Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost and environmental friendliness. However, their applications have been limited by a narrow potential window (∼1.23 V), beyond which the hydrogen and oxygen evolution reactions occur. Here we report the formation of layered Mn5O8 pseudocapacitor electrode material with a well-ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0 V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge–discharge cycles. The interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn5O8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn2+/Mn4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn5O8.

Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na0.27MnO2) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g−1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.

We report a (Ni)­MnO2 layered birnessite material with a framwork doping of Ni ions as the cathode for much enhanced aqueous Na-ion storage. Characterized by neutron total scattering and pair distribution function (PDF) analysis, in situ XRD, in situ X-ray PDF, XANES, and XPS, the synergistic interaction between disordered [NiO6] and ordered [MnO6] octahedra contribute to the enhanced specific capacity and cycle life (63 mAh g–1 at 0.2 A g–1 after 2000 full-cell cycles). Electro-kinetic analysis and structural characterizations show that stable local structure is maintained by [MO6] octahedra during charge–discharge processes, while disordered [NiO6] octahedra significantly improve pseudocapacitive redox charge storage. This finding may pave a new way for designing a new type of low-cost and high performance layered electrode materials.

A rechargeable Zn-ion battery is a promising aqueous system, where coinsertion of Zn2+ and H+ could address the obstacles of the sluggish ionic transport in cathode materials imposed by multivalent battery chemistry. However, there is a lack of fundamental understanding of this dual-ion transport, especially the potentiodynamics of the storage process. Here, a quantitative analysis of Zn2+ and H+ transport in a disordered sodium vanadate (NaV3O8) cathode material has been reported. Collectively, synchrotron X-ray analysis shows that both Zn2+ and H+ storages follow an intercalation storage mechanism in NaV3O8 and proceed in a sequential manner, where intercalations of 0.26 Zn2+ followed by 0.24 H+ per vanadium atom occur during discharging, while reverse dynamics happens during charging. Such a unique and synergistic dual-ion sequential storage favors a high capacity (265 mA h g–1) and an energy density (221 W h kg–1) based on the NaV3O8 cathode and a great cycling life (a capacity retention of 78% after 2000 cycles) in Zn/NaV3O8 full cells.

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost, and environmental friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. Herein, the development of a biphase cobalt-manganese oxide (CoMnO) nanostructured electrode material is reported, comprised of a layered MnO 2 ⋅H 2 O birnessite phase and a (Co 0.83 Mn 0.13 Va 0.04 ) tetra (Co 0.38 Mn 1.62 ) octa O 3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The biphase CoMnO material demonstrates an excellent storage capacity toward Na-ions in an aqueous electrolyte (121 mA h g −1 at a scan rate of 1 mV s −1 in the half-cell and 81 mA h g −1 at a current density of 2 A g −1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g −1 a rate of 360 C). Electrokinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the CoMnO material by facilitating both diffusion-limited redox and capacitive charge storage processes.