Voltage oscillation at subzero in sodium-ion batteries (SIBs) has been a common but overlooked scenario, almost yet to be understood. For example, the phenomenon seriously deteriorates the performance of Na3V2(PO4)3 (NVP) cathode in PC (propylene carbonate)/EC (ethylene carbonate)-based electrolyte at −20 °C. Here, the correlation between voltage oscillation, structural evolution, and electrolytes has been revealed based on theoretical calculations, in-/ex-situ techniques, and cross-experiments. It is found that the local phase transition of the Na3V2(PO4)3 (NVP) cathode in PC/EC-based electrolyte at −20 °C should be responsible for the oscillatory phenomenon. Furthermore, the low exchange current density originating from the high desolvation energy barrier in NVP-PC/EC system also aggravates the local phase transformation, resulting in severe voltage oscillation. By introducing the diglyme solvent with lower Na-solvent binding energy, the voltage oscillation of the NVP can be eliminated effectively at subzero. As a result, the high capacity retentions of 98.3% at −20 °C and 75.3% at −40 °C are achieved. The finding provides insight into the abnormal SIBs degradation and brings the voltage oscillation behavior of rechargeable batteries into the limelight.
Yao Lu,Jose A. Alonso,Qiang Yi,Liang Lu,Zhong Lin Wang,Chunwen Sun
Solid-state sodium batteries (SSSBs) are promising electrochemical energy storage devices due to their high energy density, high safety, and abundant resource of sodium. However, low conductivity of solid electrolyte as well as high interfacial resistance between electrolyte and electrodes are two main challenges for practical application. To address these issues, pure phase Na 3 Zr 2 Si 2 PO 12 (NZSP) materials with Ca 2+ substitution for Zr 4+ are synthesized by a sol-gel method. It shows a high ionic conductivity of more than 10 −3 S cm −1 at 25 °C. Moreover, a robust SSSB is developed by integrating sodium metal anodes into NZSP-type monolithic architecture, forming a 3D electronic and ionic conducting network. The interfacial resistance is remarkably reduced and the monolithic symmetric cell displays stable sodium platting/striping cycles with low polarization for over 600 h. Furthermore, by combining sodium metal anode with Na 3 V 2 (PO 4 ) 3 cathode, an SSSB is demonstrated with high rate capability and excellent cyclability. After 450 cycles, the capacity of the cell is still kept at 94.9 mAh g −1 at 1 C. This unique design of monolithic electrolyte architecture provides a promising strategy toward realizing high-performance SSSBs.
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