Kinetics and Pore Formation of the Sodium Metal Anode on NASICON-Type Na3.4Zr2Si2.4P0.6O12 for Sodium Solid-State Batteries

被引：43

作者：

Ortmann, Till ^{[1
,2
]}

Burkhardt, Simon ^{[1
,2
]}

Eckhardt, Janis Kevin ^{[2
,3
]}

Fuchs, Till ^{[1
,2
]}

Ding, Ziming ^{[4
,5
,6
]}

Sann, Joachim ^{[1
,2
]}

Rohnke, Marcus ^{[1
,2
]}

Ma, Qianli ^{[7
]}

Tietz, Frank ^{[7
]}

Fattakhova-Rohlfing, Dina ^{[7
,8
,9
]}

Kuebel, Christian ^{[4
,5
,6
,10
]}

Guillon, Olivier ^{[7
,11
]}

Heiliger, Christian ^{[2
,3
]}

Janek, Juergen ^{[1
,2
]}

机构：

[1] Justus Liebig Univ Giessen, Inst Phys Chem, D-35392 Giessen, Germany

[2] Justus Liebig Univ Giessen, Ctr Mat Res ZfM, D-35392 Giessen, Germany

[3] Justus Liebig Univ Giessen, Inst Theoret Phys, D-35392 Giessen, Germany

[4] Tech Univ Darmstadt, D-64289 Darmstadt, Germany

[5] Karlsruhe Inst Technol KIT, Inst Nanotechnol INT, D-76344 Eggenstein Leopoldshafen, Germany

[6] Karlsruhe Inst Technol KIT, Helmholtz Inst Ulm HIU, D-76344 Eggenstein Leopoldshafen, Germany

[7] Forschungszentrum Julich, Inst Energy & Climate Res Mat Synth & Proc IEK 1, D-52425 Julich, Germany

[8] Univ Duisburg Essen, Dept Engn, D-47057 Duisburg, Germany

[9] Univ Duisburg Essen, Ctr Nano Integrat Duisburg Essen CENIDE, D-47057 Duisburg, Germany

[10] Karlsruhe Inst Technol KIT, Karlsruhe Nano Micro Facil KNMF, D-76344 Eggenstein Leopoldshafen, Germany

[11] JARA Energy, Julich Aachen Res Alliance, D-52425 Julich, Germany

来源：

ADVANCED ENERGY MATERIALS | 2023年 / 13卷 / 05期

关键词：

current constriction; impedance spectroscopy; interphase growth; NASICON electrolytes; SEI formation; sodium metal anodes; LITHIUM-METAL; INTERFACIAL REACTIONS; NA; RESISTANCE; IMPEDANCE; OXYGEN; 1ST-PRINCIPLES; ELECTROLYTES; DEFORMATION; DISSOLUTION;

D O I：

10.1002/aenm.202202712

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：

In recent years, many efforts have been made to introduce reversible alkali metal anodes using solid electrolytes in order to increase the energy density of next-generation batteries. In this respect, Na3.4Zr2Si2.4P0.6O12 is a promising solid electrolyte for solid-state sodium batteries, due to its high ionic conductivity and apparent stability versus sodium metal. The formation of a kinetically stable interphase in contact with sodium metal is revealed by time-resolved impedance analysis, in situ X-ray photoelectron spectroscopy, and transmission electron microscopy. Based on pressure- and temperature-dependent impedance analyses, it is concluded that the Na|Na3.4Zr2Si2.4P0.6O12 interface kinetics is dominated by current constriction rather than by charge transfer. Cross-sections of the interface after anodic dissolution at various mechanical loads visualize the formed pore structure due to the accumulation of vacancies near the interface. The temporal evolution of the pore morphology after anodic dissolution is monitored by time-resolved impedance analysis. Equilibration of the interface is observed even under extremely low external mechanical load, which is attributed to fast vacancy diffusion in sodium metal, while equilibration is faster and mainly caused by creep at increased external load. The presented information provides useful insights into a more profound evaluation of the sodium metal anode in solid-state batteries.

引用

页数：17

共 76 条

[1] AUGER AND X-RAY PHOTOELECTRON SPECTROSCOPIC STUDY OF SODIUM METAL AND SODIUM OXIDE [J].