Achieving long-cycling sodium-ion full cells in ether-based electrolyte with vinylene carbonate additive

doi:10.1016/j.jechem.2020.10.047

Journal of Energy Chemistry

Volume 57, June 2021, Pages 650-655

https://doi.org/10.1016/j.jechem.2020.10.047 Get rights and content

Highlights

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NaCF₃SO₃-DGM + 5wt% VC electrolyte could make sodium-ion full cells applicable.
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The sodium-ion full cell with the electrolyte exhibits long term cycling stability.
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VC can be synergistically oxidized with DGM to form integrity CEI layers.

Abstract

Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously. Ether-based electrolytes, preference of anode materials, cannot match with high-potential cathodes failing to apply in full cells. Herein, vinylene carbonate (VC) as an additive into NaCF₃SO₃-Diglyme (DGM) could make sodium-ion full cells applicable without pre-activation of cathode and anode. The assembled FeS@C || Na₃V₂(PO₄)₃@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention. The deduced reason is additive VC, whose HOMO level value is close to that of DGM, not only change the solvent sheath structure of Na⁺, but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na₃V₂(PO₄)₃@C cathode, which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition. This work displays a new way to optimize the sodium-ion full cells easily with bright practical application potential.

Graphical abstract

The sodium-ion full cell can be employed in the ether-based electrolyte by the addition of VC and exhibits long term cycling stability and high capacity retention.

Introduction

Sodium-ion batteries (SIBs) are considered as one kind of the most promising candidates for large-scale energy storage applications. Their electrode materials have been widely developed in recent years [1], [2], [3], [4], [5], [6], [7] in which some materials have demonstrated delightful performance meeting the application requirements in some extent, such as phosphates and prussian blue for cathode materials, and hard carbon and chalcogenides for anode materials [8], [9], [10], [11], [12], [13], [14], [15]. However, the wicked compatibility of electrolyte between cathodes and anodes leading to the disappointing performance of the assembled full cells, though it is crucial to the practical application of SIBs.

Up to now, almost all reported cathode materials for Na storage, such as Na₄Fe₃(PO₄)₂(P₂O₇), Na₂Fe(SO₄)₂, Na₂FePO₄F, Na₃V₂(PO₄)₃, Na_xMnO₂, NaNi_1/3Fe_1/3Mn_1/3O₂, Na_xFeFe(CN)₆, Na_xTMO₂, Na₃V₂(PO₄)₂F₃, NaVPO₄F, Na₃V₂(PO₄)₂O₂F, are studied in the ester-based electrolytes owing to the higher oxidative stability [10], [12], [15], [16], [17], [18], [19], [20], [21], [22], [23]. While most researches about anode materials, for example, FeS₂, MoS₂, CuS, CoGa₂S₄, Ni₃S₄, TiO₂, Bi, P, hard carbon, Na, are investigated in ether-based electrolytes, especially NaCF₃SO₃-Diglyme (DGM), due to superior SEI layer, thereby leading to the outstanding rate property and long-term cycle stability (Tables S1 and S2) [6], [24], [25], [26], [27], [28], [29], [30]. If the outstanding characteristics of anode materials want to be kept, ether-based electrolytes with wide electrochemical stability window, especially oxidation stability, are desired to match cathode simultaneously. And the complex and time-consuming pre-activating of the cathode would be avoided when the high electrochemical stability ester-based electrolytes are employed to assemble full cells.

Introducing additives into electrolyte is an effective and simple way to improve the electrochemical property of electrolytes and electrodes [31], [32], [33], [34], [35], [36]. Positive effects of vinyl ethylene carbonate (VEC) and fluoroethylene carbonate (FEC) as additives for Na-metal and hard carbon anodes in carbonate-based electrolytes were identified. Cao et al. pointed out that FEC-derived SEI layers on Na metal and hard carbon anodes are compact and dense which could suppress the decomposition of propylene carbonate (PC) efficiently [37]. Intermetallic alloys, such as Ge, Sb, and Sn, and their composites use FEC as an additive into NaClO₄-PC induce to form a robust and thin SEI layer enabling a facile Na-ion transfer. Even though electrolyte additives have a great influence on the electrochemical performance of anode materials, the impact of them on the performance of cathodes is also needed to obtain enough attention. Komaba et al. stated that adding FEC in NaClO₄-PC is beneficial to form a stable CEI layer on the surface of NaNi_1/2Mn_1/2O₂, which can restrain the oxidation of electrolyte [38]. Lee et al. also proved that, with the presence of DEC and FEC in NaClO₄-EC/PC, NaF-lean CEI layers on Na₄Fe₃(PO₄)₂(P₂O₇) were formed, thereby improving the reversibility [39]. Nevertheless, as far as we know, there is not reported work about the effect of additives into ether-based electrolytes for SIBs to improve the compatibility of cathode materials, which would benefit the assembly of full cells without pre-activation.

Herein, ether-based electrolyte (1 M NaCF₃SO₃-DGM + 5 wt% VC) with extended electrochemical stability window owing to the additive VC could be successfully employed to FeS@C||Na₃V₂(PO₄)₃@C full cells without pre-activation of cathode and anode, respectively. The additive VC can induce to form integrity and consecutive CEI layer on Na₃V₂(PO₄)₃@C cathode, leading to the oxidation potential of ether-based electrolyte increased. Therefore, it could match with Na₃V₂(PO₄)₃@C cathode. At the same time, it can keep working well with the anode. As a result, the ether-based electrolyte (1 M NaCF₃SO₃-DGM + 5 wt% VC) can be applied in full cell delivering capacity retention of 67% after 1000 cycles at 0.5C. Furthermore, this electrolyte can be applied to match other cathode materials.

Section snippets

Results and discussion

To obtain an effective electrolyte with suitable voltage window for matching with cathode and anode simultaneously, NaCF₃SO₃-DGM electrolytes with additive VC (1 M NaCF₃SO₃-DGM + VC) was investigated and displayed in Fig. 1(a). Compared with NaCF₃SO₃-DGM whose decomposition potential is 3.60 V (vs. Na/Na⁺), 1 M NaCF₃SO₃-DGM + VC could obtain higher oxidative stability up to about 4.15 V (vs. Na/Na⁺), showing high electrochemical stability. With varied VC contents from 1% to 20%, the ionic

Conclusions

In summary, long-life sodium-ion full cells have successfully proceeded in the NaCF₃SO₃-DGM electrolyte via the help of VC. Therefore, the effects of VC as an additive in the NaCF₃SO₃-DGM electrolyte were identified carefully. The additive VC, of which the HOMO level is close to that of DGM, can be synergistically oxidized with DGM to form an undivided and consecutive CEI layer on Na₃V₂(PO₄)₃@C cathode, leading to higher oxidation stability of ether-based electrolyte, which makes NaCF₃SO₃-DGM

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. U1804129, 21771164, 21671205, U1804126), Zhongyuan Youth Talent Support Program of Henan Province, Zhengzhou University Youth Innovation Program. And we acknowledge the Zhengzhou University Supercomputing Center for the computational support.

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¹: These authors contributed equally to this work.

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Achieving long-cycling sodium-ion full cells in ether-based electrolyte with vinylene carbonate additive

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Results and discussion

Conclusions

Declaration of Competing Interest

Acknowledgments

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