In situ composite solid electrolyte interphases enabling dendrite-free sodium metal batteries

Abstract

Given the limited reserves and high cost of lithium resources, research into cost-effective, high-performance energy storage devices beyond lithium-ion batteries has gained increasing attention. Sodium metal anodes, with their abundant reserves, low cost, high specific capacity (1160 mA h g⁻¹), and low redox potential (−2.714 V vs. the Standard Hydrogen Electrode (SHE)), are considered one of the most promising next-generation anode materials. However, the unstable solid electrolyte interphase (SEI) in sodium metal anodes leads to non-uniform diffusion and deposition of Na⁺, resulting in uncontrollable dendrite growth. During repeated charging/discharging processes, the growth of dendrites and the continuous fracture and regeneration of the SEI layer lead to the continuous loss of active sodium and coulombic efficiency (CE). To address this issue, this study reports an in situ generated organic/inorganic hybrid multifunctional solid electrolyte interface to effectively enhance the stability of the sodium metal anode. The inorganic components, NaF and Na₂S, serve as high ionic conductivity components, accelerating the transfer of Na⁺. The rich amide groups in the organic component exert a polar attraction to Na⁺, regulating the Na⁺ flux and alleviating the “tip effect” during metal deposition. Experiments show that the Na‖Na symmetric battery using this anode exhibits extremely low overpotential and stable plating/stripping behavior (cycling for over 2500 hours at 1 mA cm⁻² and 1 mA h cm⁻², with an ultra-low voltage of 15 mV). The full cell assembled with Na₃V₂(PO₄)₃ (NVP) demonstrates excellent rate and cycling performance, with a capacity retention rate of 90.3% after 1000 cycles at 1C and 89.2% after 800 cycles at a high rate of 5C.

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1. Introduction

As the technology of rechargeable batteries, sodium batteries are garnering significant attention due to their low cost, high energy density, and abundance of sodium resources.¹ Sodium metal anodes are considered one of the most promising next-generation anode materials, with their high specific capacity (1160 mA h g⁻¹) and low redox potential (−2.714 V vs. SHE).² However, practical applications of sodium–metal batteries are fraught with challenges, particularly concerning anode stability.³ During charging and discharging cycles, sodium–metal anodes are prone to dendrite formation, which can penetrate the separator and cause short-circuiting, posing significant safety risks.^4–6 Furthermore, side reactions between sodium metal and the electrolyte lead to continuous electrolyte consumption and instability of the solid electrolyte interphase (SEI) film, affecting the battery's cycle life.^7,8

Various anode protection strategies have been proposed to address these challenges, each with advantages and limitations. (1) Electrolyte additive strategies: by adding beneficial components to the electrolyte, the battery performance can be improved, but the dendrite growth problem of the sodium metal negative electrode cannot be completely solved.⁹ (2) Solid-state electrolyte strategies offer better safety but typically exhibit lower ionic conductivity.¹⁰ (3) Constructing 3D current collectors, which provide more Na⁺ deposition sites but also present challenges in complex manufacturing processes and high costs.¹¹

In comparison, directly constructing an artificial solid electrolyte interphase (SEI) film on the surface of sodium metal anodes is a more straightforward approach. This method allows for external pre-design, simple manufacturing processes, and precise control over the composition and properties of the interface phase, including chemical stability, mechanical strength, and ion transport characteristics. As a result, it effectively protects sodium metal anodes, prevents continuous electrolyte consumption, and mitigates the formation of “dead sodium,” thereby significantly enhancing the battery's cycle stability.^12,13 Therefore, constructing an artificial SEI film is considered one of the most promising strategies.^14,15 For instance, Xu et al. added poly(tetrafluoroethylene) (PTFE) powder to molten sodium, triggering a spontaneous reaction between the two at high temperatures with an SEI protective layer rich in NaF and C–F species.¹⁶ Similarly, Huang et al. constructed two types of artificial SEI on the surface of sodium metal anodes through SnCl₄–Na and SnCl₂–Na electrodes. These artificial SEIs can be simply generated on the surface of sodium metal through a chemical displacement reaction, possessing both a high Na⁺ diffusion rate and uniformity, greatly enhancing the cycle stability of sodium metal anodes. Xia et al. ingeniously constructed a lithium-containing composite SEI layer on the sodium metal anode surface through a straightforward electrochemical strategy. The introduced lithium-based inorganic components (Li₃N and LiF) were able to stabilize the Na/electrolyte interface and enhance the mechanical properties and diffusion kinetics of the SEI layer, thereby reducing side reactions and gas generation. This approach regulated the Na⁺ flux during cycling and promoted rapid, uniform, and dendrite-free sodium deposition.¹⁷ Cao et al. in situ constructed a bifunctional interfacial layer (BiF₃/Na) on the sodium metal surface through a simple mechanical rolling method. This protective layer combines high ionic conductivity and electronic insulation. Within this layer, the sodium-conductive Na₃Bi component, which exhibits high sodium affinity, significantly prevents the non-uniform deposition and preferential nucleation of Na ions on the sodium metal surface. Meanwhile, the NaF phase, characterized by high interfacial energy and mechanical strength, effectively suppresses the uncontrolled growth of sodium dendrites.¹⁸ The introduction of suitable inorganic components can effectively enhance the cycling lifespan of sodium metal batteries. However, the distribution of inorganic components within the SEI layer is often inhomogeneous, leading to localized regions of excessive thickness or thinness. Additionally, their poor interfacial compatibility with the electrolyte hinders the uniform deposition of sodium ions.¹⁹ The incorporation of organic components can effectively mitigate these drawbacks. Therefore, organic/inorganic composite SEI layers will exhibit enhanced performance in sodium metal batteries.

Based on the above findings, an organic/inorganic composite artificial SEI layer was designed in this study through an in situ generation method. By precisely engineering the organic and inorganic components, the formation of sodium dendrites is effectively suppressed and the uniform transport of sodium ions is regulated. The organic/inorganic composite SEI is prepared on the sodium metal surface via a simple drop-casting method, utilizing the spontaneous reaction between sodium metal and N-fluorobenzoyl-N′-phenylthiourea (FBT) to generate an artificial SEI enriched with inorganic components of NaF and Na₂S, as well as abundant organic amide bonds. The rich polar amide groups on the surface exhibit excellent affinity for Na⁺, serving as adsorption sites for Na⁺ and rapidly homogenizing the interfacial Na⁺ flux. This process avoids the generation of localized non-uniform currents, eliminates the “tip effect,” and fundamentally eradicates the potential for dendrite formation. The inorganic components NaF and Na₂S, with their high ionic conductivity, facilitate rapid ion transfer at the interface, ensuring the high reversibility of Na⁺ plating/stripping. Symmetric cells using this anode demonstrate an ultralong cycle life, cycling for over 2500 hours at 1 mA cm⁻² and 1 mA h cm⁻².

2. Results and discussion

Fig. 1 schematically illustrates the evolution mechanisms of the SEI on different sodium metal anodes. As depicted in Fig. 1a for bare Na, the natural SEI film, primarily composed of Na₂CO₃, Na₂O, and trace amounts of NaF, forms spontaneously through reactions with the electrolyte during battery cycling.^20–22 During repeated charge/discharge cycles, the SEI membrane repeatedly fractures and reforms, leading to the continuous consumption of sodium metal and electrolyte. Consequently, a significant amount of “dead sodium” accumulates and the SEI layer thickens, hindering Na⁺ conduction and resulting in low coulombic efficiency and rapid capacity decay. Additionally, the continuous growth of sodium dendrites can easily pierce the separator, directly connecting the cathode and anode, causing battery short-circuiting.^23–25 In contrast, for FBT–Na (Fig. 1b), the main components of the organic/inorganic composite SEI membrane are NaF, Na₂S, and a large number of amide functional groups. The composite interface regulates a uniform Na⁺ flux, improves deposition kinetics, and ultimately forms a smooth deposition surface.

Fig. 1 Schematic illustration of the evolution of different solid electrolyte interphases (SEIs) on a sodium metal anode surface. (a) Unstable SEI on the bare sodium metal anode (bare Na), with severe dendrite growth and SEI rupture. (b) Stable organic/inorganic hybrid SEI on an FBT–sodium metal composite anode (FBT–Na), suppressing dendrite growth.

As shown in ESI Fig. 1,† a simple drop-casting method was employed to apply N-fluorobenzoyl-N′-phenylthiourea (FBT), dissolved in tetrahydrofuran, onto the sodium metal surface. Owing to the high reactivity of sodium, a spontaneous reaction occurs between the sodium metal and FBT. The composition of the SEI on sodium metal anodes with and without modification was examined by XPS after 20 cycles. Fig. 2a displays the high-resolution F 1s spectrum of the SEI on bare Na, with P–F and Na–F bonds originating from the decomposition of NaPF₆ in the electrolyte.²⁶Fig. 2b presents the high-resolution O 1s spectrum of bare Na, where the C–O single bond is attributed to Na₂CO₃ and the Na–O bond corresponds to Na₂O. Fig. 2c shows the N 1s spectrum of the SEI on FBT–Na, with a peak at 399 eV indicative of organic amide bonds, thus confirming the presence of polar amide functional groups in the SEI. Fig. 2d illustrates the high-resolution F 1s spectrum of the SEI on FBT–Na, where Na–F primarily results from the spontaneous reaction between sodium metal and FBT, with a minor contribution from the decomposition of hexafluorophosphate. Fig. 2e depicts the O 1s spectrum of the SEI on FBT–Na, which, unlike that of bare Na, features an additional peak at 532.2 eV corresponding to amide groups, further verifying the existence of amide functional groups. Fig. 2f presents the high-resolution S 2p spectrum of the SEI on FBT–Na, with the detection of Na₂S corresponding to a peak at 161.9 eV. XPS analysis confirmed that the natural SEI surface is mainly composed of Na₂CO₃, Na₂O, and a small amount of NaF, while the SEI on the modified sodium metal surface is a composite of organic and inorganic components, including organic amide bonds and inorganic components of NaF and Na₂S. The inorganic components (NaF and Na₂S) provide high ionic conductivity, while the organic components (amide groups) homogenize the Na⁺ flux through polar adsorption. This synergistic effect optimizes interfacial ion transfer and enhances the transport efficiency of Na⁺. Under the synergistic effect of the organic/inorganic composite components, the FBT–Na battery achieves fast ion conduction and a dendrite-free growth morphology.

Fig. 2 X-ray photoelectron spectroscopy (XPS) spectra of bare Na and FBT–Na symmetric cells after cycling. (a) F 1s spectra of the bare Na electrode after 20 cycles. (b) O 1s spectrum of the bare Na electrode after 20 cycles. (c) N 1s spectrum of the FBT–Na electrode after 20 cycles. (d) F 1s spectrum of the FBT–Na electrode after 20 cycles. (e) O 1s spectrum of the FBT–Na electrode after 20 cycles. (f) S 2p spectrum of the FBT–Na electrode after 20 cycles.

To further investigate the protective effect of the organic/inorganic composite SEI film and the deposition behavior of sodium ions, scanning electron microscopy (SEM) was employed to characterize the surface of sodium metal electrodes after 50 cycles. As depicted in Fig. 3a–c, the bare Na electrode exhibited a mossy dendritic structure and significant structural fractures after 50 cycles.^27,28 The cross-sectional view revealed a porous natural SEI film on the bare sodium surface, indicating that the electrolyte could easily penetrate and react with sodium metal, leading to side reactions. The thickness of this SEI film was measured to be 45 μm, suggesting that extensive side reactions had caused SEI accumulation, which hindered sodium ion transport. In contrast, as shown in Fig. 3d–f, the surface of the FBT–Na electrode was smooth, primarily composed of round sodium metal nanoparticles, with no significant dendrite formation. The cross-sectional view indicated a dense organic-inorganic composite protective layer with a thickness of only 20 μm, which effectively resisted electrolyte penetration, shortened the diffusion path of sodium ions, and enhanced sodium ion transport kinetics. Energy-dispersive X-ray spectroscopy (EDX) spectra (Fig. S2†) revealed the uniform distribution of F, S, and N elements on the FBT–Na surface, further confirming that the artificial protective layer was primarily composed of beneficial components of the SEI film, such as NaF, Na₂S, and amide groups.

Fig. 3 Scanning electron microscopy (SEM) images of the bare Na and FBT–Na symmetric cells after cycling. (a)–(c) SEM images of the top and cross-sectional views of bare Na electrodes after 50 cycles at 1 mA cm⁻²/1 mA h cm⁻². (d)–(f) SEM images of the top and cross-sectional views of FBT–Na electrodes after 50 cycles at 1 mA cm⁻²/1 mA h cm⁻².

In order to further confirm the effective protection of the artificial SEI on the sodium metal anode interface, Na‖Cu batteries were assembled and tested at a current density of 0.5 mA cm⁻² and an areal capacity of 1 mA h cm⁻².²⁹ Voltage-capacity profiles of bare Na‖Cu and FBT–Na‖Cu batteries after the 1st, 100th, and 200th cycles are depicted in Fig. 4a and b, respectively. The bare Na‖Cu battery exhibits unstable voltage-capacity profiles and significant capacity loss due to severe side reactions, whereas the FBT–Na‖Cu battery shows nearly overlapping voltage-capacity profiles with minimal capacity decay across different cycles. Fig. 4c compares the nucleation overpotential of bare Na‖Cu and FBT–Na‖Cu batteries at 0.5 mA cm⁻²/1 mA h cm⁻². Benefiting from the presence of high ionic conductivity and Na⁺–philic components in the artificial SEI layer, the FBT–Na‖Cu battery demonstrates low nucleation overpotential, indicating stable and reversible Na plating/stripping behavior on FBT–Na. Coulombic efficiency (CE) is a critical parameter for evaluating the reversibility of sodium plating/stripping processes.³⁰Fig. 4d compares the CE of asymmetric batteries using the two anodes. The FBT–Na‖Cu battery stably cycles for 500 cycles with an average CE of approximately 98.8%, whereas the CE of the bare Na‖Cu battery remains unstable. Data from Na‖Cu batteries further confirm that the artificial SEI effectively protects the anode interface, suppresses adverse side reactions between the electrolyte and electrode, and significantly enhances the battery's CE and cycling performance.

Fig. 4 Performance comparison of bare Na‖Cu and FBT–Na‖Cu cells. (a) Voltage profiles of bare Na on Cu foil during the first, 100th, and 200th cycles. (b) Voltage profiles of FBT–Na on Cu foil during the first, 100th, and 200th cycles. (c) Nucleation overpotentials of bare Na‖Cu and FBT–Na‖Cu cells at 0.5 mA cm⁻²/1 mA h cm⁻². (d) Coulombic efficiencies of bare Na‖Cu and FBT–Na‖Cu cells at 0.5 mA cm⁻²/1 mA h cm⁻².

To evaluate the effectiveness of the protective layer, symmetric Na‖Na cells were assembled to evaluate their cycling performance. By comparing the cycling performance of symmetric cells assembled with different concentrations of FBT (ESI Fig. 3†), we ultimately selected a mass fraction of 4% for subsequent electrochemical tests. Comparing the impedance of symmetric cells before and after cycling (Fig. 5a), the semicircle diameter of the bare Na cell increases, indicating an increase in SEI film impedance. This is due to the growth of sodium dendrites, which cause the SEI film on the bare sodium electrode surface to continuously fracture and re-form, thickening over time. Additionally, the bulk impedance increases with the number of cycles, as the continuous decomposition of the electrolyte to repair the SEI film leads to salt loss, a reduced solute concentration, and increased solution resistance. In contrast, for FBT–Na, neither the SEI resistance nor the bulk resistance shows significant changes, and the impedance values are lower than those of the bare Na cell. This indicates that its interfacial film is stable, less prone to fracture, and possesses high ionic conductivity, facilitating the rapid migration of Na⁺.³¹Fig. 5b and c show that the Tafel exchange current and CV peak current of the FBT–Na symmetric cell are greater than those of the bare Na cell. This is attributed to the high ionic conductivity of NaF and Na₂S in the protective layer, which constructs a sodiumphilic interface and promotes Na⁺ transport, resulting in faster ion transfer kinetics. As shown in Fig. 5d, under the testing conditions of 1 mA cm⁻²/1 mA h cm⁻², the bare Na cell begins to exhibit severe voltage fluctuations and gradually fails after 250 hours of cycling. This is attributed to excessive sodium dendrite growth and numerous side reactions. In contrast, the FBT–Na cell demonstrates stable cycling for over 2500 hours, representing a tenfold increase in cycle life compared to bare Na. Furthermore, the FBT–Na cell maintains an ultra-low polarization voltage (only 10 mV), indicating that the artificial SEI film effectively protects the sodium metal anode, significantly enhances the cycling performance of sodium metal batteries, and ensures rapid ion transport kinetics at the FBT–Na interface. By examining the plating/stripping behavior of the two electrodes under varying current conditions using step current tests (with current density incrementally increasing from 0.2 mA cm⁻² to 3 mA cm⁻² at a fixed capacity of 1 mA h cm⁻²), Fig. 5e reveals that the FBT–Na cell exhibits lower polarization voltage and superior cycling stability across different current densities, demonstrating excellent rate performance of the FBT–Na symmetric cell. From the magnified regions of the voltage–time curves in Fig. 5f, it is evident that the bare Na cell exhibits significant voltage fluctuations, whereas the FBT–Na cell shows smaller polarization voltage and stable voltage profiles. After 2000 hours of cycling, the bare Na cell had already short-circuited and failed, while the FBT–Na cell continued to maintain stable cycling (Fig. 5g). When the testing current and capacity were increased to 2.0 mA cm⁻²/2.0 mA h cm⁻² (ESI Fig. 4a–c†), the FBT–Na cell still achieved stable cycling for 1000 hours, whereas the bare Na cell displayed progressively increasing polarization voltage after 100 hours and short-circuited after 200 hours. Further increasing the testing current to 3.0 mA cm⁻² at a capacity of 1 mA h cm⁻² (ESI Fig. 5a–c†), the FBT–Na cell maintained stable cycling for over 700 hours, while the bare Na cell exhibited severe voltage fluctuations after approximately 30 hours. This is due to the intensified side reactions under high current conditions, leading to poorer cycling performance of the bare Na cell. In contrast, the FBT–Na cell effectively protected the sodium metal anode even at high current. Fig. 5h compares the performance of symmetric cells in this work with other reported studies on sodium metal anode protection. It is clear that the cycling performance in this work significantly outperforms others under the same current density and capacity conditions.

Fig. 5 Performance comparison of bare Na and FBT–Na symmetric cells. (a) Electrochemical impedance spectroscopy (EIS) impedance plots of the bare Na and FBT–Na symmetric battery after corresponding cycling times. (b) Tafel plots obtained from cyclic voltammetry measurements. (c) Cyclic voltammetry (CV) tests of bare Na and FBT–Na symmetric cells. (d) Cycling performance of bare Na and FBT–Na symmetric cells at 1.0 mA cm⁻²/1.0 mA h cm⁻². (e) Rate performance of bare Na and FBT–Na symmetric cells at a capacity of 1 mA h cm⁻². (f)–(g) Local magnification regions of bare Na and FBT–Na symmetric cells at different time intervals. (h) Comparison of the performance in this work with that in other published studies at 1.0 mA cm⁻²/1.0 mA h cm⁻².

To further demonstrate the practical application of the FBT protective layer, full cells were assembled by pairing bare Na and FBT–Na with Na₃V₂(PO₄)₃ (NVP) cathodes. The rate performance of the full cells was tested at different current densities, as shown in Fig. 6a. The FBT–Na‖NVP cell exhibited superior rate performance, with higher reversible capacity and capacity retention rates between 0.5C and 5C compared to the bare Na‖NVP cell. The charge/discharge curves of the bare Na‖NVP cell at 5C for the 1st, 50th, and 100th cycles are shown in Fig. 6b. The polarization voltage of the bare Na‖NVP cell increased with the number of cycles. In contrast, the charge/discharge curves of the FBT–Na‖NVP cell at the 1st, 400th, and 800th cycles (Fig. 6c) almost completely overlapped, with a smaller polarization voltage. This indicates that the FBT protective layer effectively suppresses side reactions between the electrolyte and the sodium metal anode, promoting the kinetics of Na⁺ transport. As shown in Fig. 6d, at a rate of 1C, the initial reversible capacity of the FBT–Na‖NVP cell was 107 mA h g⁻¹, with a capacity retention rate of 90.2% after 1000 cycles and a coulombic efficiency close to 100%. In contrast, the bare Na‖NVP cell suddenly failed after 400 cycles, with a capacity retention rate of only 85.8%. At a higher current density of 5C (Fig. 6e), the FBT–Na‖NVP cell still exhibited good cycling stability, with a capacity retention rate of 89.2% after 800 cycles. The bare Na‖NVP cell, however, showed significant capacity decay after only 150 cycles and completely failed after 180 cycles. This is mainly due to the more intense dendrite growth on the unmodified sodium metal surface at high current, leading to the accumulation of dead sodium that hinders Na⁺ migration at the interface, resulting in rapid capacity decay and cycling instability.³² The FBT–Na‖NVP cell, with its composite protective layer, regulates Na⁺ flux and suppresses dendrite growth, thus achieving excellent cycling performance and capacity retention.

Fig. 6 Performance comparison of bare Na‖NVP and FBT–Na‖NVP cells. (a) Rate capabilities of bare Na‖NVP and FBT–Na‖NVP cells. (b) Charge–discharge profiles of bare Na‖NVP cells at 5C for the first, 50th, and 100th cycles. (c) Charge–discharge profiles of FBT–Na‖NVP cells at 5C for the first, 400th, and 800th cycles. (d) Long-term cycling performance of bare Na‖NVP and FBT–Na‖NVP cells at a 1C rate. (e) Long-term cycling performance of bare Na‖NVP and FBT–Na‖NVP cells at a 5C rate.

3. Conclusion

In summary, a multifunctional organic/inorganic composite SEI was generated in situ via a simple drop-casting method. The abundant amide organic groups in the SEI exhibit a strong affinity for Na⁺, enabling the regulation of Na⁺ flux and the alleviation of the tip effect, thereby inhibiting the formation of sodium dendrites. Meanwhile, the inorganic components NaF and Na₂S, with their high ionic conductivity, serve as efficient pathways for Na⁺ transport, facilitating rapid ion transfer at the interface and ensuring the high reversibility of sodium plating/stripping. The FBT-protected Na‖Na symmetric cell cycled stably for over 2500 hours at 1 mA cm⁻²/1 mA h cm⁻², with an extremely low polarization voltage of only 10 mV. The full cell assembled with FBT–Na and NVP also demonstrated excellent cycling performance and capacity retention (90.2% after 1000 cycles at 1C). The composite artificial SEI design concept proposed in this study offers new insights for developing dendrite-free, high-performance sodium metal batteries.

Data availability

Data available on request from the authors. The data that support the findings of this study are available from the corresponding author, upon reasonable request.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported primarily by the National Natural Science Foundation of China (22109025) and Department of Education, Fujian Province (JAT210017).

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Footnote

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d5se00307e

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