Dataset Information

Real-time tracking the Li+-ion transition behavior and dynamics in solid Poly(vinyl alcohol)/LiClO4 electrolytes.

ABSTRACT: To delicately track the Li-ion transport in SPEs under an external electric field (EF) is a big challenge, considering the limitation of most spectroscopic methods to monitor the real-time conformational changes and track the dynamic process. Herein, real-time Li-ion transition behavior and transport dynamics in typical poly(vinyl alcohol)/LiClO4 electrolytes under an external EF have been studied by combining time-resolved Fourier transform infrared (FTIR) with two-dimensional correlation FTIR spectroscopy. Results show that no migration of Li-ions has been detected when the time scale of the EF loading is at nanosecond (less than 200?ns). However, for the first time, Li-ions have been found to significantly transfer along the EF direction as the time scale enhances to microsecond order of magnitude and the migration period is less than 10 microseconds. The Li+ migration in the SPEs under an EF is a complicated process including quasi-periodic dissociation and coordination effects between Li-ion carriers and polymeric chains.

SUBMITTER: Bao L

PROVIDER: S-EPMC5381101 | biostudies-literature | 2017 Apr

REPOSITORIES: biostudies-literature

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Publications

Real-time tracking the Li+-ion transition behavior and dynamics in solid Poly(vinyl alcohol)/LiClO4 electrolytes.

Bao Lixia L Zou Xin X Luo Xin X Pu Yanlei Y Wang Jiliang J Lei Jingxin J

Scientific reports 20170405

To delicately track the Li-ion transport in SPEs under an external electric field (EF) is a big challenge, considering the limitation of most spectroscopic methods to monitor the real-time conformational changes and track the dynamic process. Herein, real-time Li-ion transition behavior and transport dynamics in typical poly(vinyl alcohol)/LiClO4 electrolytes under an external EF have been studied by combining time-resolved Fourier transform infrared (FTIR) with two-dimensional correl ...[more]

PMID: 28378837

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Project description:Fluorinated electrolytes based on fluoroethylene carbonate (FEC) have been considered as promising alternative electrolytes for high-voltage and high-energy capacity lithium-ion batteries (LIBs). However, the compatibility of the fluorinated electrolytes with graphite negative electrodes is unclear. In this paper, we have systematically investigated, for the first time, the stability of fluorinated electrolytes with graphite negative electrodes, and the result shows that unlike the ethylene carbonate (EC)-based electrolyte, the FEC-based electrolyte (EC was totally replaced by FEC) is incapable of forming a protective and effective solid electrolyte interphase (SEI) that protects the electrolyte from runaway reduction on the graphite surface. The reason is that the lowest unoccupied molecular orbital energy levels are also lowered by the introduction of fluorine into the solvent, and the FEC solvent has poorer resistance against reduction, leading to instability on the graphite negative electrode. To tackle this problem, two lithium salts of lithium bis(oxalato)borate and lithium difluoro(oxalato)borate (LiDFOB) have been investigated as negative-electrode film-forming additives. Incorporation of only 0.5 wt % LiDFOB to a FEC-based electrolyte [1.0 M LiPF6 in 3:7 (FEC-ethyl methyl carbonate)] results in excellent cycling performance of the graphite negative electrode. This improved property originates from the generation of a thinner and better quality SEI film with little LiF by the sacrificial reduction of the LiDFOB additive on the graphite negative electrode surface. On the other hand, this additive can stabilize the electrolyte by scavenging HF. Meanwhile, the incorporated LiDFOB additive has positive influence on the interphase layer on the positive electrode surface and significantly decreases the amount of HF formation, finally leading to improved cycling stability and rate capability of LiNi0.5Mn1.5O4 electrodes at a high cutoff voltage of 5 V. The data demonstrate that the LiDFOB additive not only exhibits a superior compatibility with graphite but also improves the electrochemical properties of high-voltage spinel LiNi0.5Mn1.5O4 positive electrodes considerably, confirming its potential as a prospective, multifunctional additive for 5 V fluorinated electrolytes in high-energy capacity lithium-ion batteries (LIBs).

Dataset Information

Real-time tracking the Li+-ion transition behavior and dynamics in solid Poly(vinyl alcohol)/LiClO4 electrolytes.

Publications

Real-time tracking the Li<sup>+</sup>-ion transition behavior and dynamics in solid Poly(vinyl alcohol)/LiClO<sub>4</sub> electrolytes.

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