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

Title: Stable lithium electrodeposition in salt-reinforced electrolytes

ORCiD logo; ; ;
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); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Power Sources; Journal Volume: 279; Journal Issue: C; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory
Country of Publication:
United States

Citation Formats

Lu, Yingying, Tu, Zhengyuan, Shu, Jonathan, and Archer, Lynden A. Stable lithium electrodeposition in salt-reinforced electrolytes. United States: N. p., 2015. Web. doi:10.1016/j.jpowsour.2015.01.030.
Lu, Yingying, Tu, Zhengyuan, Shu, Jonathan, & Archer, Lynden A. Stable lithium electrodeposition in salt-reinforced electrolytes. United States. doi:10.1016/j.jpowsour.2015.01.030.
Lu, Yingying, Tu, Zhengyuan, Shu, Jonathan, and Archer, Lynden A. 2015. "Stable lithium electrodeposition in salt-reinforced electrolytes". United States. doi:10.1016/j.jpowsour.2015.01.030.
title = {Stable lithium electrodeposition in salt-reinforced electrolytes},
author = {Lu, Yingying and Tu, Zhengyuan and Shu, Jonathan and Archer, Lynden A.},
abstractNote = {},
doi = {10.1016/j.jpowsour.2015.01.030},
journal = {Journal of Power Sources},
number = C,
volume = 279,
place = {United States},
year = 2015,
month = 4
  • Secondary batteries based on lithium are the most important 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 carbonaceousmore » 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. We also 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. A promising 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
  • Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. Here, we report on electrodeposition of lithium in simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling atmore » room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolye/lithium interface and impedance analysis of the interface during different stages of cell operation. Our finding provide support for an important and recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Finally, our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.« less
  • Synthesis, characterization, and electrochemical investigations of lithium bis[5-fluoro-2-olato-1-benzenesulfonato(2-)-O,O{prime}]borate(1-), a new salt for lithium-ion cells in ethylene carbonate (EC)-dimethylcarbonate (DMC) mixtures are presented. At platinum electrodes the anodic oxidation limit is about 4.6 V, in good agreement with an estimation based on semiempirical quantum-mechanical calculations. At Al electrodes its behavior is similar to that obtained for LiPF{sub 6}/EC/DMC (1:1).
  • Disclosed is a new class of nontoxic thermally, chemically, and electrochemically stable, inexpensive lithium salts based on a chelate complex anion of boron with aromatic or aliphatic diols or carboxylic acids. The synthesis, purification and analysis of the first member of this class, lithium bis[1,2-benzenediolato(2-)-O,O{prime}]borate (Li[B(C{sub 6}H{sub 4}O{sub 2}){sub 2}]) is described and some results are given from electrochemical experiments of its solution in various aprotic solvents. The voltage window of Li[B(C{sub 6}H{sub 4}O{sub 2}){sub 2}] based solutions is limited by the oxidation of the borate at about 3.6 V vs. lithium. Lithium can be cycled in solutions of lithiummore » bis[1,2-benzenediolato(2-)-O,O{prime}]borate based on different aprotic solvents. Cycling efficiencies depend strongly on the solvents used, but scarcely on contact times of the solution with lithium, or on the use of mixed electrolytes (Li[B(C{sub 6}H{sub 4}O{sub 2}){sub 2}]/[N(CH{sub 3}){sub 4}][B(C{sub 6}H{sub 4}O{sub 2}){sub 2}]).« less