The simultaneous intercalation of protons and Zn2+ ions in aqueous electrolytes presents a significant obstacle to the widespread adoption of aqueous zinc ion batteries (AZIBs) for large-scale use, a challenge that has yet to be overcome. To address this, we have developed a MnO2/tetramethylammonium (TMA) superstructure with an enlarged interlayer spacing, designed specifically to control H+/Zn2+ co-intercalation in AZIBs. Within this superstructure, the pre-intercalated TMA+ ions work as spacers to stabilize the layered structure of MnO2 cathodes and expand the interlayer spacing substantially by 28 % to 0.92 nm. Evidence from in operando pH measurements, in operando synchrotron X-ray diffraction, and X-ray absorption spectroscopy shows that the enlarged interlayer spacing facilitates the diffusion and intercalation of Zn2+ ions (which have a large ionic radius) into the MnO2 cathodes. This spacing also helps suppress the competing H+ intercalation and the formation of detrimental Zn4(OH)6SO4·5H2O, thereby enhancing the structural stability of MnO2. As a result, enhanced Zn2+ storage properties, including excellent capacity and long cycle stability, are achieved.
Keywords: Aqueous zinc ion batteries; In operando synchrotron diffraction; MnO(2); Superstructure; X-ray absorption spectroscopy.
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