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

Title: ALD Protection of Li-Metal Anode Surfaces - Quantifying and Preventing Chemical and Electrochemical Corrosion in Organic Solvent

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Department of Materials Science and Engineering, University of Maryland, College Park MD 20742 USA; Institute for Systems Research, University of Maryland, College Park MD 20742 USA
  2. Institute for Systems Research, University of Maryland, College Park MD 20742 USA; Department of Chemistry, University of Maryland, College Park MD 20742 USA
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388261
DOE Contract Number:
SC0001160
Resource Type:
Journal Article
Resource Relation:
Journal Name: Advanced Materials Interfaces; Journal Volume: 3; Journal Issue: 21; Related Information: NEES partners with University of Maryland (lead); University of California, Irvine; University of Florida; Los Alamos National Laboratory; Sandia National Laboratories; Yale University
Country of Publication:
United States
Language:
English
Subject:
bio-inspired, energy storage (including batteries and capacitors), defects, charge transport, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Lin, Chuan-Fu, Kozen, Alexander C., Noked, Malachi, Liu, Chanyuan, and Rubloff, Gary W. ALD Protection of Li-Metal Anode Surfaces - Quantifying and Preventing Chemical and Electrochemical Corrosion in Organic Solvent. United States: N. p., 2016. Web. doi:10.1002/admi.201600426.
Lin, Chuan-Fu, Kozen, Alexander C., Noked, Malachi, Liu, Chanyuan, & Rubloff, Gary W. ALD Protection of Li-Metal Anode Surfaces - Quantifying and Preventing Chemical and Electrochemical Corrosion in Organic Solvent. United States. doi:10.1002/admi.201600426.
Lin, Chuan-Fu, Kozen, Alexander C., Noked, Malachi, Liu, Chanyuan, and Rubloff, Gary W. Wed . "ALD Protection of Li-Metal Anode Surfaces - Quantifying and Preventing Chemical and Electrochemical Corrosion in Organic Solvent". United States. doi:10.1002/admi.201600426.
@article{osti_1388261,
title = {ALD Protection of Li-Metal Anode Surfaces - Quantifying and Preventing Chemical and Electrochemical Corrosion in Organic Solvent},
author = {Lin, Chuan-Fu and Kozen, Alexander C. and Noked, Malachi and Liu, Chanyuan and Rubloff, Gary W.},
abstractNote = {},
doi = {10.1002/admi.201600426},
journal = {Advanced Materials Interfaces},
number = 21,
volume = 3,
place = {United States},
year = {Wed Aug 24 00:00:00 EDT 2016},
month = {Wed Aug 24 00:00:00 EDT 2016}
}
  • Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; andmore » chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less
  • The conventional DMSO-based electrolyte (1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in DMSO) is unstable against the Li metal anode and therefore cannot be used directly in practical Li-O2 batteries. Here, we demonstrate that a highly concentrated electrolyte based on LiTFSI in DMSO (with a molar ratio of 1:3) can greatly improve the stability of the Li metal anode against DMSO and significantly improve the cycling stability of Li-O2 batteries. This highly concentrated electrolyte contains no free DMSO solvent molecules, but only complexes of (TFSI–)a-Li+-(DMSO)b (where a + b = 4), and thus enhances their stability with Li metal anodes. In addition,more » such salt-solvent complexes have higher Gibbs activation energy barriers than the free DMSO solvent molecules, indicating improved stability of the electrolyte against the attack of superoxide radical anions. Therefore, the stability of this highly concentrated electrolyte at both Li metal anodes and carbon-based air electrodes has been greatly enhanced, resulting in improved cyclic stability of Li-O2 batteries. The fundamental stability of the electrolyte with free-solvent against the chemical and electrochemical reactions can also be used to enhance the stability of other electrochemical systems.« less
  • Pure and metal (Cu, Al, Sn, and V)-doped Li{sub 4}Ti{sub 5}O{sub 12} powders are prepared with solid-state reaction method. The effects of dopants on the physical and electrochemical properties are characterized by using TGA, XRD, and SEM. Compared with pure Li{sub 4}Ti{sub 5}O{sub 12}, metal-doped Li{sub 4}Ti{sub 5}O{sub 12} powders show structural stability and enhanced lithium ion diffusivity brought by doped metal ions. Voltage characteristics and initial charge–discharge characteristics according to the C rates in pure and metal-doped Li{sub 4}Ti{sub 5}O{sub 12} electrode materials are studied. Pure Li{sub 4}Ti{sub 5}O{sub 12} powder shows a relatively good discharge capacity of 164more » mAh/g at a rate 0.2C, and some of metal-doped Li{sub 4}Ti{sub 5}O{sub 12} powders show higher discharge capacities. Metal-doped Li{sub 4}Ti{sub 5}O{sub 12} powders are promising candidates as anode materials for lithium-ion batteries.« less