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Title: Probing the Reaction between PVDF and LiPAA vs Li 7 Si 3 : Investigation of Binder Stability for Si Anodes

Abstract

The chemical interaction of the highly reactive lithiated Si anode with other cell components, such as binders and electrolytes, is one of the most vital issues in batteries using Si electrodes. In this work, crystalline lithium silicide (LS) with Li 7Si 3 composition is synthesized to study the direct chemical reactions between the lithiated Si anodes and two typical binders, polyvinylidenefluoride (PVDF) and lithiated polyacrylic acid (LiPAA). The solid-state nuclear magnetic resonance (NMR) and Raman characterization experiments show that LiPAA binder is chemically stable against LS. On the contrary, PVDF binder reacts more readily with the LS, resulting in critical loss of Li from the bulk. 13C NMR shows the C-H bonds and C-C PVDF backbone were affected, whereas 19F MAS NMR shows the C-F bonds are relatively more stable. No LiF is detected, however HF release is confirmed by gas chromatography/mass spectrometry. The characterization results are consistent with electrochemical tests, which show the Si electrode using LiPAA as the binder has a much higher cyclability than when compared with PVDF. This work demonstrates the using of LS as an effective approach to evaluate and investigate the reactions between lithiated Si and different cell components, in order to stabilize Simore » anodes.« less

Authors:
ORCiD logo; ; ; ; ORCiD logo; ORCiD logo; ORCiD logo;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technologies (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1568908
Alternate Identifier(s):
OSTI ID: 1550792
Grant/Contract Number:  
[AC02-06CH11357]
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
[Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 12]; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Batteries; Silicon; Binder; Lithium Silicide; Silicon Anode

Citation Formats

Han, Binghong, Piernas-Muñoz, Maria Jose, Dogan, Fulya, Kubal, Joseph, Trask, Stephen E., Bloom, Ira D., Vaughey, John T., and Key, Baris. Probing the Reaction between PVDF and LiPAA vs Li 7 Si 3 : Investigation of Binder Stability for Si Anodes. United States: N. p., 2019. Web. doi:10.1149/2.0241912jes.
Han, Binghong, Piernas-Muñoz, Maria Jose, Dogan, Fulya, Kubal, Joseph, Trask, Stephen E., Bloom, Ira D., Vaughey, John T., & Key, Baris. Probing the Reaction between PVDF and LiPAA vs Li 7 Si 3 : Investigation of Binder Stability for Si Anodes. United States. doi:10.1149/2.0241912jes.
Han, Binghong, Piernas-Muñoz, Maria Jose, Dogan, Fulya, Kubal, Joseph, Trask, Stephen E., Bloom, Ira D., Vaughey, John T., and Key, Baris. Fri . "Probing the Reaction between PVDF and LiPAA vs Li 7 Si 3 : Investigation of Binder Stability for Si Anodes". United States. doi:10.1149/2.0241912jes.
@article{osti_1568908,
title = {Probing the Reaction between PVDF and LiPAA vs Li 7 Si 3 : Investigation of Binder Stability for Si Anodes},
author = {Han, Binghong and Piernas-Muñoz, Maria Jose and Dogan, Fulya and Kubal, Joseph and Trask, Stephen E. and Bloom, Ira D. and Vaughey, John T. and Key, Baris},
abstractNote = {The chemical interaction of the highly reactive lithiated Si anode with other cell components, such as binders and electrolytes, is one of the most vital issues in batteries using Si electrodes. In this work, crystalline lithium silicide (LS) with Li7Si3 composition is synthesized to study the direct chemical reactions between the lithiated Si anodes and two typical binders, polyvinylidenefluoride (PVDF) and lithiated polyacrylic acid (LiPAA). The solid-state nuclear magnetic resonance (NMR) and Raman characterization experiments show that LiPAA binder is chemically stable against LS. On the contrary, PVDF binder reacts more readily with the LS, resulting in critical loss of Li from the bulk. 13C NMR shows the C-H bonds and C-C PVDF backbone were affected, whereas 19F MAS NMR shows the C-F bonds are relatively more stable. No LiF is detected, however HF release is confirmed by gas chromatography/mass spectrometry. The characterization results are consistent with electrochemical tests, which show the Si electrode using LiPAA as the binder has a much higher cyclability than when compared with PVDF. This work demonstrates the using of LS as an effective approach to evaluate and investigate the reactions between lithiated Si and different cell components, in order to stabilize Si anodes.},
doi = {10.1149/2.0241912jes},
journal = {Journal of the Electrochemical Society},
number = [12],
volume = [166],
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/2.0241912jes

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Works referenced in this record:

Binder effect on cycling performance of silicon/carbon composite anodes for lithium ion batteries
journal, August 2006

  • Chen, Libao; Xie, Xiaohua; Xie, Jingying
  • Journal of Applied Electrochemistry, Vol. 36, Issue 10
  • DOI: 10.1007/s10800-006-9191-2

A Highly Cross-Linked Polymeric Binder for High-Performance Silicon Negative Electrodes in Lithium Ion Batteries
journal, July 2012

  • Koo, Bonjae; Kim, Hyunjung; Cho, Younghyun
  • Angewandte Chemie International Edition, Vol. 51, Issue 35
  • DOI: 10.1002/anie.201201568

Li12Si7, eine Verbindung mit trigonal-planaren Si4-Clustern und isometrischen Si5-Ringen
journal, December 1986

  • Nesper, Reinhard; von Schnering, Hans Georg; Curda, Jan
  • Chemische Berichte, Vol. 119, Issue 12
  • DOI: 10.1002/cber.19861191207

Structure and chemical bonding in zintl-phases containing lithium
journal, January 1990


An i.r. investigation of polyion-counterion interactions
journal, May 1967

  • Leyte, J. C.; Zuiderweg, L. H.; Vledder, H. J.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 23, Issue 5
  • DOI: 10.1016/0584-8539(67)80361-1

Poly(phenanthrenequinone) as a conductive binder for nano-sized silicon negative electrodes
journal, January 2015

  • Kim, Sang-Mo; Kim, Myeong Hak; Choi, Sung Yeol
  • Energy & Environmental Science, Vol. 8, Issue 5
  • DOI: 10.1039/C5EE00472A

Raman spectroscopic studies of Li x Si y compounds : Raman spectroscopic studies of Li
journal, April 2013

  • Gruber, Thomas; Thomas, Daniel; Röder, Christian
  • Journal of Raman Spectroscopy, Vol. 44, Issue 6
  • DOI: 10.1002/jrs.4308

Fluorine-19 solid-state NMR investigation of regiodefective semicrystalline α-poly(vinylidenefluoride)
journal, January 2003


Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells
journal, January 2007


Insertion Electrode Materials for Rechargeable Lithium Batteries
journal, July 1998


Silicon/Graphite Composite Electrodes for High-Capacity Anodes: Influence of Binder Chemistry on Cycling Stability
journal, January 2008

  • Hochgatterer, N. S.; Schweiger, M. R.; Koller, S.
  • Electrochemical and Solid-State Letters, Vol. 11, Issue 5
  • DOI: 10.1149/1.2888173

Li21Si5, a Zintl phase as well as a Hume-Rothery phase
journal, September 1987


Effect of polyimide binder on electrochemical characteristics of surface-modified silicon anode for lithium ion batteries
journal, December 2013


Étude de la transition conformationnelle de l'acide polyacrylique syndiotactique en solution aqueuse par spectroscopie de vibration
journal, January 1975


Toward Efficient Binders for Li-Ion Battery Si-Based Anodes: Polyacrylic Acid
journal, October 2010

  • Magasinski, Alexandre; Zdyrko, Bogdan; Kovalenko, Igor
  • ACS Applied Materials & Interfaces, Vol. 2, Issue 11
  • DOI: 10.1021/am100871y

Thermomechanical Polymer Binder Reactivity with Positive Active Materials for Li Metal Polymer and Li-Ion Batteries: An XPS and XPS Imaging Study
journal, April 2019

  • Grissa, Rabeb; Abramova, Alla; Tambio, Sacris-Jeru
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 20
  • DOI: 10.1021/acsami.9b01761

An infrared study of phase‐III poly(vinylidene fluoride)
journal, October 1979

  • Bachmann, M. A.; Gordon, W. L.; Koenig, J. L.
  • Journal of Applied Physics, Vol. 50, Issue 10
  • DOI: 10.1063/1.325780

High Capacity, Reversible Silicon Thin-Film Anodes for Lithium-Ion Batteries
journal, January 2003

  • Maranchi, J. P.; Hepp, A. F.; Kumta, P. N.
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 9
  • DOI: 10.1149/1.1596918

Si Electrodes for Li-Ion Batteries—A New Way to Look at an Old Problem
journal, January 2008

  • Beattie, S. D.; Larcher, D.; Morcrette, M.
  • Journal of The Electrochemical Society, Vol. 155, Issue 2
  • DOI: 10.1149/1.2817828

Carbon-Coated Si as a Lithium-Ion Battery Anode Material
journal, January 2002

  • Yoshio, Masaki; Wang, Hongyu; Fukuda, Kenji
  • Journal of The Electrochemical Society, Vol. 149, Issue 12
  • DOI: 10.1149/1.1518988

Designing nanostructured Si anodes for high energy lithium ion batteries
journal, October 2012


Performance Enhancing Electrolyte Additives for Lithium Ion Batteries with Silicon Anodes
journal, January 2012

  • Dalavi, Swapnil; Guduru, Pradeep; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 159, Issue 5
  • DOI: 10.1149/2.076205jes

Pair Distribution Function Analysis and Solid State NMR Studies of Silicon Electrodes for Lithium Ion Batteries: Understanding the (De)lithiation Mechanisms
journal, January 2011

  • Key, Baris; Morcrette, Mathieu; Tarascon, Jean-Marie
  • Journal of the American Chemical Society, Vol. 133, Issue 3
  • DOI: 10.1021/ja108085d

Infrared, Raman, and Near-Infrared Spectroscopic Evidence for the Coexistence of Various Hydrogen-Bond Forms in Poly(acrylic acid)
journal, February 1997

  • Dong, Jian; Ozaki, Yukihiro; Nakashima, Kenichi
  • Macromolecules, Vol. 30, Issue 4
  • DOI: 10.1021/ma960693x

A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries
journal, September 2011


Characterization of amorphous and nanocrystalline carbon films
journal, April 2006


Real-Time NMR Investigations of Structural Changes in Silicon Electrodes for Lithium-Ion Batteries
journal, July 2009

  • Key, Baris; Bhattacharyya, Rangeet; Morcrette, Mathieu
  • Journal of the American Chemical Society, Vol. 131, Issue 26
  • DOI: 10.1021/ja8086278

An NMR Study of Poly(vinylidene fluoride) Structure by 1H, 13C, and 19F Triple Resonance Method
journal, December 1994


Enhanced electrochemical properties of a Si-based anode using an electrochemically active polyamide imide binder
journal, March 2008


NMR investigations on the lithiation and delithiation of nanosilicon-based anodes for Li-ion batteries
journal, December 2010

  • Trill, Jan-Henning; Tao, Chuangqi; Winter, Martin
  • Journal of Solid State Electrochemistry, Vol. 15, Issue 2
  • DOI: 10.1007/s10008-010-1260-0

Poly(vinylidene fluoride) (PVDF) Binder Degradation in Li–O 2 Batteries: A Consideration for the Characterization of Lithium Superoxide
journal, February 2017

  • Papp, Joseph K.; Forster, Jason D.; Burke, Colin M.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 6
  • DOI: 10.1021/acs.jpclett.7b00040

In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous Silicon
journal, January 2004

  • Hatchard, T. D.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 151, Issue 6
  • DOI: 10.1149/1.1739217

Fluorine-19 solid state NMR study of vinylidenefluoride polymers using selective relaxation filters
journal, September 2006

  • Wormald, Philip; Ameduri, Bruno; Harris, Robin K.
  • Solid State Nuclear Magnetic Resonance, Vol. 30, Issue 2
  • DOI: 10.1016/j.ssnmr.2006.05.003

Electrochemical lithiation of tin and tin-based intermetallics and composites
journal, September 1999


Effect of porosity on electrochemical and mechanical properties of composite Li-ion anodes
journal, January 2015

  • Antartis, Dimitrios; Dillon, Shen; Chasiotis, Ioannis
  • Journal of Composite Materials, Vol. 49, Issue 15
  • DOI: 10.1177/0021998314568653