期刊
ACS APPLIED MATERIALS & INTERFACES
卷 11, 期 1, 页码 674-682出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.8b16284
关键词
aqueous Zn-ion batteries; charge storage mechanism; oxide vs nonoxide hosts; Zn2+ vs proton intercalation; layered double hydroxide precipitation; consequence of proton intercalation
资金
- Swiss National Science Foundation (SNSF)
- National Center of Competence in Research (NCCR) Materials' Revolution: Computational Design and Discovery of Novel Materials (MARVEL) of the Swiss National Science Foundation
Aqueous Zn-ion batteries, which are being proposed as large-scale energy storage solutions because of their unparalleled safety and cost advantage, are composed of a positive host (cathode) material, a metallic zinc anode, and a mildly acidic aqueous electrolyte (pH approximate to 3-7). Typically, the charge storage mechanism is believed to be reversible Zn2+ (de)intercalation in the cathode host, with the exception of alpha-MnO2, for which multiple vastly different and contradicting mechanisms have been proposed. However, our present study, combining electrochemical, operando X-ray diffraction, electron microscopy in conjunction with energy-dispersive X-ray spectroscopy, and in situ pH evolution analyses on two oxide hosts-tunneled alpha-MnO2 and layered V3O7 center dot H2O vis-a-vis two nonoxide hosts-layered VS2 and tunneled Zn-3[Fe(CN)(6)](2), suggests that oxides and nonoxides follow two dissimilar charge storage mechanisms. While the oxides behave as dominant proton intercalation materials, the nonoxides undergo exclusive zinc intercalation. Stabilization of H+ on the hydroxyl-terminated oxide surface is revealed to facilitate the proton intercalation by a preliminary molecular dynamics simulation study. Proton intercalation for both oxides leads to the precipitation of layered double hydroxide (LDH)-Zn4SO4(OH)(6)center dot 5H(2)O with a ZnSO4/H2O electrolyte and a triflate anion (CF3SO3-)-based LDH with a Zn(SO3CF3)(2)/H2O electrolyte-on the electrode surface. The LDH precipitation buffers the pH of the electrolytes to a mildly acidic value, sustaining the proton intercalation to deliver large specific capacities for the oxides. Moreover, we also show that the stability of the LDH precipitate is crucial for the rechargeability of the oxide cathodes, revealing a critical link between the charge storage mechanism and the performance of the oxide hosts in aqueous zinc batteries.
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