P2- a2=3Mn2=3M1=3O2 (M = Fe, Co, Ni) cathode materials in localized high concentration electrolyte for the long-cycling performance of sodium-ion batteries

K. Lê, Huynh Thi Mong Tuyen, T. Vo, Hoang V. Nguyen, N. Tran, M. Tran, P. Le
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Abstract

Introduction: Localized high concentration electrolytes (LHCE) have been intensively studied due to their unique properties, especially in suppressing the Na dendrite formation and long-term cycling. Therefore, the low electrochemical performance of the P2-type cathode can be overcome by using LHCE. Methods: P2-type sodium layered oxides Na2=3Mn2=3M1=3O2 (M = Fe, Co, Ni) cathode materials were synthesized via a simple co-precipitation following a supported solid-state reaction. XRD and Rietveld method analyzed the phase composition and lattice parameters. SEM images observed the morphology of materials. The half-cell of three cathode were performed in LHCE consisting of 2.1 M sodium bis(fluorosulfonyl)imide (NaFSI) dissolved in 1,2-dimethoxyethane (DME) and bis(2,2,2-trifluoroethyl) ether (BTFE) (solvent molar ratio 1:2). The galvanostatic charge-discharge, striping-plating, and linear sweep voltage tests were carried out to investigate the electrochemical behaviors. Results: As-prepared electrode materials exhibited discharge capacities of 94.5, 147.1, and 142.9 mAh/g at C/10 in the potential range of 1.5-4.2 V for Na2=3Mn2=3Fe1=3O2 (MFO), Na2=3Mn2=3Co1=3O2 (MCO) and Na2=3Mn2=3Ni1=3O2 (MNO), respectively. Interestingly, the MNO cathode material has a superior cycling performance with 86.5% capacity retention after 100 cycles than MCO and MFO. Conclusion: Such superior electrochemical performance of synthesized MNO could be ascribed to the combined synergistic effects between the nickel partially substituted MNO cathode structure and using LHCE 2.1 M NaFSI/DME-BTFE (1:2). Nickel substituted MNO cathode exhibited the enhancement of discharge capacity and the long cycling stability in LHCE due to the mitigation of dendrite formation on sodium metal anode.
局部高浓度电解液中P2- a2=3Mn2=3M1=3O2 (M = Fe, Co, Ni)正极材料对钠离子电池长循环性能的影响
局部高浓度电解质(LHCE)由于其独特的性能,特别是在抑制Na枝晶形成和长期循环方面,受到了广泛的研究。因此,利用LHCE可以克服p2型阴极电化学性能低的问题。方法:采用固载共沉淀法合成了p2型钠层状氧化物Na2=3Mn2=3M1=3O2 (M = Fe, Co, Ni)正极材料。XRD和Rietveld法分析了相组成和晶格参数。SEM图像观察了材料的形貌。以2.1 M氟磺酰基亚胺钠(NaFSI)与1,2-二甲氧基乙烷(DME)和2,2,2-三氟乙基醚(BTFE)(溶剂摩尔比1:2)为溶剂,在LHCE中制备了三阴极半电池。通过恒流充放电、条纹镀和线性扫描电压试验研究了其电化学行为。结果:在1.5 ~ 4.2 V电势范围内,在C/10条件下,Na2=3Mn2=3Fe1=3O2 (MFO)、Na2=3Mn2=3Co1=3O2 (MCO)和Na2=3Mn2=3Ni1=3O2 (MNO)的放电容量分别为94.5、147.1和142.9 mAh/g。有趣的是,MNO正极材料的循环性能优于MCO和MFO,循环100次后容量保持率为86.5%。结论:镍部分取代MNO的阴极结构与LHCE 2.1 M NaFSI/DME-BTFE(1:2)的协同作用是合成MNO具有优异电化学性能的主要原因。由于减少了金属钠阳极枝晶的形成,镍取代MNO阴极在LHCE中表现出了增强的放电容量和长循环稳定性。
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