NASICON型Na1+x Zr2Si x P3-x O12固态电解质及其钠金属电池研究进展

doi:10.19964/j.issn.1006-4990.2024-0275

Abstract

Abstract:

Lithium-ion batteries are commercialized due to their high working voltage and energy density.However，the limited lithium resources have hampered their widespread application.Sodium-ion batteries（SIBs） have similar electrochemical behavior and rich sodium salt resources，which have attracted wide attention.The current SIBs use organic electrolytes，which have many safety issues such as leakage and combustion，and the use of solid-state electrolytes can effectively solve the above problems.However，the ionic conductivity of this electrolyte needs to be further improved，and the problems of the consistency of the synthesized material and the large interface impedance between the electrode and electrolyte limit its practical application.To settle the problem of ionic conductivity，the effects of substituted different multi-valence metal ions were summarized and analyzed.In view of the interface problems，the existing interface modification methods of Na₁₊_x Zr₂Si _x P_3-_x O₁₂ electrolytes from the cathode and anode sides were reviewed and analyzed.Finally，the development direction of Na₁₊_x Zr₂Si _x P_3-_x O₁₂ solid electrolytes was forecasted，which was expected to promote the development of solid SIBs.

Key words: sodium ion batteries, solid-state electrolyte, Na₁₊_x Zr₂Si _x P_3-_x O₁₂, ionic conductivity, interface modification

CLC Number:

TM911

XU Xijun, LIN Jianfeng, LUO Xiongwei, ZHAO Jingwei, HUO Yanping. Recent progress of NASICON-type Na₁₊_x Zr₂Si _x P_3-_x O₁₂ solid electrolyte for sodium metal batteries[J]. Inorganic Chemicals Industry, 2024, 56(11): 1-14.

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化学式	取代离子	离子电导率/ （S·cm^-1）
Na_2.9K_0.1Zr₂Si₂PO₁₂^［78］	K⁺	7.7×10^-4
Na_3.456Zr_1.872Mg_0.128Si_2.2P_0.8O₁₂^［54］	Mg²⁺	3.2×10^-3
Na_3.1Zr_1.95Mg_0.05Si₂PO₁₂^［55］	Mg²⁺	3.5×10^-3
Na_3.4Zr_1.9Zn_0.1Si_2.2P_0.8O₁₂^［46］	Zn²⁺	5.27×10^-3
Na_3.325Zr_{1.937 5}Mg_{0.062 5}Si_2.2P_0.8O₁₂^［53］	Mg²⁺	2.7×10^-3
Na_3.4Zr_1.8Cu_0.2Si₂PO₁₂^［79］	Cu²⁺	1.94×10^-3
Na_3.4Zr_1.8Ca_0.2Si₂PO₁₂^［35］	Ca²⁺	1.67×10^-3
Na_3.4Zr_1.8Fe_0.2Si₂PO₁₂^［80］	Fe²⁺	3.9×10^-4
Na_3.2Zr_1.9Co_0.1Si₂PO₁₂^［80］	Co²⁺	3.3×10^-4
Na_3.6Zr_1.7Ni_0.3Si₂PO₁₂^［80］	Ni²⁺	1.1×10^-4
Na_3.4Zr_1.6Sc_0.4Si₂PO₁₂^［64］	Sc³⁺	1.77×10^-3
Na_3.12Zr_1.88Y_0.12Si₂PO₁₂^［81］	Y³⁺	2.0×10^-3
Na_3.3Zr_1.7Pr_0.3Si₂PO₁₂^［82］	Pr³⁺	1.3×10^-3
Na_3.3Zr_1.7La_0.3Si₂PO₁₂^［83］	La³⁺	1.3×10^-3
Na_3.1Zr_1.9La_0.1Si₂PO₁₂^［60］	La³⁺	1.1×10^-3
Na_3.1Zr_1.9Ga_0.1Si₂PO₁₂^［84］	Ga³⁺	1.1×10^-3
Na_3.3Zr_1.7Eu_0.3Si₂PO₁₂^［82］	Eu³⁺	1.1×10^-3
Na_3.3Zr_1.7Lu_0.3Si₂PO₁₂^［82］	Lu³⁺	8.3×10^-4
Na_3.2Zr_1.8Fe_0.2Si₂PO₁₂^［56］	Fe³⁺	7.5×10^-4
Na_3.1Zr_1.9Nd_0.1Si₂PO₁₂^［60］	Nd³⁺	6.9×10^-4
Na_3.2Zr_1.8Al_0.2Si₂PO₁₂^［56］	Al³⁺	4.4×10^-4
Na₃Zr_1.98Ce_0.02Si₂PO₁₂^［66］	Ce⁴⁺	4.1×10^-2
Na₃Zr_1.9Ce_0.1Si₂PO₁₂^［66］	Ce⁴⁺	4.01×10^-2
Na_3.4Zr₂Si_2.4P_0.6O₁₂^［85］	Si⁴⁺	5.0×10^-3
Na₃Zr₂Si_1.85Ge_0.15PO₁₂^［75］	Ge⁴⁺	1.4×10^-3
Na₃Zr_1.9Ti_0.1Si₂PO₁₂^［57］	Ti⁴⁺	3.8×10^-4
Na_3.3Zr_1.9Nb_0.1Si_2.4P_0.6O₁₂^［67］	Nb⁵⁺	5.5×10^-3
Na_3.125Zr_1.75Sc_0.125Ge_0.125Si₂PO₁₂^［76］	Sc³⁺、Ge⁴⁺	4.64×10^-3
Na_3.33Zr_1.65Sc_0.33Ce_0.02Si₂PO₁₂^［77］	Sc³⁺、Ce⁴⁺	2.4×10^-3
Na_3.33Zr_1.67Sc_0.29Yb_0.04Si₂PO₁₂^［63］	Sc³⁺、Yb³⁺	1.62×10^-3
Na_3.2Hf_1.9Ca_0.1Si₂PO₁₂^［86］	Hf²⁺、Ca²⁺	1.07×10^-3
Na_3.2Hf₂Si_2.2P_0.8O₁₂^［87］	Hf⁴⁺、Si⁴⁺	2.3×10^-3
Na_3.325Zr_{1.937 5}Mg_{0.062 5}Si_2.2P_0.8O₁₂^［53］	Mg²⁺、Si⁴⁺	2.7×10^-3
Na_3.1Zr_1.9Y_0.1Si₂PO₁₂-1%B₂O₃^［88］	Y³⁺	1.21×10^-3

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[4]	DONG Peng,ZHOU Yingjie,HOU Minjie,YANG Dongrong,DAI Yongnian,LIANG Feng. Research progress on Na3V₂（PO₄）₃ cathode materials for sodium ion batteries [J]. Inorganic Chemicals Industry, 2022, 54(5): 1-10.

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Recent progress of NASICON-type Na₁₊_x Zr₂Si _x P_3-_x O₁₂ solid electrolyte for sodium metal batteries

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