Revealing the Intrinsic Atomic Structure and Chemistry of Amorphous LiO2-Containing Products in Li-O2Batteries Using Cryogenic Electron Microscopy

Zhang，Peng1,2; Han，Bing1,3; Yang，Xuming1; Zou，Yucheng1; Lu，Xinzhen1; Liu，Xiao4; Zhu，Yuanmin1,5; Wu，Duojie1; Shen，Shaocheng6; Li，Lei1; Zhao，Yong4; Francisco，Joseph S.7; Gu，Meng1

2022-02-09

10.1021/jacs.1c10146

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

Aprotic lithium-oxygen batteries (LOBs) are promising energy storage systems characterized by ultrahigh theoretical energy density. Extensive research has been devoted to this battery technology, yet the detailed operational mechanisms involved, particularly unambiguous identification of various discharge products and their specific distributions, are still unknown or are subjects of controversy. This is partly because of the intrinsic complexity of the battery chemistry but also because of the lack of atomic-level insight into the oxygen electrodes acquired via reliable techniques. In the current study, it is demonstrated that electron beam irradiation could induce crystallization of amorphous discharge products. Cryogenic conditions and a low beam dosage have to be used for reliable transmission electron microscopy (TEM) characterization. High-resolution cryo-TEM and electron energy loss spectroscopy (EELS) analysis of toroidal discharge particles unambiguously identified the discharge products as a dominating amorphous LiO2 phase with only a small amount of nanocrystalline Li2O2 islands dispersed in it. In addition, uniform mixing of carbon-containing byproducts is identified in the discharge particles with cryo-EELS, which leads to a slightly higher charging potential. The discharge products can be reversibly cycled, with no visible residue after full recharge. We believe that the amorphous superoxide dominating discharge particles can lead researchers to reconsider the chemistry of LOBs and pay special attention to exclude beam-induced artifacts in traditional TEM characterizations.

SCI ; EI

英语

NI期刊

第一 ; 通讯

Guangdong Innovative and Entrepreneurial Research Team Program[2019ZT08C044];National Natural Science Foundation of China[21802065];

Chemistry

Chemistry, Multidisciplinary

WOS:000766221400016

AMER CHEMICAL SOC

20220611606219

Cryogenics ; Electrodes ; Electron energy levels ; Electron energy loss spectroscopy ; Electron scattering ; Electrons ; Energy dissipation ; Lithium ; Lithium batteries ; Lithium compounds ; Nanocrystals ; Oxygen

Energy Losses (industrial and residential):525.4 ; Lithium and Alloys:542.4 ; Alkali Metals:549.1 ; Cryogenics:644.4 ; Primary Batteries:702.1.1 ; Optical Devices and Systems:741.3 ; Nanotechnology:761 ; Chemical Products Generally:804 ; Crystalline Solids:933.1

2-s2.0-85124158267

Scopus

1.Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.Department of Chemistry,College of Sciences,Northeastern University,Shenyang,Liaoning,110819,China
3.Department of Nano Engineering,University of California San Diego,La Jolla,92093-0448,United States
4.Key Lab for Special Functional Materials of Ministry of Education,School of Materials Science and Engineering,Henan University,Kaifeng,475004,China
5.School of Material Science and Engineering,Dongguan University of Technology,Dongguan,Guangdong,523808,China
6.Department of Materials Science and Nano Engineering,Rice University,Houston,77251,United States
7.Department of Earth and Environmental Sciences,Department of Chemistry,University of Pennsylvania,Philadelphia,19104,United States

Zhang，Peng,Han，Bing,Yang，Xuming,et al. Revealing the Intrinsic Atomic Structure and Chemistry of Amorphous LiO2-Containing Products in Li-O2Batteries Using Cryogenic Electron Microscopy[J]. Journal of the American Chemical Society,2022,144(5):2129-2136.

Zhang，Peng.,Han，Bing.,Yang，Xuming.,Zou，Yucheng.,Lu，Xinzhen.,...&Gu，Meng.(2022).Revealing the Intrinsic Atomic Structure and Chemistry of Amorphous LiO2-Containing Products in Li-O2Batteries Using Cryogenic Electron Microscopy.Journal of the American Chemical Society,144(5),2129-2136.

Zhang，Peng,et al."Revealing the Intrinsic Atomic Structure and Chemistry of Amorphous LiO2-Containing Products in Li-O2Batteries Using Cryogenic Electron Microscopy".Journal of the American Chemical Society 144.5(2022):2129-2136.