Weiqi Li, Liwei Jiang, Zhenjie Zhang, Chunliu Xu, Lin Zhou, Rongbing Dang, Junmei Zhao, Yong-Sheng Hu
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引用次数: 0
Abstract
NaV(PO) is a promising cathode for Na-ion batteries (NIBs) owing to the high electrochemical reversibility. The NaV(PO) has two typical polymorphs including rhombohedral and monoclinic phases; the former has been extensively studied, whereas the latter is rarely reported. Here, we successfully designed monoclinic NaV(PO)-based cathode via Ga and Fe substitutions owing to the lowered lattice energy. In addition, we revealed that Ga substitution improves average voltage owing to the activation of the V/V redox couple and the Fe substitution enhances rate capability due to the decreased band gap and Na-ion diffusion activation energy. As a result, the designed monoclinic NaVGaFe(PO) cathode exhibits high voltage plateaus (3.4 V and 4 V) and high-rate capability (from 116.8 mA h/g at 0.2 C to 103 mA h/g at 20 C) as well as superior cycling stability (99.9% capacity retention over 4,500 cycles at 5 C). Moreover, the assembled NaVGaFe(PO)//hard carbon full cell delivers a high-energy density of 313.8 Wh/kg with 86.4% capacity retention after 100 cycles at 1 C. This work demonstrates the design of monoclinic NaV(PO)-based cathode via bimetallic substitution, providing a new route for development of high-energy and long-lifespan NIBs.
由于具有很高的电化学可逆性,NaV(PO) 是一种很有前途的钠离子电池(NIBs)阴极。NaV(PO)有两种典型的多晶型,包括斜方晶相和单斜晶相;前者已被广泛研究,而后者则鲜有报道。在这里,我们通过镓和铁的置换成功地设计出了单斜NaV(PO)基阴极,因为它的晶格能降低了。此外,我们还发现,由于 V/V 氧化还原偶的激活,镓的取代提高了平均电压;由于带隙和 Na 离子扩散激活能的降低,铁的取代提高了速率能力。因此,所设计的单斜 NaVGaFe(PO)阴极具有较高的电压高原(3.4 V 和 4 V)和较高的速率能力(从 0.2 C 时的 116.8 mA h/g 到 20 C 时的 103 mA h/g),以及卓越的循环稳定性(在 5 C 下循环 4,500 次,容量保持率为 99.9%)。此外,组装后的 NaVGaFe(PO)//硬碳全电池在 1 C 下循环 100 次后,能量密度高达 313.8 Wh/kg,容量保持率为 86.4%。这项工作展示了通过双金属置换设计单斜 NaV(PO)基阴极的方法,为开发高能量、长寿命无电池组件提供了一条新途径。
期刊介绍:
Materials Today Energy is a multi-disciplinary, rapid-publication journal focused on all aspects of materials for energy.
Materials Today Energy provides a forum for the discussion of high quality research that is helping define the inclusive, growing field of energy materials.
Part of the Materials Today family, Materials Today Energy offers authors rigorous peer review, rapid decisions, and high visibility. The editors welcome comprehensive articles, short communications and reviews on both theoretical and experimental work in relation to energy harvesting, conversion, storage and distribution, on topics including but not limited to:
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