2022, Volume 8, Issue 1
Engineering >> 2022, Volume 8, Issue 1 doi: 10.1016/j.eng.2021.04.028
Modification of NASICON Electrolyte and Its Application in Real Na-Ion Cells
a Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
b Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
c Xiamen Institute of Rare-Earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China
d State Key Laboratory of Physical Chemistry of Solid Surfaces & Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
e HiNa Battery Technology Co., Ltd., Liyang 213300, China
f Yangtze River Delta Physics Research Center Co., Ltd., Liyang 213300, China
# These authors contributed equally to this work.
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Abstract
The low ionic conductivity of solid-state electrolytes (SSEs) and the inferior interfacial reliability between SSEs and solid-state electrodes are two urgent challenges hindering the application of solid-state sodium batteries (SSSBs). Herein, sodium (Na) super ionic conductor (NASICON)-type SSEs with a nominal composition of Na3+2xZr2–xMgxSi2PO12 were synthesized using a facile two-step solid-state method, among which Na3.3Zr1.85Mg0.15Si2PO12 (x = 0.15, NZSP-Mg0.15) showed the highest ionic conductivity of 3.54 mS∙cm–1 at 25 °C. By means of a thorough investigation, it was verified that the composition of the grain boundary plays a crucial role in determining the total ionic conductivity of NASICON. Furthermore, due to a lack of examination in the literature regarding whether NASICON can provide enough anodic electrochemical stability to enable high-voltage SSSBs, we first adopted a high-voltage Na3(VOPO4)2F (NVOPF) cathode to verify its compatibility with the optimized NZSP-Mg0.15 SSE. By comparing the electrochemical performance of cells with different configurations (low-voltage cathode vs high-voltage cathode, liquid electrolytes vs SSEs), along with an X-ray photoelectron spectroscopy (XPS) evaluation of the after-cycled NZSP-Mg0.15, it was demonstrated that the NASICON SSEs are not stable enough under high voltage, suggesting the importance of investigating the interface between the NASICON SSEs and high-voltage cathodes. Furthermore, by coating NZSP-Mg0.15 NASICON powder onto a polyethylene (PE) separator (PE@NASICON), a 2.42 A∙h non-aqueous Na-ion cell of carbon|PE@NASICON|NaNi2/9Cu1/9Fe1/3Mn1/3O2 was found to deliver an excellent cycling performance with an 88% capacity retention after 2000 cycles, thereby demonstrating the high reliability of a separator coated with NASICON-type SSEs.
Keywords
Solid-state electrolytes ; Solid-state sodium batteries ; NASICON ; Interface ; Separator ; Coating
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