TY - JOUR
T1 - Aliovalent cation substitution in Na3Zr2Si2PO12 for practical solid-state sodium metal batteries
AU - He, Jingxin
AU - Yang, Shuaishuai
AU - Xiao, Xiong
AU - Fang, Debao
AU - Miao, Runqing
AU - Wang, Chengzhi
AU - Chen, Lai
AU - Li, Ning
AU - Li, Jingbo
AU - Su, Yuefeng
AU - Jin, Haibo
N1 - Publisher Copyright:
© 2025
PY - 2025/2
Y1 - 2025/2
N2 - High-performance solid electrolytes with high conductivity and good electrode compatibility are critical for the operable solid-state sodium metal batteries. With the Na+ superionic conductor-typed Na3Zr2Si2PO12 as a matrix, an aliovalent cation substitution strategy using Ni2+, Mn3+, Nb5+, Mo6+ substituting Zr4+ is investigated on the ionic conductivity and interfacial performance of solid-state sodium metal batteries. The low-valence Ni2+ and Mn3+ show notable effect on both enlarging the bottlenecks in the grain lattices and reducing the barriers across the grain boundaries for Na+ migration, while the high-valence Nb5+ and Mo6+ mainly facilitate Na+ migration across the grain boundaries. By tuning the doping ratios, the Ni2+ doped Na3.4Zr1.8Ni0.2Si2PO12 achieves the optimal total conductivity of 2.284 mS cm-1 at 30 °C which is 6 times higher than the undoped Na3Zr2Si2PO12. Moreover, the aliovalent cation substitution essentially improves the interface compatibility with the sodium metal, achieving reduced interfacial resistances as low as 7.80 ohm cm2 and enlarged critical current densities as high as 1.0 mA cm-2. Besides, stable charge/discharge cycles at high rates for both the symmetric Na||Na cells over 3400 h and the full cells over 2400 cycles are achieved to signify the practical merits of the neat aliovalent cation substitution strategy.
AB - High-performance solid electrolytes with high conductivity and good electrode compatibility are critical for the operable solid-state sodium metal batteries. With the Na+ superionic conductor-typed Na3Zr2Si2PO12 as a matrix, an aliovalent cation substitution strategy using Ni2+, Mn3+, Nb5+, Mo6+ substituting Zr4+ is investigated on the ionic conductivity and interfacial performance of solid-state sodium metal batteries. The low-valence Ni2+ and Mn3+ show notable effect on both enlarging the bottlenecks in the grain lattices and reducing the barriers across the grain boundaries for Na+ migration, while the high-valence Nb5+ and Mo6+ mainly facilitate Na+ migration across the grain boundaries. By tuning the doping ratios, the Ni2+ doped Na3.4Zr1.8Ni0.2Si2PO12 achieves the optimal total conductivity of 2.284 mS cm-1 at 30 °C which is 6 times higher than the undoped Na3Zr2Si2PO12. Moreover, the aliovalent cation substitution essentially improves the interface compatibility with the sodium metal, achieving reduced interfacial resistances as low as 7.80 ohm cm2 and enlarged critical current densities as high as 1.0 mA cm-2. Besides, stable charge/discharge cycles at high rates for both the symmetric Na||Na cells over 3400 h and the full cells over 2400 cycles are achieved to signify the practical merits of the neat aliovalent cation substitution strategy.
KW - Aliovalent cation substitution
KW - Conductivity
KW - Interfacial resistance
KW - Sodium metal batteries
KW - Solid electrolyte
UR - http://www.scopus.com/inward/record.url?scp=85215099242&partnerID=8YFLogxK
U2 - 10.1016/j.ensm.2025.104037
DO - 10.1016/j.ensm.2025.104037
M3 - Article
AN - SCOPUS:85215099242
SN - 2405-8297
VL - 75
JO - Energy Storage Materials
JF - Energy Storage Materials
M1 - 104037
ER -