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Title: Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

Journal Article · · Journal of Physical Chemistry. C
 [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li+. For LiBF4 and LiPF6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li+. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1337952
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 33; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (40)

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  • Maia, Julio Daniel Carvalho; Urquiza Carvalho, Gabriel Aires; Mangueira, Carlos Peixoto
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9 https://doi.org/10.1021/ct3004645
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Cited By (4)

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells journal December 2016
Understanding and development of olivine LiCoPO 4 cathode materials for lithium-ion batteries journal January 2018
Structures and dynamic properties of the LiPF 6 electrolytic solution under electric fields – a theoretical study journal January 2019
Hybrid electrolyte enables safe and practical 5 V LiNi 0.5 Mn 1.5 O 4 batteries journal January 2019

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aluminum collector corrosion
coordination polymer
electrolyte
lithium ion batteries