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Title: In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles

 [1];  [2];  [3];  [4];  [1]
  1. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh PA 15261 USA
  2. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque NM 87185 USA
  3. School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 China
  4. Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qin Huang Dao Hebei Province 066004 China
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Advanced Materials; Journal Volume: 29; Journal Issue: 26; Related Information: NEES partners with University of Maryland (lead); University of California, Irvine; University of Florida; Los Alamos National Laboratory; Sandia National Laboratories; Yale University
Country of Publication:
United States
bio-inspired, energy storage (including batteries and capacitors), defects, charge transport, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Zhong, Li, Liu, Yang, Han, Wei-Qiang, Huang, Jian Yu, and Mao, Scott X. In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles. United States: N. p., 2017. Web. doi:10.1002/adma.201700236.
Zhong, Li, Liu, Yang, Han, Wei-Qiang, Huang, Jian Yu, & Mao, Scott X. In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles. United States. doi:10.1002/adma.201700236.
Zhong, Li, Liu, Yang, Han, Wei-Qiang, Huang, Jian Yu, and Mao, Scott X. Fri . "In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles". United States. doi:10.1002/adma.201700236.
title = {In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles},
author = {Zhong, Li and Liu, Yang and Han, Wei-Qiang and Huang, Jian Yu and Mao, Scott X.},
abstractNote = {},
doi = {10.1002/adma.201700236},
journal = {Advanced Materials},
number = 26,
volume = 29,
place = {United States},
year = {Fri May 05 00:00:00 EDT 2017},
month = {Fri May 05 00:00:00 EDT 2017}
  • Although a non-equilibrium single-phase reaction, with the absence of nucleation and growth of a second phase, is believed to be a key factor for high-rate performance of lithium-ion batteries, it is thermodynamically unfavorable and usually proceeds in electrode materials with small particle sizes (tens of nanometers). Unfortunately, the phase evolutions inside such small particles are often shrouded by the macroscopic inhomogeneous reactions of electrodes containing millions of particles, leading to intensive debate over the size-dependent microscopic reaction mechanisms. Here, we provide a generally applicable methodology based on in-situ electron diffraction study on a multi-particle system to track the lithiation pathwaysmore » in individual nanoparticles, and unambiguously reveal that lithiation of anatase TiO 2, previously long believed to be biphasic, converts to a single-phase reaction when the particle size is below ~25 nm. Our results imply the prevalence of such a size-dependent transition in lithiation mechanism among intercalation compounds whose lithium miscibility gaps are associated with a prominent size effect, and therefore provide important guidelines for designing high-power electrodes, especially cathodes.« less
  • Cited by 1
  • This paper reports development of a lithium-ion battery nanostructure device using a single nanowire for in-stu TEM study of the battery. This prototype lithium ion battery was built using a single SnO₂ nanowire as the anode, an air stable salt: lithium bis(trifluoromethansulfonyl) imide (LiTFSI) in a hydrophobic ionic liquid: 1-butyl-1-methylpyrrolidium TFSI (P14TFSI) as the electrolyte, and LiCoO₂ as the cathode. The microstructure evolution of the single nanowire anode was studied using TEM imaging, electron diffraction, and electron energy-loss spectroscopy during the operation of the battery. It has been observed that during initial charging, the electrolyte was found to decompose andmore » subsequently be electrodeposited on the anode, leading to the formation of a coating layer on the anode. This coating layer was enriched with Li. Formation of this layer will retard the Li intercalation of SnO₂. This in situ TEM observation provides direct evidence that accounts for the observed low capacity and fast fading of the Li battery when LiTFSI-P14TFSI is used as the electrolyte.« less
  • Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less