Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution

Lun, Zhengyan; Ouyang, Bin; Kitchaev, Daniil A.; Clément, Raphaële J.; Papp, Joseph K.; Balasubramanian, Mahalingam; Tian, Yaosen; Lei, Teng; Shi, Tan; McCloskey, Bryan D.; Lee, Jinhyuk; Ceder, Gerbrand

doi:10.1002/aenm.201802959

Title: Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution

Journal Article · Fri Nov 16 00:00:00 EST 2018 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201802959· OSTI ID:1493873

Lun, Zhengyan ^[1]; Ouyang, Bin ^[1]; Kitchaev, Daniil A. ^[2]; Clément, Raphaële J. ^[3]; Papp, Joseph K. ^[4]; Balasubramanian, Mahalingam ^[5]; Tian, Yaosen ^[3]; Lei, Teng ^[4]; Shi, Tan ^[1]; McCloskey, Bryan D. ^[6]; Lee, Jinhyuk ^[3];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

We report the recent discovery of Li-excess cation-disordered rock salt cathodes has greatly enlarged the design space of Li-ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn³⁺–Nb⁵⁺-based cation-disordered oxyfluorides, Li_1.2Mn³⁺_0.6+0.5xNb⁵⁺_0.2-0.5xO_2-xF_x (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition-metal redox (Mn³⁺/Mn⁴⁺) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn³⁺-induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn-redox capacity to the overall capacity.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); Robert Bosch GmbH; Umicore

Grant/Contract Number:: AC02-06CH11357; AC02‐05CH11231; AC02-05CH11231; NSF DMR 1720256

OSTI ID:: 1493873

Alternate ID(s):: OSTI ID: 1482427

Journal Information:: Advanced Energy Materials, Vol. 9, Issue 2; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 119 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
cyclability
DFT
fluorination
Jahn–Teller distortion
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Title: Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution

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