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Title: Investigating Li Microstructure Formation on Li Anodes for Lithium Batteries by $In Situ$ 6Li/7Li NMR and SEM

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [1];  [3];  [2]
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry; Univ. of Cambridge (United Kingdom). Dept. of Chemistry
  3. New York Univ. (NYU), NY (United States) Dept. of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
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The growth of lithium microstructures during battery cycling has, to date, prohibited the use of Li metal anodes and raises serious safety concerns even in conventional lithium-ion rechargeable batteries, particularly if they are charged at high rates. The electrochemical conditions under which these Li microstructures grow have, therefore, been investigated by in situ nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and susceptibility calculations. Lithium metal symmetric bag cells containing LiPF6 in EC/DMC electrolytes were used. Distinct 7Li NMR resonances were observed due to the Li metal bulk electrodes and microstructures, the changes in peak positions and intensities being monitored in situ during Li deposition. The changes in the NMR spectra, observed as a function of separator thickness and porosity (using Celgard and Whatmann glass microfiber membranes) and different applied pressures, were correlated with changes in the type of microstructure, by using SEM. Isotopically enriched 6Li metal electrodes were used against natural abundance predominantly 7Li metal counter electrodes to investigate radiofrequency (rf) field penetration into the Li anode and to confirm the assignment of the higher frequency peak to Li dendrites. The conclusions were supported by calculations performed to explore the effect of the different microstructures on peak position/broadening, the study showing that Li NMR spectroscopy can be used as a sensitive probe of both the amount and type of microstructure formation.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001294
OSTI ID:
1387803
Journal Information:
Journal of Physical Chemistry. C, Vol. 119, Issue 29; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 113 works
Citation information provided by
Web of Science

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Cited By (12)

Effect of Initial State of Lithium on the Propensity for Dendrite Formation: A Theoretical Study journal December 2016
Impact of External Pressure and Electrolyte Transport Properties on Lithium Dendrite Growth journal January 2018
Real-time 3D imaging of microstructure growth in battery cells using indirect MRI journal September 2016
Use of Asymmetric Average Charge- and Average Discharge- Voltages as an Indicator of the Onset of Unwanted Lithium Deposition in Lithium-Ion Cells journal January 2018
Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid-State NMR journal March 2017
In situ 7 Li-NMR analysis of lithium metal surface deposits with varying electrolyte compositions and concentrations journal January 2019
Correlating Structure and Properties of Super‐Concentrated Electrolyte Solutions: 17 O NMR and Electrochemical Characterization journal May 2019
Long-run in operando NMR to investigate the evolution and degradation of battery cells journal January 2018
Real-time 3D imaging of microstructure growth in battery cells using indirect MRI. journalarticle January 2016
Multiscale characterization of a lithium/sulfur battery by coupling operando X-ray tomography and spatially-resolved diffraction journal June 2017
7Li NMR Chemical Shift Imaging To Detect Microstructural Growth of Lithium in All-Solid-State Batteries. journalarticle January 2019
Ionic and Electronic Conduction in TiNb2O7. journalarticle January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
energy storage (including batteries and capacitors)
defects
charge transport
materials and chemistry by design
synthesis (novel materials)