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Metal dissolution from first principles: Potential-dependent kinetics and charge transfer

Journal Article · · Electrochimica Acta
 [1];  [2];  [1];  [3];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
  2. Univ. of Nebraska, Lincoln, NE (United States)
  3. Michigan Technological Univ., Houghton, MI (United States)
+ Show Author Affiliations
Metal dissolution and its inverse process are integral to both corrosion and electrodeposition; however, many mechanistic details regarding the dissolution process are challenging to decipher. These include how ion dissolution kinetics and charge transfer are influenced by the competition between metal and solvent interactions under an electrode potential. Here, in this work, we introduce a computational framework based on density functional theory with grand-canonical treatment of electrons to directly predict the potential energy landscape for metal dissolution at a constant potential. Using aluminum as an example, we demonstrate that dissolution kinetics is governed by competing kinetics between two physical processes associated with metal–metal bond breaking and ion-migration within the electrical double layer, respectively. We identify a kinetic transition between regimes dominated by each of these processes and show that this transition depends on the operating electrode potential, among other key factors. It is further found that kinetics and thermodynamics of these processes can be described with a simple, one-parameter Marcus-theory-type model. Beyond offering new understanding of charge transfer during dissolution, our simulation protocol provides a recipe for directly predicting other important quantities in electrochemical reactions from first principles that are difficult to measure, such as the symmetry factor.
Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
2202562
Alternate ID(s):
OSTI ID: 1962120
Report Number(s):
LLNL--JRNL-855973; 1085283
Journal Information:
Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 437; ISSN 0013-4686
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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