期刊
JOURNAL OF POWER SOURCES
卷 369, 期 -, 页码 146-153出版社
ELSEVIER
DOI: 10.1016/j.jpowsour.2017.09.079
关键词
Prussian blue analogues; Copper hexacyanoferrate; Zinc; Aqueous electrochemical energy storage; In operando X-ray diffraction; Synchrotron radiation
资金
- Consortium for Crystal Chemistry, C3 within the Rontgen Angstrom cluster, Swedish Research Council VR [2011-6512]
- Swedish Research Council (FORMAS) [245- 2014-668]
- StandUp for Energy
The storage process of Zn2+ in the Prussian blue analogue (PBA) copper hexacyanoferrate (Cu[Fe(CN)(6)](2/3)-nH(2) O-CuHCF) framework structure in a context of rechargeable aqueous batteries is examined by means of in operando synchrotron X-ray diffraction. Via sequential unit-cell parameter refinements of time-resolved diffraction data, it is revealed that the step-profile of the cell output voltage curves during repeated electrochemical insertion and removal of Zn2+ in the CuHCF host structure is associated with a non-linear contraction and expansion of the unit-cell in the range 0.36 < x < 1.32 for Znx/3Cu[Fe(CN)(6)](2/3)-nH(2)O. For a high insertion cation content there is no apparent change in the unit-cell contraction. Furthermore, a structural analysis with respect to the occupancies of possible Zn2+ sites suggests that the Fe(CN)(6) vacancies within the CuHCF framework play an important role in the structural-electrochemical behavior of this particular system. More specifically, it is observed that Zn2+ swaps position during electrochemical cycling, hopping between cavity sites to vacant ferricyanide sites. (C) 2017 The Authors. Published by Elsevier B.V.
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