Highly conductive Na2.804Sb0.879W0.046S3.7F0.075 with moisture tolerance enables stable all-solid-state sodium batteries

IF 16.8 1区 材料科学 Q1 CHEMISTRY, PHYSICAL
Lan Wang , Dongyang Liu , Gaozhan Liu , Huilin Pan , Liangfeng Huang , Xiayin Yao
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Abstract

The low ionic conductivity of sodium solid electrolytes and the instability with moisture and sodium metal are the main challenges for the development of all-solid-state sodium batteries. In this work, a Na3SbS4 solid electrolyte with coexisting W and F dopants (Na2.804Sb0.879W0.046S3.7F0.075) is synthesized and achieves a high ionic conductivity of 11.13 mS cm−1. Density-functional-theory calculations indicate that both the reduced Na-vacancy formation energy and Na-ion diffusion barrier by such co-doping strategy contribute to the improved ionic conductivity. Furthermore, although the promoted H2O dissociation by W doping results in the extremely low stability of Na2.95Sb0.95W0.05S4 in moisture, the added F dopant dramatically increases the energy costs for H2O adsorption and dissociation, effectively inhibiting the hydrolysis of Na2.804Sb0.879W0.046S3.7F0.075. Moreover, the NaF layer formed at the interfaces of Na/Na2.804Sb0.879W0.046S3.7F0.075/Na symmetric cell significantly ameliorates the interfacial instability caused by W, realizing four times longer stable cycle time to 800 h. As a result, the TiS2/Na2.804Sb0.879W0.046S3.7F0.075/Na battery shows an initial reversible capacity of 173.3 mAh g−1, with a capacity retention of 85 % after 100 cycles at 0.1 C.

Abstract Image

高导电性Na2.804Sb0.879W0.046S3.7F0.075耐湿,使全固态钠电池稳定
钠固体电解质离子电导率低,与水分和金属钠的不稳定性是发展全固态钠电池的主要挑战。本文合成了W和F掺杂共存的Na3SbS4固体电解质(Na2.804Sb0.879W0.046S3.7F0.075),离子电导率高达11.13 mS cm-1。密度泛函理论计算表明,这种共掺杂策略降低了na空位形成能和na离子扩散势垒,有助于提高离子电导率。此外,虽然W掺杂促进H2O解离导致Na2.95Sb0.95W0.05S4在水中的稳定性极低,但添加F掺杂显著增加了H2O吸附和解离的能量成本,有效抑制了Na2.804Sb0.879W0.046S3.7F0.075的水解。此外,在Na/Na2.804Sb0.879W0.046S3.7F0.075/Na对称电池的界面处形成的NaF层显著改善了W引起的界面不稳定性,实现了4倍的稳定循环时间,达到800 h。因此,TiS2/Na2.804Sb0.879W0.046S3.7F0.075/Na电池的初始可逆容量为173.3 mAh g-1,在0.1 C下循环100次后容量保持率为85%。
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来源期刊
Nano Energy
Nano Energy CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY
CiteScore
30.30
自引率
7.40%
发文量
1207
审稿时长
23 days
期刊介绍: Nano Energy is a multidisciplinary, rapid-publication forum of original peer-reviewed contributions on the science and engineering of nanomaterials and nanodevices used in all forms of energy harvesting, conversion, storage, utilization and policy. Through its mixture of articles, reviews, communications, research news, and information on key developments, Nano Energy provides a comprehensive coverage of this exciting and dynamic field which joins nanoscience and nanotechnology with energy science. The journal is relevant to all those who are interested in nanomaterials solutions to the energy problem. Nano Energy publishes original experimental and theoretical research on all aspects of energy-related research which utilizes nanomaterials and nanotechnology. Manuscripts of four types are considered: review articles which inform readers of the latest research and advances in energy science; rapid communications which feature exciting research breakthroughs in the field; full-length articles which report comprehensive research developments; and news and opinions which comment on topical issues or express views on the developments in related fields.
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