Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries

Yao, Zhenpeng; Kim, Soo; He, Jiangang; Hegde, Vinay I.; Wolverton, Chris

doi:10.1126/sciadv.aao6754

Title: Interplay of cation and anion redox in Li₄Mn₂O₅ cathode material and prediction of improved Li₄(Mn,M)₂O₅ electrodes for Li-ion batteries

Journal Article · Fri May 18 00:00:00 EDT 2018 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aao6754· OSTI ID:1543999

^[1];

^[2]; He, Jiangang ^[1];

^[1]; Wolverton, Chris ^[1]

Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

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⁺ (Li_xMn₂O₅, 4 > x > 2); (ii) followed by anion oxidation, O^2– → O^1– (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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1543999

Journal Information:: Science Advances, Vol. 4, Issue 5; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 53 works

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Title: Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries

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Title: Interplay of cation and anion redox in Li₄Mn₂O₅ cathode material and prediction of improved Li₄(Mn,M)₂O₅ electrodes for Li-ion batteries