
Tallahassee, FL 32310;
Department of Industrial and Manufacturing
Florida A&M University—Florida State
University College of Engineering,
Tallahassee, FL 32310

J. P. Zheng

Aero-Propulsion, Mechatronics and Energy
Center (AME),
Florida State University,
Tallahassee, FL 32310;
Department of Electrical and Computer
Florida A&M University—Florida State University
College of Engineering,
Tallahassee, FL 32310
e-mail: zheng@eng.fsu.edu

Manuscript received December 23, 2015; final manuscript received March 20, 2016; published online xxxx x, xxxx. Assoc. Editor: Partha Mukherjee.

J. Electrochem. En. Conv. Stor. 13(1), 011004 (Apr 19, 2016) (6 pages) Paper No: JEECS-15-1026; doi: 10.1115/1.4033180 History: Received December 23, 2015; Revised March 20, 2016

Freestanding flexible Si nanoparticles–multiwalled carbon nanotubes (SiNPs–MWNTs) composite paper anodes for Li-ion batteries (LIBs) have been prepared using a combination of ultrasonication and pressure filtration. No conductive additive, binder, or metal current collector is used. The SiNPs–MWNTs composite electrode material achieves first cycle specific discharge and charge capacities of 2298 and 1492 mAh/g, respectively. To address the first cycle irreversibility, stabilized Li metal powder (SLMP) has been utilized to prelithiate the composite anodes. As a result, the first cycle irreversible capacity loss is reduced from 806 to 28 mAh/g and the first cycle coulombic efficiency is increased from 65% to 98%. The relationship between different SLMP loadings and cell performance has been established to understand the prelithiation process of SLMP and to optimize the construction of Si-based cells. A cell containing the prelithiated anode is able to deliver charge capacity over 800 mAh/g without undergoing the initial discharge process, which enables the exploration of novel cathode materials.

Copyright © 2016 by ASME
Your Session has timed out. Please sign back in to continue.


Szczech, J. R. , and Jin, S. , 2011, “ Nanostructured Silicon for High Capacity Lithium Battery Anodes,” Energy Environ. Sci., 4(1), pp. 56–72. [CrossRef]
Wu, H. , and Cui, Y. , 2012, “ Designing Nanostructured Si Anodes for High Energy Lithium Ion Batteries,” Nano Today, 7(5), pp. 414–429. [CrossRef]
Chan, C. K. , Patel, R. N. , O'Connell, M. J. , Korgel, B A. , and Cui, Y. , 2010, “ Solution-Grown Silicon Nanowires for Lithium-Ion Battery Anodes,” ACS Nano, 4(3), pp. 1443–1450. [CrossRef] [PubMed]
Hanrath, T. , and Korgel, B. A. , 2003, “ Supercritical Fluid-Liquid-Solid (SFLS) Synthesis of Si and Ge Nanowires Seeded by Colloidal Metal Nanocrystals,” Adv. Mater., 15(5), pp. 437–440. [CrossRef]
Liu, N. , Hu, L. B. , McDowell, M. T. , Jackson, A. , and Cui, Y. , 2011, “ Prelithiated Silicon Nanowires as an Anode for Lithium Ion Batteries,” ACS Nano, 5(8), pp. 6487–6493. [CrossRef] [PubMed]
Chan, C. K. , Peng, H. L. , Liu, G. , McIlwrath, K. , Zhang, X. F. , Huggins, R. A. , and Cui, Y. , 2008, “ High-Performance Lithium Battery Anodes Using Silicon Nanowires,” Nat. Nanotechnol., 3(1), pp. 31–35 [CrossRef] [PubMed]
Ge, M. Y. , Rong, J. P. , Fang, X. , and Zhou, C. , 2012, “ Porous Doped Silicon Nanowires for Lithium Ion Battery Anode With Long Cycle Life,” Nano Lett., 12(5), pp. 2318–2323. [CrossRef] [PubMed]
Rong, J. P. , Fang, X. , Ge, M. Y. , Chen, H. , Xu, J. , and Zhou, C. , 2013, “ Coaxial Si/Anodic Titanium Oxide/Si Nanotube Arrays for Lithium-Ion Battery Anodes,” Nano Res., 6(3), pp. 182–190. [CrossRef]
Wu, H. , Chan, G. , Choi, J. W. , Ryu, I. , Yao, Y. , McDowell, M. T. , Lee, S. W. , Jackson, A. , Yang, Y. , Hu, L. , and Cui, Y. , 2012, “ Stable Cycling of Double-Walled Silicon Nanotube Battery Anodes Through Solid-Electrolyte Interphase Control,” Nat. Nanotechnol., 7(5), pp. 310–315. [CrossRef] [PubMed]
Ge, M. Y. , Rong, J. P. , Fang, X. , Zhang, A. , Lu, Y. , and Zhou, C. , 2013, “ Scalable Preparation of Porous Silicon Nanoparticles and Their Application for Lithium-Ion Battery Anodes,” Nano Res., 6(3), pp. 174–181. [CrossRef]
Liu, X. H. , Zhong, L. , Huang, S. , Mao, S. X. , Zhu, T. , and Huang, J. Y. , 2012, “ Size-Dependent Fracture of Silicon Nanoparticles During Lithiation,” ACS Nano, 6(2), pp. 1522–1531. [CrossRef] [PubMed]
Iwamura, S. , Nishihara, H. , and Kyotani, T. , 2013, “ Fast and Reversible Lithium Storage in a Wrinkled Structure Formed From Si Nanoparticles During Lithiation/Delithiation Cycling,” J. Power Sources, 222, pp. 400–409. [CrossRef]
Lee, J. K. , Smith, K. B. , Hayner, C. M. , and Kung, H. H. , 2010, “ Silicon Nanoparticles-Graphene Paper Composites for Li Ion Battery Anodes,” Chem. Commun., 46(12), pp. 2025–2027. [CrossRef]
Magasinski, A. , Dixon, P. , Hertzberg, B. , Kvit, A. , Ayala, J. , and Yushin, G. , 2010, “ High-Performance Lithium-Ion Anodes Using a Hierarchical Bottom-Up Approach,” Nat. Mater., 9(4), pp. 353–358. [CrossRef] [PubMed]
Wang, W. , and Kumta, P. N. , 2007, “ Reversible High Capacity Nanocomposite Anodes of Si/C/SWNTs for Rechargeable Li-Ion Batteries,” J. Power Sources, 172(2), pp. 650–658. [CrossRef]
Sun, W. , Hu, R. , Liu, H. , Zeng, M. , Yang, L. , Wang, H. , and Zhu, M. , 2014, “ Embedding Nano-Silicon in Graphene Nanosheets by Plasma Assisted Milling for High Capacity Anode Materials in Lithium Ion Batteries,” J. Power Sources, 268, pp. 610–618. [CrossRef]
Cui, L. F. , Hu, L. B. , Choi, J. W. , and Cui, Y. , 2010, “ Light-Weight Free-Standing Carbon Nanotube-Silicon Films for Anodes of Lithium Ion Batteries,” ACS Nano, 4(7), pp. 3671–3678. [CrossRef] [PubMed]
Forney, M. W. , DiLeo, R. A. , Raisanen, A. , Ganter, M. J. , Staub, J. W. , Rogers, R. E. , Ridgley, R. D. , and Landi, B. J. , 2013, “ High Performance Silicon Free-Standing Anodes Fabricated by Low-Pressure and Plasma-Enhanced Chemical Vapor Deposition Onto Carbon Nanotube Electrodes,” J. Power Sources, 228, pp. 270–280. [CrossRef]
Wang, W. , and Kumta, P. N. , 2010, “ Nanostructured Hybrid Silicon/Carbon Nanotube Heterostructures: Reversible High-Capacity Lithium-Ion Anodes,” ACS Nano, 4(4), pp. 2233–2241. [CrossRef] [PubMed]
Chou, S. L. , Zhao, Y. , Wang, J. Z. , Chen, Z.-X. , Liu, H.-K. , and Dou, S.-H. , 2010, “ Silicon/Single-Walled Carbon Nanotube Composite Paper as a Flexible Anode Material for Lithium Ion Batteries,” J. Phys. Chem. C, 114(37), pp. 15862–15867. [CrossRef]
Park, K. S. , Min, K. M. , Seo, S. D. , Lee, G.-H. , Shim, H.-W. , and Kim, D.-W. , 2013, “ Self-Supported Multi-Walled Carbon Nanotube-Embedded Silicon Nanoparticle Films for Anodes of Li-Ion Batteries,” Mater. Res. Bull., 48(4), pp. 1732–1736. [CrossRef]
Smithyman, J. , Moench, A. , Liang, R. , Zheng, J. P. , Wang, B. , and Zhang, C. , 2012, “ Binder-Free Composite Electrodes Using Carbon Nanotube Networks as a Host Matrix for Activated Carbon Microparticles,” Appl. Phys. A, 107(3), pp. 723–731. [CrossRef]
Jarvis, C. R. , Lain, M. J. , Yakovleva, M. V. , and Gao, Y. , 2006, “ A Prelithiated Carbon Anode for Lithium-Ion Battery Applications,” J. Power Sources, 162(2), pp. 800–802. [CrossRef]
Jarvis, C. R. , Lain, M. J. , Gao, Y. , and Yakovleva, M. V. , 2005, “ A Lithium Ion Cell Containing a Non-Lithiated Cathode,” J. Power Sources, 146(1–2), pp. 331–334. [CrossRef]
Li, Y. , and Fitch, B. , 2011, “ Effective Enhancement of Lithium-Ion Battery Performance Using SLMP,” Electrochem. Commun., 13(7), pp. 664–667. [CrossRef]
Wang, Z. H. , Fu, Y. B. , Zhang, Z. C. , Yuan, S. , Amine, K. , Battaglia, V. , and Liu, G. , 2014, “ Application of Stabilized Lithium Metal Powder (SLMP®) in Graphite Anode—A High Efficient Prelithiation Method for Lithium-Ion Batteries,” J. Power Sources, 260, pp. 57–61. [CrossRef]
Cao, W. J. , and Zheng, J. P. , 2012, “ Li-Ion Capacitors With Carbon Cathode and Hard Carbon/Stabilized Lithium Metal Powder Anode Electrodes,” J. Power Sources, 213, pp. 180–185. [CrossRef]
Cao, W. J. , and Zheng, J. P. , 2013, “ The Effect of Cathode and Anode Potentials on the Cycling Performance of Li-Ion Capacitors,” J. Electrochem. Soc., 160(9), pp. 1572–1576. [CrossRef]
Cao, W. J. , Shih, J. , Zheng, J. P. , and Doung, T. , 2014, “ Development and Characterization of Li-Ion Capacitor Pouch Cells,” J. Power Sources, 257, pp. 388–393. [CrossRef]
Cao, W. , Li, Y. , Fitch, B. , Shih, J. , Doung, T. , and Zheng, J. , 2014, “ Strategies to Optimize Lithium-Ion Supercapacitors Achieving High-Performance: Cathode Configurations, Lithium Loadings on Anode, and Types of Separator,” J. Power Sources, 268, pp. 841–847. [CrossRef]
Forney, M. W. , Ganter, M. J. , Staub, J. W. , Ridgley, R. D. , and Landi, B. J. , 2013, “ Prelithiation of Silicon-Carbon Nanotube Anodes for Lithium Ion Batteries by Stabilized Lithium Metal Powder (SLMP),” Nano Lett., 13(9), pp. 4158–4163. [CrossRef] [PubMed]
Chew, S. Y. , Ng, S. H. , Wang, J. Z. , Novak, P. , Krumeich, F. , Chou, S. L. , Chen, J. , and Liu, H. K. , 2009, “ Flexible Free-Standing Carbon Nanotube Films for Model Lithium-Ion Batteries,” Carbon, 47(13), pp. 2976–2983. [CrossRef]


Grahic Jump Location
Fig. 1

(a) A freestanding SiNPs–MWCNTs composite paper demonstrating its flexibility, (b) half-inch composite paper electrode, and (c) the electrode in (b) with SLMP pressed onto the surface

Grahic Jump Location
Fig. 2

(a) Cross-sectional and (b) top-view SEM images of SiNPs–MWCNTs composite paper

Grahic Jump Location
Fig. 3

Voltage profiles from first and second cycles of SiNPs–MWCNTs anode

Grahic Jump Location
Fig. 4

Representative first cycle voltage profile of SLMP-prelithiated composite paper anode

Grahic Jump Location
Fig. 5

(a) Open circuit potential, (b) first cycle charge/discharge capacity ratio, and (c) first cycle discharge (triangles) and charge (circles) capacities of SLMP-prelithiated cells as a function of SLMP to anode mass ratio. Inset in (b) shows the relationship for SLMP/anode mass ratio in the range of 0–0.4.

Grahic Jump Location
Fig. 6

First cycle specific charge capacity (without first discharge) of SLMP-prelithiated cells and SLMP utilization versus SLMP/anode mass ratio

Grahic Jump Location
Fig. 7

Schematic of three possible outcomes of SLMP toward Si particles. Note that the sizes of SLMP and Si particles are not true to scale.

Grahic Jump Location
Fig. 8

SEM image of SiNPs–MWCNTs composite anode after prelithiation by SLMP



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In