High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions

doi:10.1016/j.joule.2018.11.014

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Title: High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions

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Abstract

The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na _2/3Mg _1/3Mn _2/3O ₂. Here, the bulk Mn redox emerges from initial discharge and is quantified by inverse partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen redox reversibility during the initial cycle, with 87% capacity sustained after 100 cycles. In Li _1.17Ni _0.21Co _0.08Mn _0.54O ₂, lattice oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice oxygen redox in both Li-ion and Na-ion systems. The contrast between Na _2/3Mg _1/3Mn _2/3O ₂ and Li _1.17Ni _0.21Co _0.08Mn _0.54O ₂ systems suggests the importance of distinguishing lattice oxygen redox from other oxygen activities for clarifying its intrinsic properties.

Authors:

Dai, Kehua ^[1]; Wu, Jinpeng ^[2]; Zhuo, Zengqing ^[3]; Li, Qinghao ^[4]; Sallis, Shawn ^[5]; Mao, Jing ^[6]; Ai, Guo ^[7]; Sun, Chihang ^[8]; Li, Zaiyuan ^[8]; Gent, William E. ^[9]; Chueh, William C. ^[10]; Chuang, Yi-de ^[11]; Zeng, Rong ^[12]; Shen, Zhi-xun ^[9]; Pan, Feng ^[13]; Yan, Shishen ^[14]; Piper, Louis F. J. ^[15]; Hussain, Zahid ^[11]; Liu, Gao ^[11];

^[11]

Northeastern Univ., Shenyang (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Stanford Univ., Stanford, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Peking Univ. Shenzhen Graduate School, Shenzhen (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shandong Univ., Jinan (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Binghamton Univ., Binghamton, NY (United States)
Zhengzhou Univ., Zhengzhou (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Tianjin Normal Univ., Tianjin (China)
Northeastern Univ., Shenyang (China)
Stanford Univ., Stanford, CA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Tsinghua Univ., Beijing (China)
Peking Univ. Shenzhen Graduate School, Shenzhen (China)
Shandong Univ., Jinan (China)
Binghamton Univ., Binghamton, NY (United States)

Publication Date:: 2018-12-12

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1564006

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Joule

Additional Journal Information:: Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2542-4351

Publisher:: Elsevier - Cell Press

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; anionic redox reaction; quantification; Na-ion battery; Li-ion battery; soft X-ray spectroscopy; cathode material layered oxide; Li-rich material; mapping of resonant inelastic X-ray scattering (mRIXS); reversibility of oxygen redox

Citation Formats


                    Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, and Yang, Wanli. High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions.  United States: N. p., 2018. 
        Web.  doi:10.1016/j.joule.2018.11.014.

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                    Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, & Yang, Wanli. High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions.  United States.  doi:10.1016/j.joule.2018.11.014.

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                    Dai, Kehua, Wu, Jinpeng, Zhuo, Zengqing, Li, Qinghao, Sallis, Shawn, Mao, Jing, Ai, Guo, Sun, Chihang, Li, Zaiyuan, Gent, William E., Chueh, William C., Chuang, Yi-de, Zeng, Rong, Shen, Zhi-xun, Pan, Feng, Yan, Shishen, Piper, Louis F. J., Hussain, Zahid, Liu, Gao, and Yang, Wanli. Wed .  
        "High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions".  United States.  doi:10.1016/j.joule.2018.11.014.

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@article{osti_1564006,

  title        = {High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions},

  author       = {Dai, Kehua and Wu, Jinpeng and Zhuo, Zengqing and Li, Qinghao and Sallis, Shawn and Mao, Jing and Ai, Guo and Sun, Chihang and Li, Zaiyuan and Gent, William E. and Chueh, William C. and Chuang, Yi-de and Zeng, Rong and Shen, Zhi-xun and Pan, Feng and Yan, Shishen and Piper, Louis F. J. and Hussain, Zahid and Liu, Gao and Yang, Wanli},

  abstractNote = {The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. Here, the bulk Mn redox emerges from initial discharge and is quantified by inverse partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen redox reversibility during the initial cycle, with 87% capacity sustained after 100 cycles. In Li1.17Ni0.21Co0.08Mn0.54O2, lattice oxygen redox is 76% initial-cycle reversible but with only 44% capacity retention after 500 cycles. These results unambiguously show the high reversibility of lattice oxygen redox in both Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing lattice oxygen redox from other oxygen activities for clarifying its intrinsic properties.},

  doi          = {10.1016/j.joule.2018.11.014},

  journal      = {Joule},

  number       = 2,

  volume       = 3,

  place        = {United States},

  year         = {2018},

  month        = {12}

}

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