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Title: Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

Abstract

In this study, batteries that shuttle multivalent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity, thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn 2O 4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalentmore » cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

Authors:
 [1];  [2];  [2];  [2];  [1];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1214558
Alternate Identifier(s):
OSTI ID: 1512123
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Miao, Rong, Ziqin, Malik, Rahul, Canepa, Pieremanuele, Jain, Anubhav, Ceder, Gerbrand, and Persson, Kristin A. Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations. United States: N. p., 2014. Web. doi:10.1039/C4EE03389B.
Liu, Miao, Rong, Ziqin, Malik, Rahul, Canepa, Pieremanuele, Jain, Anubhav, Ceder, Gerbrand, & Persson, Kristin A. Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations. United States. doi:10.1039/C4EE03389B.
Liu, Miao, Rong, Ziqin, Malik, Rahul, Canepa, Pieremanuele, Jain, Anubhav, Ceder, Gerbrand, and Persson, Kristin A. Tue . "Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations". United States. doi:10.1039/C4EE03389B. https://www.osti.gov/servlets/purl/1214558.
@article{osti_1214558,
title = {Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations},
author = {Liu, Miao and Rong, Ziqin and Malik, Rahul and Canepa, Pieremanuele and Jain, Anubhav and Ceder, Gerbrand and Persson, Kristin A.},
abstractNote = {In this study, batteries that shuttle multivalent ions such as Mg2+ and Ca2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity, thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn2O4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.},
doi = {10.1039/C4EE03389B},
journal = {Energy & Environmental Science},
issn = {1754-5692},
number = 3,
volume = 8,
place = {United States},
year = {2014},
month = {12}
}

Journal Article:
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Cited by: 72 works
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Figures / Tables:

Fig. 1 Fig. 1 : The spinel crystal structure where the ‘A’ atoms occupy the tetrahedral sites, and the ‘B’ atoms occupy the octahedral site. Throughout this paper, the ‘A’ atoms are multivalent intercalating ions selected from the set {Mg2+, Ca2+, Zn2+, Y3+, Al3+}, and the ‘B’ atoms are transition redox-active ions,more » selected from the set {Ti, V, Cr, Mn, Fe, Co, Ni}.« less

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