Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries
Abstract
Significant research effort has focused on improving the specific energy of lithium-ion batteries for emerging applications, such as electric vehicles. Recently, a rock salt–type Li4Mn2O5 cathode material with a large discharge capacity (~350 mA·hour g–1) was discovered. However, a full structural model of Li4Mn2O5 and its corresponding phase transformations, as well as the atomistic origins of the high capacity, warrants further investigation. We use first-principles density functional theory (DFT) calculations to investigate both the disordered rock salt–type Li4Mn2O5 structure and the ordered ground-state structure. The ionic ordering in the ground-state structure is determined via a DFT-based enumeration method. We use both the ordered and disordered structures to interrogate the delithiation process and find that it occurs via a three-step reaction pathway involving the complex interplay of cation and anion redox reactions: (i) an initial metal oxidation, Mn3+→Mn4+ (LixMn2O5, 4 > x > 2); (ii) followed by anion oxidation, O2– → O1– (2 > x > 1); and (iii) finally, further metal oxidation, Mn4+ → Mn5+ (1 > x > 0). This final step is concomitant with the Mn migration from the original octahedral site to the adjacent tetrahedral site, introducing a kinetic barrier to reversible charge/discharge cycles. Armed with thismore »
- Authors:
-
[1];
[2];
[1];
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1543999
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Science Advances
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2375-2548
- Publisher:
- AAAS
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Science & Technology; Other Topics
Citation Formats
Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., and Wolverton, Chris. Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries. United States: N. p., 2018.
Web. doi:10.1126/sciadv.aao6754.
Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., & Wolverton, Chris. Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries. United States. https://doi.org/10.1126/sciadv.aao6754
Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., and Wolverton, Chris. Fri .
"Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries". United States. https://doi.org/10.1126/sciadv.aao6754. https://www.osti.gov/servlets/purl/1543999.
@article{osti_1543999,
title = {Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries},
author = {Yao, Zhenpeng and Kim, Soo and He, Jiangang and Hegde, Vinay I. and Wolverton, Chris},
abstractNote = {Significant research effort has focused on improving the specific energy of lithium-ion batteries for emerging applications, such as electric vehicles. Recently, a rock salt–type Li4Mn2O5 cathode material with a large discharge capacity (~350 mA·hour g–1) was discovered. However, a full structural model of Li4Mn2O5 and its corresponding phase transformations, as well as the atomistic origins of the high capacity, warrants further investigation. We use first-principles density functional theory (DFT) calculations to investigate both the disordered rock salt–type Li4Mn2O5 structure and the ordered ground-state structure. The ionic ordering in the ground-state structure is determined via a DFT-based enumeration method. We use both the ordered and disordered structures to interrogate the delithiation process and find that it occurs via a three-step reaction pathway involving the complex interplay of cation and anion redox reactions: (i) an initial metal oxidation, Mn3+→Mn4+ (LixMn2O5, 4 > x > 2); (ii) followed by anion oxidation, O2– → O1– (2 > x > 1); and (iii) finally, further metal oxidation, Mn4+ → Mn5+ (1 > x > 0). This final step is concomitant with the Mn migration from the original octahedral site to the adjacent tetrahedral site, introducing a kinetic barrier to reversible charge/discharge cycles. Armed with this knowledge of the charging process, we use high-throughput DFT calculations to study metal mixing in this compound, screening potential new materials for stability and kinetic reversibility. We predict that mixing with M = V and Cr in Li4(Mn,M)2O5 will produce new stable compounds with substantially improved electrochemical properties.},
doi = {10.1126/sciadv.aao6754},
journal = {Science Advances},
number = 5,
volume = 4,
place = {United States},
year = {Fri May 18 00:00:00 EDT 2018},
month = {Fri May 18 00:00:00 EDT 2018}
}
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