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Title: Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries

Abstract

Ca-ion batteries (CIBs) show promise to achieve the high energy density required by emerging applications like electric vehicles because of their potentially improved capacities and high operating voltages. The development of CIBs is hindered by the failure of traditional graphite and calcium metal anodes due to the intercalation difficulty and the lack of efficient electrolytes. Recently, a high voltage (4.45 V) CIB cell using Sn as the anode has been reported to achieve a remarkable cyclability (>300 cycles). The calciation of Sn is observed to end at Ca7Sn6, which is surprising, since higher Ca-content compounds are known (e.g., Ca2Sn). In our paper, the Sn electrochemical calciation reaction process is investigated computationally and the reaction driving force as a function of Ca content is explored using density functional theory (DFT) calculations. This exploration allows the identification of threshold voltages which govern the limits of the calciation process. This information is then used to design a four-step screening strategy and high-throughput DFT is utilized to search for anode materials with higher properties. Finally, many metalloids (Si, Sb, Ge), (post-)transition metals (Al, Pb, Cu, Cd, CdCu2) are predicted to be promising inexpensive anode candidates and warrant further experimental investigations.

Authors:
ORCiD logo [1];  [2];  [3];  [2]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Univ. of Toronto, Toronto, ON (Canada). Dept. of Chemistry, and Dept. of Computer Science; Vector Inst. for Artificial Intelligence, Toronto, ON (Canada); Canadian Inst. for Advanced Research (CIFAR), Toronto, ON (Canada)
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC), Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530588
Grant/Contract Number:  
SC0008688; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; alloy-type electrodes; calcium-ion batteries; high-energy-density electrodes; high-throughout screening

Citation Formats

Yao, Zhenpeng, Hegde, Vinay I., Aspuru-Guzik, Alán, and Wolverton, Chris. Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries. United States: N. p., 2019. Web. doi:10.1002/aenm.201802994.
Yao, Zhenpeng, Hegde, Vinay I., Aspuru-Guzik, Alán, & Wolverton, Chris. Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries. United States. doi:10.1002/aenm.201802994.
Yao, Zhenpeng, Hegde, Vinay I., Aspuru-Guzik, Alán, and Wolverton, Chris. Fri . "Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries". United States. doi:10.1002/aenm.201802994. https://www.osti.gov/servlets/purl/1530588.
@article{osti_1530588,
title = {Discovery of Calcium-Metal Alloy Anodes for Reversible Ca-Ion Batteries},
author = {Yao, Zhenpeng and Hegde, Vinay I. and Aspuru-Guzik, Alán and Wolverton, Chris},
abstractNote = {Ca-ion batteries (CIBs) show promise to achieve the high energy density required by emerging applications like electric vehicles because of their potentially improved capacities and high operating voltages. The development of CIBs is hindered by the failure of traditional graphite and calcium metal anodes due to the intercalation difficulty and the lack of efficient electrolytes. Recently, a high voltage (4.45 V) CIB cell using Sn as the anode has been reported to achieve a remarkable cyclability (>300 cycles). The calciation of Sn is observed to end at Ca7Sn6, which is surprising, since higher Ca-content compounds are known (e.g., Ca2Sn). In our paper, the Sn electrochemical calciation reaction process is investigated computationally and the reaction driving force as a function of Ca content is explored using density functional theory (DFT) calculations. This exploration allows the identification of threshold voltages which govern the limits of the calciation process. This information is then used to design a four-step screening strategy and high-throughput DFT is utilized to search for anode materials with higher properties. Finally, many metalloids (Si, Sb, Ge), (post-)transition metals (Al, Pb, Cu, Cd, CdCu2) are predicted to be promising inexpensive anode candidates and warrant further experimental investigations.},
doi = {10.1002/aenm.201802994},
journal = {Advanced Energy Materials},
number = 9,
volume = 9,
place = {United States},
year = {2019},
month = {1}
}

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