Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy.
A family of mixed transition-metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1-3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy-loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance.
Zhejiang Provincial Key Laboratory of Solid State Optoelectronic Devices, Zhejiang Normal University, Jinhua, 321004, China.
Qingmei
Q
Su
Zhejiang Provincial Key Laboratory of Solid State Optoelectronic Devices, Zhejiang Normal University, Jinhua, 321004, China.
Shixin
S
Wang
Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Libing
L
Yao
Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Haojie
H
Li
Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Gaohui
G
Du
Zhejiang Provincial Key Laboratory of Solid State Optoelectronic Devices, Zhejiang Normal University, Jinhua, 321004, China.
Huiqun
H
Ye
Zhejiang Provincial Key Laboratory of Solid State Optoelectronic Devices, Zhejiang Normal University, Jinhua, 321004, China.
Yunzhang
Y
Fang
D011211:Electric Power Supplies; D004563:Electrochemistry; D004566:Electrodes; D005290:Ferric Compounds / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008422:Materials Testing / Q000379:methods; D053768:Metal Nanoparticles / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D015032:Zinc / Q000737:chemistry*
D005290:Ferric Compounds; C000499:ferric oxide; D008094:Lithium; D015032:Zinc