Cryo-Electron Tomography of Highly Deformable and Adherent Solid-Electrolyte Interphase Exoskeleton in Li-Metal Batteries with Ether-Based Electrolyte

Han, Bing1,2; Li, Xiangyan1,3; Wang, Qi1; Zou, Yucheng1; Xu, Guiyin4,5; Cheng, Yifeng1,3; Zhang, Zhen1; Zhao, Yusheng6; Deng, Yonghong1; Li, Ju4,5; Gu, Meng1,6

2022-02-01

10.1002/adma.202108252

ADVANCED MATERIALS   影响因子和分区

0935-9648

1521-4095

The 3D nanocomposite structure of plated lithium (Li-Metal) and solid electrolyte interphases (SEI), including a polymer-rich surficial passivation layer (SEI exoskeleton) and inorganic SEI "fossils" buried inside amorphous Li matrix, is resolved using cryogenic transmission electron microscopy. With ether-based DOLDME-LiTFSI electrolyte, LiF and Li2O nanocrystals are formed and embedded in a thin but tough amorphous polymer in the SEI exoskeleton. The fast Li-stripping directions are along [1 over bar 10] or [121 over bar ], which produces eight exposed {111} planes at halfway charging. Full Li stripping produces completely sagging, empty SEI husks that can sustain large bending and buckling, with the smallest bending radius of curvature observed approaching tens of nanometers without apparent damage. In the 2nd round of Li plating, a thin Li-BCC sheet first nucleates at the current collector, extends to the top end of the deflated SEI husk, and then expands its thickness. The apparent zero wetting angle between Li-BCC and the SEI interior means that the heterogeneous nucleation energy barrier is zero. Due to its complete-wetting property and chemo-mechanical stability, the SEI largely prevents further reactions between the Li metal and the electrolyte, which explains the superior performance of Li-metal batteries with ether-based electrolytes. However, uneven refilling of the SEI husks results in dendrite protrusions and some new SEI formation during the 2nd plating. A strategy to form bigger SEI capsules during the initial cycle with higher energy density than the following cycles enables further enhanced Coulombic efficiency to above 99%.

lithium-metal batteries lithium plating lithium stripping solid electrolyte interphase husks surface passivation layers

SCI ; EI

英语

NI论文

第一 ; 通讯

Guangdong Innovative and Entrepreneurial Research Team Program[2019ZT08C044] ; Guangdong-HongKong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices[2019B121205001] ; Shenzhen DRC project[[2018]1433] ; Shenzhen Science and Technology Program["KQTD20190929173815000",20200925154115001,"JCYJ20210324115809026"] ; NSF[CBET-2034902]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Multidisciplinary ; Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:000754485200001

WILEY-V C H VERLAG GMBH

20220711643911

Ethers ; II-VI semiconductors ; Lithium batteries ; Lithium compounds ; Mechanical stability ; Metallic matrix composites ; Nucleation ; Passivation ; Phosphorus compounds ; Polymer matrix composites ; Solid electrolytes ; Solid-State Batteries ; Sulfur compounds ; Wetting

Metallurgy and Metallography:531 ; Protection Methods:539.2.1 ; Primary Batteries:702.1.1 ; Secondary Batteries:702.1.2 ; Semiconducting Materials:712.1 ; Optical Devices and Systems:741.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Organic Compounds:804.1 ; Polymeric Materials:815.1 ; Crystal Growth:933.1.2

MATERIALS SCIENCE

Web of Science

1.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
2.Univ Calif San Diego, Dept Nano Engn, La Jolla, CA 92093 USA
3.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China
4.MIT, Dept Nucl Sci & Engn, 77 Massachusetts Ave, Cambridge, MA 02139 USA
5.MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA
6.Southern Univ Sci & Technol, Guangdong HongKong Macao Joint Lab Photon Thermal, Shenzhen 518055, Peoples R China

Han, Bing,Li, Xiangyan,Wang, Qi,et al. Cryo-Electron Tomography of Highly Deformable and Adherent Solid-Electrolyte Interphase Exoskeleton in Li-Metal Batteries with Ether-Based Electrolyte[J]. ADVANCED MATERIALS,2022,34.

Han, Bing.,Li, Xiangyan.,Wang, Qi.,Zou, Yucheng.,Xu, Guiyin.,...&Gu, Meng.(2022).Cryo-Electron Tomography of Highly Deformable and Adherent Solid-Electrolyte Interphase Exoskeleton in Li-Metal Batteries with Ether-Based Electrolyte.ADVANCED MATERIALS,34.

Han, Bing,et al."Cryo-Electron Tomography of Highly Deformable and Adherent Solid-Electrolyte Interphase Exoskeleton in Li-Metal Batteries with Ether-Based Electrolyte".ADVANCED MATERIALS 34(2022).