Title: Elucidating the structure of the magnesium aluminum chloride complex electrolyte for magnesium-ion batteries

Abstract

Non-aqueous Mg-ion batteries offer a promising way to overcome safety, costs, and energy density limitations of state-of-the-art Li-ion battery technology. Here, we present a rigorous analysis of the magnesium aluminum chloride complex (MACC) in tetrahydrofuran (THF), one of the few electrolytes that can reversibly plate and strip Mg. We use ab initio calculations and classical molecular dynamics simulations to interrogate the MACC electrolyte composition with the goal of addressing two urgent questions that have puzzled battery researchers: (i) the functional species of the electrolyte, and (ii) the complex equilibria regulating the MACC speciation after prolonged electrochemical cycling, a process termed as conditioning, and after prolonged inactivity, a process called aging. A general computational strategy to untangle the complex structure of electrolytes, ionic liquids and other liquid media is presented. The analysis of formation energies and grand-potential phase diagrams of Mg–Al–Cl–THF suggests that the MACC electrolyte bears a simple chemical structure with few simple constituents, namely the electro-active species MgCl ⁺ and AlCl ₄- in equilibrium with MgCl ₂ and AlCl ₃. Knowledge of the stable species of the MACC electrolyte allows us to determine the most important equilibria occurring during electrochemical cycling. We observe that Al deposition is always preferredmore » to Mg deposition, explaining why freshly synthesized MACC cannot operate and needs to undergo preparatory conditioning. Similarly, we suggest that aluminum displacement and depletion from the solution upon electrolyte resting (along with continuous MgCl ₂ regeneration) represents one of the causes of electrolyte aging. Finally, we compute the NMR shifts from shielding tensors of selected molecules and ions providing fingerprints to guide future experimental investigations.« less

Authors:

Canepa, Pieremanuele ^[1]; Jayaraman, Saivenkataraman ^[2]; Cheng, Lei ^[3]; Rajput, Nav Nidhi ^[4]; Richards, William D. ^[2]; Gautam, Gopalakrishnan Sai  ^[1];

• Search DOE PAGES for author "Gautam, Gopalakrishnan Sai"
• Search DOE PAGES for ORCID "0000-0002-1303-0976"
• Search orcid.org for ORCID "0000-0002-1303-0976"

Curtiss, Larry A. ^[3]; Persson, Kristin A. ^[4]; Ceder, Gerbrand ^[5]

---

+ Show Author Affiliations

1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering

Publication Date:

2015-10-27

Research Org.:

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Joint Center for Energy Storage Research (JCESR) and Scientific User Facilities Division

OSTI Identifier:

1474898

Grant/Contract Number:  

AC02-05CH11231; 3F-31144

Resource Type:

Accepted Manuscript

Journal Name:

Energy & Environmental Science

Additional Journal Information:

Journal Volume: 8; Journal Issue: 12; Related Information: © 2015 The Royal Society of Chemistry.; Journal ID: ISSN 1754-5692

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

25 ENERGY STORAGE; 36 MATERIALS SCIENCE