The structural collapse of manganese-based materials during cycling greatly restricts its development in Sodium-ion batteries (SIBs). Hence, two-phase structures with different manganese valence states are designed based on an alternating voltage approach to mitigate volume expansion via two-phase coordination. Here distinct manganese valence states of precursor are driven via atmosphere. And in the following heat-induced phase transition, the elemental valence state is the decisive key for the structural and compositional evolution. In a batch of synthetic materials, MnO/MnS with bivalent states of manganese performs best as expected. Furthermore, NaPF6 in DEGDME is taken to replace the traditional carbonate electrolyte which is prone to produce unstable SEI film and leading to polarization. A series of characterization methods confirm that the energy barrier of charge transfer at the interface between electrolyte and electrode is the main factor determining the electrochemical characteristics of the interface and thus the energy storage performance. Ultimately, carbon dots (CDS) with rich functional groups are introduced in an effort to further promote the conductivity of MnO/MnS, and the in-situ generated C-S-Mn bond enhances electrochemical kinetic behaviors. This work provides an approach for designing manganese-based materials and the selection of electrolytes in sodium energy storage.