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

被引：278

作者：

Dai, Kehua ^{[1
,2
,3
]}

Wu, Jinpeng ^{[2
,4
]}

Zhuo, Zengqing ^{[2
,5
]}

Li, Qinghao ^{[2
,6
]}

Sallis, Shawn ^{[2
,7
]}

Mao, Jing ^{[8
]}

Ai, Guo ^{[3
,9
]}

Sun, Chihang ^{[1
]}

Li, Zaiyuan ^{[1
]}

Gent, William E. ^{[10
]}

Chueh, William C. ^{[11
,12
]}

Chuang, Yi-de ^{[2
]}

Zeng, Rong ^{[13
]}

Shen, Zhi-xun ^{[4
]}

Pan, Feng ^{[5
]}

Yan, Shishen ^{[6
]}

Piper, Louis F. J. ^{[7
]}

Hussain, Zahid ^{[2
]}

Liu, Gao ^{[3
]}

Yang, Wanli ^{[2
]}

机构：

[1] Northeastern Univ, Sch Met, Shenyang 110819, Liaoning, Peoples R China

[2] Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA

[3] Lawrence Berkeley Natl Lab, Energy Storage & Distributed Resources Div, Energy Technol Area, Berkeley, CA 94720 USA

[4] Stanford Univ, Geballe Lab Adv Mat, Stanford, CA 94305 USA

[5] Peking Univ, Shenzhen Grad Sch, Sch Adv Mat, Shenzhen 518055, Peoples R China

[6] Shandong Univ, Sch Phys, Natl Key Lab Crystal Mat, Jinan 250100, Shandong, Peoples R China

[7] SUNY Binghamton, Dept Mat Sci & Engn, Binghamton, NY 13902 USA

[8] Zhengzhou Univ, Sch Mat Sci & Engn, Zhengzhou 450001, Henan, Peoples R China

[9] Tianjin Normal Univ, Coll Phys & Mat Sci, Tianjin 300387, Peoples R China

[10] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[11] Stanford Univ, Dept Mat Sci & Engn, Stanford, CA 94305 USA

[12] SLAC Natl Accelerator Lab, Stanford Inst Mat & Energy Sci, Menlo Pk, CA 94025 USA

[13] Tsinghua Univ, Dept Elect Engn, Beijing 100084, Peoples R China

来源：

JOULE | 2019年 / 3卷 / 02期

基金：

中国国家自然科学基金;

关键词：

POSITIVE ELECTRODE MATERIAL; HIGH-CAPACITY; CATHODE MATERIAL; CHARGE-COMPENSATION; LAYERED OXIDES; ION BATTERIES; LI; NA; CHEMISTRY; EVOLUTION;

D O I：

10.1016/j.joule.2018.11.014

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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. 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.

引用

页码：518 / 541

页数：24

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