Poly(Ethylene Oxide)-based Electrolyte for Solid-State-Lithium-Batteries with High Voltage Positive Electrodes: Evaluating the Role of Electrolyte Oxidation in Rapid Cell Failure

被引:217
作者
Homann, Gerrit [1 ]
Stolz, Lukas [1 ]
Nair, Jijeesh [1 ]
Laskovic, Isidora Cekic [1 ]
Winter, Martin [1 ,2 ]
Kasnatscheew, Johannes [1 ]
机构
[1] Forschungszentrum Julich, Helmholtz Inst Munster, IEK 12, Corrensstr 46, D-48149 Munster, Germany
[2] Univ Munster, MEET Battery Res Ctr, Inst Phys Chem, Corrensstr 46, D-48149 Munster, Germany
关键词
POLYMER ELECTROLYTES; ELECTROCHEMICAL PROPERTIES; ION; METAL; PERFORMANCE; LINI1/3CO1/3MN1/3O2; CONDUCTIVITY; RELAXATION; INTERPHASE; CAPACITY;
D O I
10.1038/s41598-020-61373-9
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Polyethylene oxide (PEO)-based solid polymer electrolytes (SPEs) typically reveal a sudden failure in Li metal cells particularly with high energy density/voltage positive electrodes, e.g. LiNi0.6Mn0.2Co0.2O2 (NMC622), which is visible in an arbitrary, time - and voltage independent, "voltage noise" during charge. A relation with SPE oxidation was evaluated, for validity reasons on different active materials in potentiodynamic and galvanostatic experiments. The results indicate an exponential current increase and a potential plateau at 4.6 V vs. Li vertical bar Li+, respectively, demonstrating that the main oxidation onset of the SPE is above the used working potential of NMC622 being < 4.3V vs. Li vertical bar Li+. Obviously, the SPE vertical bar NMC622 interface is unlikely to be the primary source of the observed sudden failure indicated by the "voltage noise". Instead, our experiments indicate that the Li vertical bar SPE interface, and in particular, Li dendrite formation and penetration through the SPE membrane is the main source. This could be simply proven by increasing the SPE membrane thickness or by exchanging the Li metal negative electrode by graphite, which both revealed "voltage noise"-free operation. The effect of membrane thickness is also valid with LiFePO4 electrodes. In summary, it is the cell set-up (PEO thickness, negative electrode), which is crucial for the voltage-noise associated failure, and counterintuitively not a high potential of the positive electrode.
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页数:9
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