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Title: Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

Abstract

Secondary batteries based on lithium are the most significant energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to somemore » extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. Furthermore, we review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. An enticing finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.« less

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Cornell Univ., Ithaca, NY (United States)
  2. Zhejiang Univ., (China)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); King Abdullah University of Science and Technology (KAUST); National Science Foundation (NSF)
OSTI Identifier:
1370439
Grant/Contract Number:  
SC0001086; DMR-1006323
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 48; Journal Issue: 11; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Tu, Zhengyuan, Nath, Pooja, Lu, Yingying, Tikekar, Mukul D., and Archer, Lynden A. Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries. United States: N. p., 2015. Web. doi:10.1021/acs.accounts.5b00427.
Tu, Zhengyuan, Nath, Pooja, Lu, Yingying, Tikekar, Mukul D., & Archer, Lynden A. Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries. United States. doi:10.1021/acs.accounts.5b00427.
Tu, Zhengyuan, Nath, Pooja, Lu, Yingying, Tikekar, Mukul D., and Archer, Lynden A. Fri . "Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries". United States. doi:10.1021/acs.accounts.5b00427. https://www.osti.gov/servlets/purl/1370439.
@article{osti_1370439,
title = {Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries},
author = {Tu, Zhengyuan and Nath, Pooja and Lu, Yingying and Tikekar, Mukul D. and Archer, Lynden A.},
abstractNote = {Secondary batteries based on lithium are the most significant energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. Furthermore, we review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. An enticing finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.},
doi = {10.1021/acs.accounts.5b00427},
journal = {Accounts of Chemical Research},
issn = {0001-4842},
number = 11,
volume = 48,
place = {United States},
year = {2015},
month = {10}
}

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Works referencing / citing this record:

Linear Stability Analysis of Transient Electrodeposition in Charged Porous Media: Suppression of Dendritic Growth by Surface Conduction
journal, January 2019

  • Khoo, Edwin; Zhao, Hongbo; Bazant, Martin Z.
  • Journal of The Electrochemical Society, Vol. 166, Issue 10
  • DOI: 10.1149/2.1521910jes

Linear Stability Analysis of Transient Electrodeposition in Charged Porous Media: Suppression of Dendritic Growth by Surface Conduction
journal, January 2019

  • Khoo, Edwin; Zhao, Hongbo; Bazant, Martin Z.
  • Journal of The Electrochemical Society, Vol. 166, Issue 10
  • DOI: 10.1149/2.1521910jes