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Title: On the Balance of Intercalation and Conversion Reactions in Battery Cathodes

Abstract

A thermodynamic analysis of the driving forces is presented for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, the importance of polymorph selection as well as chemical composition on the ability of a host cathode to support intercalation reactions is analyzed. It is found that the accessibility of high energy charged polymorphs in oxides generally leads to larger intercalation voltages favoring intercalation reactions, whereas sulfides and selenides tend to favor conversion reactions. Furthermore, it is observed that Cr-containing cathodes favor intercalation more strongly than those with other transition metals. It is concluded that two-electron reduction of transition metals (as is possible with the intercalation of a 2 + ion) will favor conversion reactions in the compositions studied.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543466
Alternate Identifier(s):
OSTI ID: 1433450
Grant/Contract Number:  
[3F-31144]
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
[ Journal Volume: 8; Journal Issue: 20]; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; chemistry; energy & fuels; materials science; physics; batteries; cathodes; conversion reactions; density functional theory; thermodynamics

Citation Formats

Hannah, Daniel C., Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, and Ceder, Gerbrand. On the Balance of Intercalation and Conversion Reactions in Battery Cathodes. United States: N. p., 2018. Web. doi:10.1002/aenm.201800379.
Hannah, Daniel C., Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, & Ceder, Gerbrand. On the Balance of Intercalation and Conversion Reactions in Battery Cathodes. United States. doi:10.1002/aenm.201800379.
Hannah, Daniel C., Sai Gautam, Gopalakrishnan, Canepa, Pieremanuele, and Ceder, Gerbrand. Mon . "On the Balance of Intercalation and Conversion Reactions in Battery Cathodes". United States. doi:10.1002/aenm.201800379. https://www.osti.gov/servlets/purl/1543466.
@article{osti_1543466,
title = {On the Balance of Intercalation and Conversion Reactions in Battery Cathodes},
author = {Hannah, Daniel C. and Sai Gautam, Gopalakrishnan and Canepa, Pieremanuele and Ceder, Gerbrand},
abstractNote = {A thermodynamic analysis of the driving forces is presented for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, the importance of polymorph selection as well as chemical composition on the ability of a host cathode to support intercalation reactions is analyzed. It is found that the accessibility of high energy charged polymorphs in oxides generally leads to larger intercalation voltages favoring intercalation reactions, whereas sulfides and selenides tend to favor conversion reactions. Furthermore, it is observed that Cr-containing cathodes favor intercalation more strongly than those with other transition metals. It is concluded that two-electron reduction of transition metals (as is possible with the intercalation of a 2 + ion) will favor conversion reactions in the compositions studied.},
doi = {10.1002/aenm.201800379},
journal = {Advanced Energy Materials},
number = [20],
volume = [8],
place = {United States},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 8 works
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Figures / Tables:

Figure 1 Figure 1: Summary of the structure selection scheme for the voltage calculations described in the manuscript. A is the working ion (Li, Na, Mg, Ca, or Zn), M is the 3d transition metal, and X is the anion (O, S, or Se). $γ, λ, β, α$ refer to different polymorphsmore » for M2X4. Energy refers to the Gibbs energy of the different polymorphs considered. For each chemistry, we calculate two voltages for both intercalation ($V$int, blue arrows) and conversion ($V$conv, red arrows), considering the lowest energy discharged polymorph ($V$ LDP, solid arrows) and the lowest energy charged polymorph ($V$ LCP, dashed arrows). The explicit intercalation and conversion reactions used for the voltage calculations are indicated in the highlighted blue and red boxes, respectively.« less

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