The Impact of La Doping on the Ionic Conductivity of Na3+xLaxZr2-xSi2PO12 Solid-State Electrolytes

被引：0
作者：
Chen, Chunying [1 ,2 ]
Ren, Jinjun [1 ,2 ]
Jiao, Qing [3 ]
Tang, Jingping [1 ]
Hu, Lili [1 ]
机构：
[1] Chinese Acad Sci, Shanghai Inst Opt & Fine Mech, Special Glasses & Fibers Res Ctr, Adv Laser & Optoelect Funct Mat Dept, Shanghai 201800, Peoples R China
[2] Univ Chinese Acad Sci, Ctr Mat Sci & Optoelect Engn, Beijing 100049, Peoples R China
[3] Ningbo Univ, Adv Technol Res Inst, Lab Infrared Mat & Devices, Ningbo 315211, Peoples R China
来源：
JOURNAL OF PHYSICAL CHEMISTRY C | 2025年 / 129卷 / 07期
关键词：
TO-CRYSTAL TRANSITION; DOUBLE-RESONANCE NMR; ADIABATIC PULSES; NASICON; BATTERIES; CHEMISTRY; TRANSPORT; PHASE; ER; NA;
D O I：
10.1021/acs.jpcc.4c07861
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Joint doping with trivalent and monovalent ions is a widely adopted strategy to enhance the ionic conductivities of NASICON-type solid-state electrolytes (SSEs) with the general formula Na1+x Zr2Si x P3-x O12, but the underlying microscopic mechanism remains unclear. In this study, we synthesized a series of Na3+x La x Zr2-x Si2PO12 (NLZSPx, 0 <= x <= 0.4) ceramics and characterized their electrical properties and structures by using electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and advanced solid-state nuclear magnetic resonance (SSNMR). Among all of the samples, the composition with x = 0.2 exhibited the highest ionic conductivity, achieving 1.05 x 10-3 S/cm at 25 degrees C, which is 3.65 times higher than that of the undoped sample. XRD and SSNMR results prove that La3+ ions did not integrate into the main phase lattice to replace Zr4+ ions. Instead, they formed a heterogeneous phase predominantly composed of Na3La(PO4)2 at the grain boundaries. The content of Na3La(PO4)2 and the composition of the NASICON main phase were accurately determined by SSNMR. This impurity resulted in changes in the Si/P and Na/Zr ratios within the main phase. Some comparison experiments are carried out and prove that these changes were not the principal drivers of the increased conductivity. SEM results further indicated that doping with an appropriate amount of La3+ ions significantly increased the sample densification, thus promoting Na+ ions transport between grain boundaries-this being the key factor driving the observed improvement in ionic conductivity.
引用
收藏
页码：3414 / 3423
页数：10
相关论文
共 48 条
  • [1] Schroder C., Ren J., Rodrigues A.C.M., Eckert H., Glass-to-Crystal Transition in Li<sub>1+x</sub>Al<sub>x</sub>Ge<sub>2-x</sub>(PO<sub>4</sub>)<sub>3</sub>: Structural Aspects Studied by Solid State NMR, J. Phys. Chem. C, 118, pp. 9400-9411, (2014)
  • [2] Bradtmuller H., Nieto-Munoz A.M., Ortiz-Mosquera J.F., Rodrigues A.C.M., Eckert H., Glass-to-crystal transition in the NASICON glass-ceramic system Na<sub>1+x</sub>Al<sub>x</sub>M<sub>2-x</sub>(PO<sub>4</sub>)<sub>3</sub> (M = Ge, Ti), J. Non-Cryst. Solids, 489, pp. 91-101, (2018)
  • [3] Zhang Z., Hu L., Tao H., Ren J., Li super ionic conducting glasses and glass ceramics in the Li<sub>1+x</sub>Ga<sub>x</sub>Ge<sub>2-x</sub>P<sub>3</sub>O<sub>12</sub> system: Solid state nuclear magnetic resonance and electrical conductivity study, J. Power Sources, 442, (2019)
  • [4] d'Anciaes Almeida Silva I., Nieto-Munoz A.M., Rodrigues A.C.M., Eckert H., Structure and lithium-ion mobility in Li<sub>1.5</sub>M0<sub>.5</sub>Ge<sub>1.5</sub>(PO<sub>4</sub>)<sub>3</sub> (M = Ga, Sc, Y) NASICON glass-ceramics, J. Am. Ceram. Soc., 103, pp. 4002-4012, (2020)
  • [5] Zhang Y., Fei H., An Y., Wei C., Feng J., High Voltage, Flexible and Low Cost All-Solid-State Lithium Metal Batteries with a Wide Working Temperature Range, ChemistrySelect, 5, pp. 1214-1219, (2020)
  • [6] Shi N., Xiong S., Wu F., Bai J., Chu Y., Mao H., Feng J., Xi B., Hydrothermal Synthesis of ZnWO<sub>4</sub> Hierarchical Hexangular Microstars for Enhanced Lithium-Storage Properties, Eur. J. Inorg. Chem., 2017, pp. 734-740, (2017)
  • [7] Li C., Li R., Liu K., Si R., Zhang Z., Hu Y., NaSICON: A promising solid electrolyte for solid-state sodium batteries, Interdiscip. Mater., 1, pp. 396-416, (2022)
  • [8] Rao Y.B., Bharathi K.K., Patro L.N., Review on the synthesis and doping strategies in enhancing the Na ion conductivity of Na<sub>3</sub>Zr<sub>2</sub>Si<sub>2</sub>PO<sub>12</sub> (NASICON) based solid electrolytes, Solid State Ionics, 366-367, (2021)
  • [9] Palomares V., Serras P., Villaluenga I., Hueso K.B., Carretero-Gonzalez J., Rojo T., Na-ion batteries, recent advances and present challenges to become low cost energy storage systems, Energy Environ. Sci., 5, pp. 5884-5901, (2012)
  • [10] Chen D., Luo F., Zhou W., Zhu D., Influence of Nb<sup>5+</sup>, Ti<sup>4+</sup>, Y<sup>3+</sup> and Zn<sup>2+</sup> doped Na<sub>3</sub>Zr<sub>2</sub>Si<sub>2</sub>PO<sub>12</sub> solid electrolyte on its conductivity, J. Alloys Compd., 757, pp. 348-355, (2018)
12345