skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li–S Batteries with High Sulfur Mass Loading

Abstract

Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium—electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of longlife batteries using lithium anodes. In this study, we deposit a Lithium Metal Alucone-coated Uthnun conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly crosslinking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium—sulfur (Li—S) batteries with a high sulfur mass loading of —5 mg/cm2. After 140 cycles at a high current rate of —1 mA/cm2, alucone-coated Li—S batteries delivered a capacitymore » of 657.7 mAh/g, 39.5% better than that of a bare lithium—sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li—S batteries.« less

Authors:
 [1];  [2]; ORCiD logo [2];  [1];  [3];  [3]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Illinois, Chicago, IL (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1473942
Report Number(s):
SAND-2018-9889J
Journal ID: ISSN 1944-8244; 667715
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 8; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Chen, Lin, Huang, Zhennan, Shahbazian-Yassar, Reza, Libera, Joseph A., Klavetter, Kyle C., Zavadil, Kevin R., and Elam, Jeffrey W. Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li–S Batteries with High Sulfur Mass Loading. United States: N. p., 2018. Web. https://doi.org/10.1021/acsami.7b15879.
Chen, Lin, Huang, Zhennan, Shahbazian-Yassar, Reza, Libera, Joseph A., Klavetter, Kyle C., Zavadil, Kevin R., & Elam, Jeffrey W. Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li–S Batteries with High Sulfur Mass Loading. United States. https://doi.org/10.1021/acsami.7b15879
Chen, Lin, Huang, Zhennan, Shahbazian-Yassar, Reza, Libera, Joseph A., Klavetter, Kyle C., Zavadil, Kevin R., and Elam, Jeffrey W. Tue . "Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li–S Batteries with High Sulfur Mass Loading". United States. https://doi.org/10.1021/acsami.7b15879. https://www.osti.gov/servlets/purl/1473942.
@article{osti_1473942,
title = {Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li–S Batteries with High Sulfur Mass Loading},
author = {Chen, Lin and Huang, Zhennan and Shahbazian-Yassar, Reza and Libera, Joseph A. and Klavetter, Kyle C. and Zavadil, Kevin R. and Elam, Jeffrey W.},
abstractNote = {Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium—electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of longlife batteries using lithium anodes. In this study, we deposit a Lithium Metal Alucone-coated Uthnun conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly crosslinking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium—sulfur (Li—S) batteries with a high sulfur mass loading of —5 mg/cm2. After 140 cycles at a high current rate of —1 mA/cm2, alucone-coated Li—S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium—sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li—S batteries.},
doi = {10.1021/acsami.7b15879},
journal = {ACS Applied Materials and Interfaces},
number = 8,
volume = 10,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Schematic synthesis and characterization of alucone. (a) Schematic of the first cycle of alucone MLD beginning with a hydroxylated surface. (b) Facile MLD process directly coats alucone on lithium metal, forming highly cross-linking-structured alucone on the lithium foil. (c) Transmission electron microscopy (TEM) image of molecular-layer-deposited alucone filmmore » on 100 nm Si02 nanospheres. (d) Energy-dispersive Xray spectroscopy (EDS) mapping of molecular-layer-deposited alucone film on 100 nm SiO2, nanospheres.« less

Save / Share:

Works referenced in this record:

Battery materials for ultrafast charging and discharging
journal, March 2009

  • Kang, Byoungwoo; Ceder, Gerbrand
  • Nature, Vol. 458, Issue 7235, p. 190-193
  • DOI: 10.1038/nature07853

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

High-performance lithium battery anodes using silicon nanowires
journal, December 2007

  • Chan, Candace K.; Peng, Hailin; Liu, Gao
  • Nature Nanotechnology, Vol. 3, Issue 1, p. 31-35
  • DOI: 10.1038/nnano.2007.411

Recent advances in lithium–sulfur batteries
journal, December 2014


Operating through oxygen
journal, June 2016


The Birth of the Lithium-Ion Battery
journal, February 2012


A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries
journal, February 2013

  • Suo, Liumin; Hu, Yong-Sheng; Li, Hong
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2513

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000

  • Poizot, P.; Laruelle, S.; Grugeon, S.
  • Nature, Vol. 407, Issue 6803, p. 496-499
  • DOI: 10.1038/35035045

Nanostructured sulfur cathodes
journal, January 2013

  • Yang, Yuan; Zheng, Guangyuan; Cui, Yi
  • Chemical Society Reviews, Vol. 42, Issue 7, p. 3018-3032
  • DOI: 10.1039/c2cs35256g

Metallic anodes for next generation secondary batteries
journal, January 2013

  • Kim, Hansu; Jeong, Goojin; Kim, Young-Ugk
  • Chemical Society Reviews, Vol. 42, Issue 23
  • DOI: 10.1039/c3cs60177c

Li 2 S encapsulated by nitrogen-doped carbon for lithium sulfur batteries
journal, January 2014

  • Chen, Lin; Liu, Yuzi; Ashuri, Maziar
  • J. Mater. Chem. A, Vol. 2, Issue 42
  • DOI: 10.1039/C4TA04103H

Interconnected hollow carbon nanospheres for stable lithium metal anodes
journal, July 2014

  • Zheng, Guangyuan; Lee, Seok Woo; Liang, Zheng
  • Nature Nanotechnology, Vol. 9, Issue 8
  • DOI: 10.1038/nnano.2014.152

Lithium metal anodes for rechargeable batteries
journal, January 2014

  • Xu, Wu; Wang, Jiulin; Ding, Fei
  • Energy Environ. Sci., Vol. 7, Issue 2
  • DOI: 10.1039/C3EE40795K

High rate and stable cycling of lithium metal anode
journal, February 2015

  • Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7362

Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism
journal, March 2013

  • Ding, Fei; Xu, Wu; Graff, Gordon L.
  • Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456
  • DOI: 10.1021/ja312241y

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode
journal, March 2016

  • Liu, Yayuan; Lin, Dingchang; Liang, Zheng
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10992

Ionic Liquid-Nanoparticle Hybrid Electrolytes and their Application in Secondary Lithium-Metal Batteries
journal, July 2012

  • Lu, Yingying; Das, Shyamal K.; Moganty, Surya S.
  • Advanced Materials, Vol. 24, Issue 32
  • DOI: 10.1002/adma.201201953

Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes
journal, March 2016

  • Lin, Dingchang; Liu, Yayuan; Liang, Zheng
  • Nature Nanotechnology, Vol. 11, Issue 7
  • DOI: 10.1038/nnano.2016.32

Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode
journal, September 2014

  • Yan, Kai; Lee, Hyun-Wook; Gao, Teng
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503125u

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles
journal, December 2015

  • Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10101

PVP-Assisted Synthesis of Uniform Carbon Coated Li 2 S/CB for High-Performance Lithium–Sulfur Batteries
journal, November 2015

  • Chen, Lin; Liu, Yuzi; Zhang, Fan
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 46
  • DOI: 10.1021/acsami.5b07331

Attainable Gravimetric and Volumetric Energy Density of Li–S and Li Ion Battery Cells with Solid Separator-Protected Li Metal Anodes
journal, October 2015


Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries
journal, October 2013

  • Pieczonka, Nicholas P. W.; Yang, Li; Balogh, Michael P.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 44
  • DOI: 10.1021/jp408717x

Prop-1-ene-1,3-sultone as SEI formation additive in propylene carbonate-based electrolyte for lithium ion batteries
journal, April 2012


On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries
journal, February 2002


Methoxyethoxyethoxyphosphazenes as ionic conductive fire retardant additives for lithium battery systems
journal, April 2010


Additives-containing functional electrolytes for suppressing electrolyte decomposition in lithium-ion batteries
journal, October 2004


Nanocomposites of Titanium Dioxide and Polystyrene-Poly(ethylene oxide) Block Copolymer as Solid-State Electrolytes for Lithium Metal Batteries
journal, January 2013

  • Gurevitch, Inna; Buonsanti, Raffaella; Teran, Alexander A.
  • Journal of The Electrochemical Society, Vol. 160, Issue 9
  • DOI: 10.1149/2.117309jes

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013

  • Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid
  • Nature Materials, Vol. 12, Issue 5
  • DOI: 10.1038/nmat3602

Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries
journal, May 2014

  • Khurana, Rachna; Schaefer, Jennifer L.; Archer, Lynden A.
  • Journal of the American Chemical Society, Vol. 136, Issue 20
  • DOI: 10.1021/ja502133j

Next-Generation Lithium Metal Anode Engineering via Atomic Layer Deposition
journal, May 2015


Lithium metal protected by atomic layer deposition metal oxide for high performance anodes
journal, January 2017

  • Chen, Lin; Connell, Justin G.; Nie, Anmin
  • Journal of Materials Chemistry A, Vol. 5, Issue 24
  • DOI: 10.1039/C7TA03116E

Improved Cycle Life and Stability of Lithium Metal Anodes through Ultrathin Atomic Layer Deposition Surface Treatments
journal, September 2015


An Artificial Solid Electrolyte Interphase Layer for Stable Lithium Metal Anodes
journal, December 2015


A simple composite protective layer coating that enhances the cycling stability of lithium metal batteries
journal, June 2015


Molecular Layer Deposition of Alucone Polymer Films Using Trimethylaluminum and Ethylene Glycol
journal, May 2008

  • Dameron, A. A.; Seghete, D.; Burton, B. B.
  • Chemistry of Materials, Vol. 20, Issue 10
  • DOI: 10.1021/cm7032977

Surface Chemistry for Molecular Layer Deposition of Organic and Hybrid Organic−Inorganic Polymers
journal, April 2009

  • George, Steven M.; Yoon, Byunghoon; Dameron, Arrelaine A.
  • Accounts of Chemical Research, Vol. 42, Issue 4
  • DOI: 10.1021/ar800105q

Alucone Alloys with Tunable Properties Using Alucone Molecular Layer Deposition and Al 2 O 3 Atomic Layer Deposition
journal, February 2012

  • Lee, Byoung H.; Yoon, Byunghoon; Anderson, Virginia R.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 5
  • DOI: 10.1021/jp209003h

Inorganic–Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode
journal, August 2017


Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives
journal, January 2011

  • Quartarone, Eliana; Mustarelli, Piercarlo
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00081g

Barrier properties of Al2O3 and alucone coatings and nanolaminates on flexible biopolymer films
journal, September 2012


Thermomechanical properties of aluminum alkoxide (alucone) films created using molecular layer deposition
journal, October 2009


Morphology and ionic conductivity of some lithium ion complexes with poly(ethylene oxide)
journal, May 1982


Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer
journal, September 2016


Effect of Discharge Cutoff Voltage on Reversibility of Lithium/Sulfur Batteries with LiNO 3 -Contained Electrolyte
journal, January 2012

  • Zhang, Sheng S.
  • Journal of The Electrochemical Society, Vol. 159, Issue 7
  • DOI: 10.1149/2.002207jes

The Effect of Interactions and Reduction Products of LiNO 3 , the Anti-Shuttle Agent, in Li-S Battery Systems
journal, December 2014

  • Rosenman, Ariel; Elazari, Ran; Salitra, Gregory
  • Journal of The Electrochemical Society, Vol. 162, Issue 3
  • DOI: 10.1149/2.0861503jes

A Rechargeable Li–O 2 Battery Using a Lithium Nitrate/ N , N -Dimethylacetamide Electrolyte
journal, January 2013

  • Walker, Wesley; Giordani, Vincent; Uddin, Jasim
  • Journal of the American Chemical Society, Vol. 135, Issue 6
  • DOI: 10.1021/ja311518s

Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition
journal, August 2002

  • Elam, J. W.; Groner, M. D.; George, S. M.
  • Review of Scientific Instruments, Vol. 73, Issue 8, p. 2981-2987
  • DOI: 10.1063/1.1490410

    Works referencing / citing this record:

    High Dielectric, Robust Composite Protective Layer for Dendrite‐Free and LiPF 6 Degradation‐Free Lithium Metal Anode
    journal, September 2019

    • Jang, Eun Kwang; Ahn, Jinhyeok; Yoon, Sukeun
    • Advanced Functional Materials, Vol. 29, Issue 48
    • DOI: 10.1002/adfm.201905078

    A Novel Organic “Polyurea” Thin Film for Ultralong-Life Lithium-Metal Anodes via Molecular-Layer Deposition
    journal, December 2018


    Recent developments and insights into the understanding of Na metal anodes for Na-metal batteries
    journal, January 2018

    • Zhao, Yang; Adair, Keegan R.; Sun, Xueliang
    • Energy & Environmental Science, Vol. 11, Issue 10
    • DOI: 10.1039/c8ee01373j

    Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms
    journal, May 2018

    • Sun, Qian; Lau, Kah Chun; Geng, Dongsheng
    • Batteries & Supercaps, Vol. 1, Issue 2
    • DOI: 10.1002/batt.201800024

    Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries
    journal, July 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.