Electrochemical properties and evolution of the phase transformation behavior in the NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) cathodes for Na-ion batteries

被引:63
作者
Zakharkin, Maxim, V [1 ,2 ]
Drozhzhin, Oleg A. [1 ,2 ]
Ryazantsev, Sergey, V [1 ,2 ]
Chernyshov, Dmitry [3 ,4 ]
Kirsanova, Maria A. [1 ]
Mikheev, Ivan, V [2 ]
Pazhetnov, Egor M. [1 ]
Antipov, Evgeny, V [1 ,2 ]
Stevenson, Keith J. [1 ]
机构
[1] Skolkovo Inst Sci & Technol, 3 Nobel St, Moscow 121205, Russia
[2] Lomonosov Moscow State Univ, 1-3 Leninskie Gory, Moscow 119991, Russia
[3] European Synchrotron, Swiss Norwegian Beamlines, 71 Rue Martyrs, F-38043 Grenoble, France
[4] Peter Great St Petersburg Polytech Univ, 29 Polytekh Skaya St, St Petersburg 195251, Russia
基金
俄罗斯科学基金会;
关键词
Sodium-ion battery; NASICON; Cathode material; Na4MnV(PO4)(3); Phase transitions; Operando XRD; SODIUM; OPERANDO; NA3V2(PO4)(3); SUBSTITUTION; DIFFRACTION; PERFORMANCE; EXTRACTION; CELL; FE;
D O I
10.1016/j.jpowsour.2020.228231
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
NASICON-structured cathode materials are considered as possible candidates for high-performance Na-ion batteries. Further increase of energy density of the Na3V2(PO4)(3) may be achieved by substitution of the V cations by other transition metals. Here, we show that a family of Na3+xMnxV2-x(PO4)(3) (0 <= x <= 1, Delta x=0.2) cathode materials demonstrates remarkable diversity of the electrochemical properties and phase transformations depending on degree of substitution and cut-off voltage. An intermediate "Na2M2(PO4)(3)" phase was found for all compounds studied by means of operando powder X-ray diffraction. When Mn content is low (x similar to 0-0.4), it coexists with Na3+xMnxV2-x(PO4)(3) or Na1+xMnxV2-x(PO4)(3). Increase in Mn content extends the length of the solid solution region corresponding to sodiated, intermediate and desodiated phases. All Mn-substituted samples are characterized by additional high-voltage plateau (-3.9 V) at charge-discharge curves. Na3+xMnxV2-x(PO4)(3) (x >= 0.4) compositions exhibit 8-10% energy density gain in comparison to Na3V2(PO4)(3) material, Na3.2Mn0.2V1.8(PO4)(3) and Na3.4Mn0.4V1.6(PO4)(3) are most preferable in terms of cycling stability.
引用
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页数:8
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