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Review

Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes

by
Pengcheng Shi
1,†,
Xu Wang
2,†,
Xiaolong Cheng
1 and
Yu Jiang
1,*
1
School of Materials Science and Engineering, Anhui University, Hefei 230601, China
2
School of Computer Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Batteries 2023, 9(7), 345; https://doi.org/10.3390/batteries9070345
Submission received: 20 May 2023 / Revised: 17 June 2023 / Accepted: 23 June 2023 / Published: 27 June 2023
(This article belongs to the Special Issue Solid State Batteries: From Materials Research to Design and Applications)
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Abstract

:
Nature-abundant sodium metal is regarded as ideal anode material for advanced batteries due to its high specific capacity of 1166 mAh g−1 and low redox potential of −2.71 V. However, the uncontrollable dendritic Na formation and low coulombic efficiency remain major obstacles to its application. Notably, the unstable and inhomogeneous solid electrolyte interphase (SEI) is recognized to be the root cause. As the SEI layer plays a critical role in regulating uniform Na deposition and improving cycling stability, SEI modification, especially artificial SEI modification, has been extensively investigated recently. In this regard, we discuss the advances in artificial interface engineering from the aspects of inorganic, organic and hybrid inorganic/organic protective layers. We also highlight key prospects for further investigations.

1. Introduction

To date, sodium (Na) ion batteries have been commercialized as a supplemental technology for lithium (Li) ion batteries due to natural-abundant Na resources and low costs [1]. However, the energy density of Na ion batteries appears to be unsatisfactory as compared to updated Li ion batteries [2,3]. To meet the rapidly growing demands for the energy density of Na ion batteries, the development of advanced electrode materials with high capacity is highly desired [4].
Among various materials, the metal Na has been proposed as an ideal candidate due to its high specific capacity (1166 mAh g−1) and low redox potential (−2.71 V) [5,6,7]. In this regard, investigations regarding Na-based batteries, including Na-S, Na-O2 and Na-CO2 batteries, have been widely reported [5]. However, the cycling performances and safety issues of Na anodes remain unsatisfactory. It has been reported that growth of dendrites may be the root reason. The spontaneous reaction between Na and electrolytes can form a chemically/mechanically unstable solid electrolyte interphase (SEI), which cannot maintain long-term cycling of the Na anode [8,9]. During plating/stripping, the SEI would be thickened, broken and collapsed [7,9], inducing dendrite formation. Additionally, the thickness change during Na plating/stripping can lead to great local stress, making the SEI much more unstable and more easily cracked [10,11]. In particular, the dendritic Na can penetrate through the separator and detach from the matrix easily to form “dead” Na, leading to battery short circuits and a short cycle life [11,12,13,14]. Therefore, effective efforts to modify Na metal anodes are highly necessary.
Under this background, several approaches have been proposed to stabilize Na anodes: for instance, constructing a 3D host to resolve infinite volume expansion [6,14,15], coating the separator to block Na dendrites [16,17] and employing an Na alloy to build stable anodes [18,19,20]. Although these approaches have some positive effects in suppressing dendritic Na formation, the properties of SEI films remain unsatisfactory, and the irreversible side reactions cannot be totally suppressed. The electrolyte modification seems to be promising for increasing the stability of the SEI interphase. However, the additives, salts and solvents cannot hold for long-term cycling due to continuous consumption [11,21]. Accordingly, the ideal SEI for Na metal should possesses excellent chemical/electrochemical stability, good ionic conductivity, even Na+ flux/electric field distribution, sufficient Young’s module, good flexibility and robustness [22]. In this regard, artificial interphase engineering is of vital importance, since the protective layer can be precisely designed and easily adjusted. More importantly, the artificial SEI boasts most of the above-mentioned merits of an ideal SEI. So far, extensive research has been conducted on artificial interphase configuration to improve the stability of the SEI [23,24]. Therefore, it is necessary to summarize the research progress in artificial SEI design in recent years.
In this review, we discuss the advances in artificial interface engineering from the aspects of inorganic, organic and hybrid inorganic/organic protective layers, as shown in Figure 1. The specific modified materials, synthetic processes and properties of the artificial SEI layers are systematically reviewed. Meanwhile, the working mechanism of these artificial SEIs is also briefly analyzed. We also conclude by outlining future directions of artificial interphase chemistry for advanced Na metal anodes. We hope this review can deepen the understanding of artificial SEI layers by exploring stable and dendrite-free Na anodes.

2. Challenges for Dendrite-Free Na Metal Anodes

Like other alkali metals, Na is thermodynamically unstable; this is the root cause of uncontrollable parasitic reactions and the formation of chemically/mechanically unstable SEIs [23,24]. Figure 2a shows the main challenges of Na metal anodes. As compared with Li metal, Na metal is more prone to deposits in dendritic morphology and suffers from severe volume expansion [25,26]. During plating/stripping, the SEI can be cracked and form “dead” and isolated Na. Meanwhile, the growth of dendrites can lead to battery short-circuiting. The overall challenges regarding dendrite-free Na metal anodes are discussed below.

2.1. High Reactivity

The Na atom can lose electrons to form Na+ easily. In dry air, the Na metal can react with O2 and CO2. When contacting water or moist air, the Na metal can form flammable H2 to cause fire or even explosions. Due to high reactivity, the Na metal will induce unavoidable side reactions with liquid electrolytes, resulting in SEI formation, Na corrosion and poor cycling performance, as shown in Figure 2b. Even worse, the leakage or breakage of batteries can cause safety issues.

2.2. Unstable SEIs

It is expected that the ideal SEI layer is dense and inert so as to effectively isolate electron transfer and prevent further parasitic reactions [24,27]. Nevertheless, the structure of the SEI layer formed in common electrolytes is demonstrated to be porous and fragile.
As it is recognized, the properties of the SEI layer formed in common electrolytes depend on the solvents, additives and Na salts. Typically, the SEI layer is mainly composed of inorganic species (e.g., NaF, Na2O and Na2CO3) and organic species (e.g., RONa, ROCO2Na and RCOONa; where R is the alkyl group) [25]. The possible formation mechanism is summarized in the following equations [28,29].
C3H4O3(EC) + 2Na+ + 2e− → Na2CO3↓ + C2H4↑
C3H6O3(PC) + 2Na+ + 2e− → Na2CO3↓ + C3H6↑
C3H3FO3(FEC) + Na+ + e− → NaF↓ + CO2↑ + CH2CHO↑
PF6− + 3Na+ + 2e− → 3NaF↓ + PF3
Na + 3Na+ + 2e− → 3NaF↓ + PF3
Meanwhile, the reduction of solvents can supply a large amount of oxygen atoms, leading to the formation of Na2O. Owing to the lack of advanced characterization techniques, the formation mechanism and detailed composition of the SEI layer remain controversial. Further investigations are needed for understanding the mechanism. Additionally, the SEI layer formed on the Na metal is dissolved in electrolytes more easily than that of Li [30,31]. Due to the non-uniform distribution of compositions, the ionic conductivity of the SEI layer is spatial varying, resulting in uneven distribution of the Na+ flux. Meanwhile, due to the “host-less” nature of the Na matrix, the SEI layer cracks easily during repeated Na+ plating/stripping, which in turn accelerates dendrite growth due to increased Na+ flux and preferential Na+ plating around the cracks. Furthermore, the repeated breakage of the SEI layer also leads to uncontrollable electrolyte consumption, followed by low coulombic efficiency and high SEI impedance [32,33]. As a result, Na metal with unsatisfied SEI properties inevitably suffers from poor performance.
Based on previous research [34,35], further progress on building ideal SEI layers for dendrite-free Na metal should be centered around the following characteristics: firstly, high Na+ conductivity so as to facilitate uniform Na+ deposition and regulate preferential Na plating; secondly, electrochemical stability and electronic insulation to prevent further side reactions; thirdly, sufficiently robust to maintain long-term large volume expansion and dendrite propagation; finally, homogeneous in composition to decentralize the Na+ flux.

2.3. Uncontrollable Dendritic Na Formation

Dendrite growth is also a serious problem, as shown in Figure 2b. The dendrite growth can penetrate the separator and form “dead” Na, leading to battery short circuiting and poor cycling stability. The morphology of Na dendrites can be divided into needle-like, tree-like and mossy-like types; however, it is difficult to distinguish them clearly. In most case, these types of dendrites can co-exist in rechargeable batteries [36,37].
Based on previous research [38], it is widely accepted that the concentration of Na+ will decrease to zero near the surface in Sand’s time. Due to the spatial variation in ionic conductivity and the localized electric field, the rough surface will induce uneven Na+ plating/stripping, resulting in dendrite formation. Subsequently, the tips of dendrites become hot sites for further dendritic Na nucleation and growth due to their larger electric field and ionic concentration gradients. Once the dendrite is nucleated, the growth rate of dendrites is a key parameter to determine the lifetime of Na anode. According to Sand’s law, the speed of dendrite formation is inversely proportional to the square of the deposition current [32,37,39,40].
Dendrite growth can expose the fresh Na surface to depletion of electrolytes and active Na. Meanwhile, the unstable dendrites detach from the matrix to form “dead” Na. Through microscopy observation, it has been proven that the porous Na dendrites can break away from the bulk Na matrix easily, as compared with Li dendrites. The dendrites intrinsically exhibit much higher chemical reactivity and weaker mechanical stability [39].

2.4. Severe Volume Expansion

The severe volume expansion can be regarded as the root cause of the continuous side reactions. Theoretically, the thickness would increase by 8.86 µm with 1 mAh cm−2 Na. To satisfy industrial requirements, the deposited capacity would be above 3.5 mAh cm−2 [34,41]. Due to uneven deposition, the practical volume variation would be more evident than theoretically expected. In addition, due to the host-less nature, the volume expansion is considered to be relatively infinite [42]. Meanwhile, due to lack of flexibility, the SEI can be cracked easily during volume expansion, which accelerates the formation of “dead” Na and consumption of electrolytes, as shown in Figure 2b.
To alleviate the volume expansion and mitigate the inner strain, nanostructured hosts such as Cu foam [43,44,45], carbon matrix [42,46,47] and Mxene [48,49] are proposed to accommodate Na. Nevertheless, these hosts increase the total weight and volume of the Na anode at the expense of total energy density. The recent development of hosts for dendrite-free Na metal has been discussed in several reviews [26,50].

3. Advances in Artificial SEI Interphase

A stable SEI is the ultimate pursuit for achieving dendrite-free Na metal anodes. With a deep understanding of the plating/stripping mechanism, several strategies (e.g., chemical pretreatment, building protective film by advanced deposition technologies and free-standing protective layers) for building artificial interphase have been proposed [36,37,39]. Typically, the chemical composition, structure and thickness of artificial SEI layers can be precisely controlled by optimizing the reagent species, concentration, and reaction temperature, time, etc. [36]. As reported, the artificial SEI can be classified into inorganic rich or organic rich or their hybrids [24,51,52]. The characteristics of the inorganic rich and organic rich SEI are schematically presented in Figure 3a,b. In this section, we will discuss the recent advances in constructing artificial SEIs for stable Na metal anodes.

3.1. Inorganic Interphase

Adopting the experiences and knowledge of LiX (X = F, Cl, Br, I) for dendrite suppression in Li metal batteries, NaX are proposed for inorganic interphase configuration through chemical pretreatment methods [22,36,53]. In the early stage, Wang et al. proposed a simple chemical pretreatment of Na with a SbF3/DMC solution. Through an exchange reaction, an inorganic SEI rich in NaF and Na3Sb alloy is formed. By taking advantage of the synergistic effect of NaF and Na3Sb, the hybrid NaF/Na3Sb interphase greatly reduces the surface reactivity and interfacial impedance [54,55]. Recently, the NaF-rich interphase has also been reported by reaction with 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BdmimBF4) [56], CoF2 [57], AlF3-coated solid-state electrolytes [58] and triethylamine trihydrofluoride [59]. The shear modulus of NaF is 31.4 GPa, which is much higher than that of metallic Na (3.3 GPa); thus, it plays an important role in suppressing Na dendrite growth [57,60]. Inspired by these works, NaCl-rich interphases have also been investigated. For instance, Huang et al. adopted SnCl2 to treat Na with the formation of the NaCl/Na-Sn alloy interphase [61]. As expected, both rapid ion transportation and suppressed parasitic reactions were obtained, which jointly achieved a nondendritic morphology over 500 h in Na||Na batteries. Similar treatment methods have also been reported using ZnCl2 and SnCl4 [62,63,64]. Analogous to NaF and NaCl, the NaI- and NaBr-rich interphases were reported by reaction with 1-iodopropane and 1-bromopropane, respectively [65,66]. In Na||Na cells, the NaI-coated Na was stable for 500 h under 0.25 mA cm−2 and 0.75 mAh cm−2, while the NaBr-coated Na was stable for 250 h under 1.0 mA cm−2 and 1.0 mAh cm−2. According to the density functional theory calculations in Figure 4a, the energy barriers for interface ion diffusion decrease in the following order: NaF > NaCl ≈ NaI > NaBr [66]. The lower energy barrier is more favorable for nondendritic deposition.
The S-containing protective layer is also attractive for nondendritic Na plating/stripping due to its high ionic conductivity. Sun et al. synthesized Na3PS4 as an artificial protective layer by reacting Na with P4S16 in diethylene glycol dimethyl ether. By controlling the concentrations of P4S16 and the reacting time, the thickness and composition of the Na3PS4 can be optimized. The thin Na3PS4 layer can reduce unwanted side reactions and uniform Na+ flux during plating/stripping [67]. The Mo6S8 and MoS2 were also used for building NaxMo6S8 and Na2S protective layers, as shown in Figure 4b,c, respectively [68,69]. In addition to NaX and the S-containing protective layer, the Na3N layer is also attractive due to its high ionic conductivity. In 2021, Sun et al. directly embedded NaNO3 into the Na matrix to form Na3N and NaNxOy. As shown in Figure 4d,e, the Na3N and NaNxOy provide good SEI stability and Na+ conductivity, while the remaining NaNO3 works as an SEI stabilized for long-term cycling [70].
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Figure 4. (a) Calculated energy barriers for Mg, Na and Li atom diffusion on the surface with noted chemistry [66]. In this paper, the * symbol marks the data points obtained from ref. [14]. Copyright 2017, Nature. (b) The function of Mo6S8-formed NaxMo6S8 protective layer [68]. Copyright 2019, American Chemistry Society. (c) The fabrication of Mo2S-based protective layer and the corresponding conversion reaction [69]. Copyright 2017, American Chemistry Society. (d) Mechanically fabricated NaNO3-derived Na3N/NaNxOy protective layer. (e) Image of the Na anodes with and without NaNO3 [70]. Copyright 2021, American Chemistry Society. (f) Schematic illustration of red phosphorus formed Na3P layer and the dendrite suppression mechanism [71]. Copyright 2021, Wiely-VCH.
Figure 4. (a) Calculated energy barriers for Mg, Na and Li atom diffusion on the surface with noted chemistry [66]. In this paper, the * symbol marks the data points obtained from ref. [14]. Copyright 2017, Nature. (b) The function of Mo6S8-formed NaxMo6S8 protective layer [68]. Copyright 2019, American Chemistry Society. (c) The fabrication of Mo2S-based protective layer and the corresponding conversion reaction [69]. Copyright 2017, American Chemistry Society. (d) Mechanically fabricated NaNO3-derived Na3N/NaNxOy protective layer. (e) Image of the Na anodes with and without NaNO3 [70]. Copyright 2021, American Chemistry Society. (f) Schematic illustration of red phosphorus formed Na3P layer and the dendrite suppression mechanism [71]. Copyright 2021, Wiely-VCH.
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Recently, Yu’s group built a Na3P protective layer to protect Na metal by treating it with red phosphorus. As shown in Figure 4f, the Na3P layer can provide high ionic conductivity of ~0.12 mS cm−1 and high Young’s modulus of 8.6 GPa, which regulates uniform Na+ flux and prevents the dendrite growth. As proven by cryo-TEM, the Na3P phase can remain after repeated plating/stripping, which is highly attractive for achieving stable Na anodes. Benefiting from these advantages, the Na||Na cells with a Na3P artificial layer present a nondendritic morphology for 780 h at 1.0 mA cm−2 and 1.0 mAh cm−2. In addition, the artificial phosphorus derived protection layer was also applied for dendrite-free potassium metal, with satisfactory performance [71]. More recently, Yu’s group also proved that the Na2Te artificial interfacial layer showed similar advantages [72]. At 1.0 mA cm−2 and 1.0 mAh cm−2, the Na@Na2Te provides excellent cyclic stability for 700 h. As interfaces with a single component cannot meet all the requirements of an ideal SEI, Wu et al. and Ji et al. further developed a hybrid Na3P/NaBr interphase with faster ionic conductivity compared with Na3P [73,74]. Rui et al. also adopted V2S3 [75], VN [13], VSe [76], VP2 [77] and BiOCl [78] as precursors to build artificial heterogeneous interphase layers. With vanadium and Na3Bi, a more uniform deposition of Na+ is promoted and better cycling performance is achieved.
The Na alloy interphases are also attractive. Due to the low reduction potential of Na, the metal cations dissolved in solvents can spontaneously alloy with Na. For Li metal, Li et al. immersed Li in Mg(TFSI)2 containing electrolytes, with the formation of Li-Mg alloy [79]. The pre-alloying with Mg avoids the nucleation of Li at the hot points for dendrite growth and prevents electrolyte corrosion. This approach also applies to Na metal anodes. By taking advantage of Sn(TFSI)2, a Na-Sn alloy interphase rich in Na9Sn4 and Na14.7Sn4 can be obtained. Under 0.25 mAh cm−2, the Na||Na cells can physically mitigate dendrite growth for 1700 h due to their fast ion transport properties. Despite the surface alloy, some cations can be reduced as metals, usually acting as nucleation seeds for dendrite suppression [80]. Chen’s group used Bi(SO3CF3)3 to treat Na with the formation of Bi. Under 0.5 mA cm−2, the Na-Bi anode can cycle for 1000 h without overpotential increase [81]. Analogous AgTFSI and AgCF3SO3 were also achieved with the formation of Ag seeds [82,83]. Notably, these species are also powerful for using as additives for electrolyte modification [39]. More recently, Yu et al. also alloyed the Na surface with Ga liquid metal and Sn foil via in-suit rolling [84,85,86].
In addition to chemical pretreatment methods for inorganic SEI configuration, the physical deposition method is also proposed. Among the different technologies, the atomic layer deposition (ALD) technology is most attractive, since it has long been used for building advanced protective layers for batteries. Early in 2017, a thin Al2O3 protective layer was achieved on Na through low-temperature plasma-enhanced ALD, as shown in Figure 5a [87,88,89]. The low-temperature ALD can avoid the melting of Na (98 °C) due to its low working temperature of 75 °C. Based on the growth rate of Al2O3, the thickness of 10, 25 and 50 cycles of ALD Al2O3 is confirmed to be 1.4, 3.5 and 7 nm, respectively. Attractively, the Al2O3 can convert into highly conductive NaAlOx during cycling. The Na@Al2O3 displayed an island-like morphology up to 500 cycles, even at 3 mA cm−2. Analogous to ALD, the molecular layer deposition (MLD) technology is also proposed for building hybrid inorganic/organic protective layers [90]. The MLD will be discussed in the following hybrid interphase section.
Another type of inorganic SEI is designed by using prefabricated free-standing films. Typically, these free-standing films can improve the surface sodiophilicity with functional groups. Meanwhile, with these free-standing films, the average plating/stripping coulombic efficiency and cycling stability of Na||Cu batteries is increased during long-term cycling, indicating reduced side reactions. Peng et al. presented an O-functionalized 3D carbon nanotube film (Of-CNT), as shown in Figure 5b [91]. According to DFT calculation, the oxygen function group strongly interacts with Na+, as shown in Figure 5c, which provides a robust sodiophilic interphase. Benefiting from the sodiophilic nature, the Of-CNT offers preferential Na nucleation with a reduced overpotential and improves the reaction kinetics. Similar free-standing films are also proposed with O and N functioning 3D nanofibers (ONCNFs) [92]. Despite 3D carbon nanofibers, 2D materials such as MXenes, graphene, silicene, germanene, phosphorene, h-BN, SnS, SnSe and g-C3N4 film have also attracted tremendous attention [93,94,95]. In order to accelerate surface Na+ transfer and improve the ionic conductivity of the protective layer, the introduction of defects, the increase in bond length and the proximity effect should be seriously considered, as confirmed by first-principles calculations. Meanwhile, their balance with surface stiffness for dendrite suppression is also a critical factor. In this regard, Chen et al. used MXene and carbon nanotubes (CNTs) to construct a 3D MXene/CNTs sodiophilic layer for rapid Na+ diffusion and dendrite suppression [96]. Li et al. also prepared Sn2+ pillared Ti3C2 MXene [97]. The Sn2+ can act as sodiophilic seeds and form highly conductive Na15Sn4 alloy to balance the electric field. Tian et al. also reported Mg2+-decorated Ti3C2 MXene as a protective layer for Na metal [98]. In addition to these, Wang et al. prepared a 3D sodiophilic Ti3C2 MXene@g-C3N4 hetero-interphase in Figure 5d, in which MXene acts as the highly conductive substrate, and the g-C3N4 acts as an interfacial modulation layer to regulate Na+ deposition. As shown in Figure 5e, the Ti3C2 MXene@g-C3N4 hetero-interphase shows the largest adsorption energy, contributing to the formation of a sodiophilic surface [99]. In conclusion, these free-standing protective layers possess tuned electronic properties, strong sodiophilicity and structural robustness.
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Figure 5. (a) Schematic of the ALD deposition of Al2O3 with TMA and O2 plasma [87]. Copyright 2017, Wiely-VCH. (b) The function of the Of−CNT network in homogeneous nucleation and smooth Na deposition. (c) Binding energies of Na with various functional groups [91]. Copyright 2019, Wiely-VCH. (d) The fabrication process of Ti3C2 MXene@g−C3N4 hetero−interphase for dendrite suppression. (e) Binding energies of Na with Cu, Ti3C2 MXene, g−C3N4 and Ti3C2 MXene@g−C3N4 [99]. Copyright 2022, American Chemistry Society.
Figure 5. (a) Schematic of the ALD deposition of Al2O3 with TMA and O2 plasma [87]. Copyright 2017, Wiely-VCH. (b) The function of the Of−CNT network in homogeneous nucleation and smooth Na deposition. (c) Binding energies of Na with various functional groups [91]. Copyright 2019, Wiely-VCH. (d) The fabrication process of Ti3C2 MXene@g−C3N4 hetero−interphase for dendrite suppression. (e) Binding energies of Na with Cu, Ti3C2 MXene, g−C3N4 and Ti3C2 MXene@g−C3N4 [99]. Copyright 2022, American Chemistry Society.
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3.2. Organic Interphase

Apart from the inorganic interphase, the organic interphase is also attractive, since the precursor can be precisely designed and optimized at the molecular level [24,100,101]. The organic SEI layer is capable of alleviating the volume expansion and preventing dendrite growth due to its excellent flexibility.
Previously, the polar polymers (poly(dimethylsiloxane)(PDMS), polyacrylic acid(PAA), etc.) were proven to be strongly interacting with Li+, which would be effective for regulating uniform distribution of ion flux [102,103,104]. Inspired by these works, Ma’s group prepared a fibrillar poly(1,1-difluoroethylene) (PVDF) fiber film (f-PVDF) with non-through pores by electro-spinning. By working as a blocking interlayer for dendrite suppression, the f-PVDF film is superior to the conventional compact PVDF film, PVDF film with through pores, polyethylene oxide (PEO) film, and polytetrafluoroethylene (PTFE) film. It is noticed that the polar C-F group affinity to Na+ is stronger than C-O groups in PEO, which provides a better environment for uniform Na+ deposition. Meanwhile, the f-PVDF shows better electrolyte uptake for faster ion conductivity. More recently, Lu et al. protected Na metal anodes by soaking them in 1,3-dioxolane (DOL), as shown in Figure 6a. The polar C-O of DOL can break with the formation of poly(DOL), which enables a faster interfacial transport and a lower interfacial resistance. In detail, the polymerization of DOL forms Na alkoxides (CH3OCH2CH2ONa and CH3CH2OCH2ONa) and HCOONa. Then, the Na alkoxides transform into RONa by further reacting with Na. Finally, the RONa and HCOONa in turn react with DOL continuously. With protected poly(DOL), a cycling life over 2800 h at 1mA cm−2 can be obtained in symmetric cells. Lu et al. also proposed spraying DOL for large-scale manufacturing [105]. Meanwhile, as shown in Figure 6b, Wei et al. also used imidazolium ionic liquid monomers to prepare ionic membranes through in-suit electro-polymerization. The obtained ionic membrane (about 50 nm thick) can regulate the electric field and stabilize the Na anode [106].
In addition to polymer-based SEI, organic Na benzenedithiolate (PhS2Na2) and HCOONa have also been reported, as shown in Figure 6c,d. In 2020, Wu et al. reported a PhS2Na2-rich protection layer for Na metal. They first chemically treated Na metal with S8 and para-dichlorobenzene (p-DB) in tetrahydrofuran solution, along with the formation of poly(phenylene sulfides) (PPS), NaCl, and Na2Sy. Then, it was converted into PhS2Na2 upon cycling. Using DFT calculations, they established the function of PhS2Na2 species. Since the binding energy of Na+ in PhS2Na2 (−2.3 eV) and Ph-S-Na (−2.13 eV) is much lower than that of CH3ONa (−2.49 eV), CH3OCO2Na (−2.497 eV) and Na2CO3 (−3.5 eV), a higher ionic conductivity is proven for the PhS2Na2-based SEI [107]. More recently, Zheng et al. treated Na with formic acid vapor via a solid–gas reaction strategy. After 10 s, the silvery-white Na surface changed into dark-red HCOONa, as confirmed by X-ray diffraction and Raman spectroscopy. Then, the organic HCOONa layer could work as a robust interfacial layer with a low Na+ diffusion barrier. Additionally, the HCOONa interface could also extend to anode-free batteries with format-modified collectors [108].
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Figure 6. (a) Process of preparing poly(DOL)−protected Na metal [105]. Copyright 2021, Royal Society of Chemistry. (b) In−suit polymerization of imidazolium ionic liquid monomers on Na [106]. Copyright 2017, Wiely-VCH. (c) The fabrication of a PhS2Na2−rich protection layer on Na [107]. Copyright 2019, Wiely-VCH. (d) The HCOONa protective layer on Na metal and Cu foil for Na||Na3V2(PO4)3 and HCOONa-Cu|| Na3V2(PO4)3 batteries [108]. Copyright 2023, Wiely-VCH. (e) Deposition of Na morphology on Cu foil without and with the MOFs layer [109]. Copyright 2019, Elsevier.
Figure 6. (a) Process of preparing poly(DOL)−protected Na metal [105]. Copyright 2021, Royal Society of Chemistry. (b) In−suit polymerization of imidazolium ionic liquid monomers on Na [106]. Copyright 2017, Wiely-VCH. (c) The fabrication of a PhS2Na2−rich protection layer on Na [107]. Copyright 2019, Wiely-VCH. (d) The HCOONa protective layer on Na metal and Cu foil for Na||Na3V2(PO4)3 and HCOONa-Cu|| Na3V2(PO4)3 batteries [108]. Copyright 2023, Wiely-VCH. (e) Deposition of Na morphology on Cu foil without and with the MOFs layer [109]. Copyright 2019, Elsevier.
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Recently, metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have been reported to serve as ionic sieves to control uniform Na+ plating. In 2019, Chen et al. prepared MOF-199 and ZIF-8 as a coating layer on a Cu substrate [109]. By acting as a compact and robust shield, the MOF-199 layer can physically prevent dendrite growth, thus regulating dense Na deposition and producing less excess SEI formation, as shown in Figure 6e. Similar Mg-based MOF-74 has also been proposed by Yang et al. They first prove that the main group II metals (Be, Mg, and Ba) can act as nucleation seeds for homogeneous Na deposition. Benefiting from these merits, the Mg-based MOF-74 is used to control Na deposition. With eliminated nucleation barriers, a uniform morphology can be obtained [110]. The liquid MOF of ZIF-62 has also been proposed for building protective layers for solid batteries [111]. The ZIF-62 interlayer is synthesized from the high-temperature monophase of liquid MOF. The uniform ZIF-62 layer can increase interfacial sodiophilicity and improve e−/Na+ transport kinetics. More recently, the sp2 carbon COF (sp2c-COF) functional separator has also been built to induce a robust SEI [16]. The high-polarity architecture shows a good affinity toward Na+, which helps to achieve a uniform ion flux and a nondendritic morphology during plating/stripping [112,113]. To date, reports on applying MOFs and COFs to prevent dendrite growth of Na metal remain limited.

3.3. Hybrid Interphase

To combine the advantages of artificial inorganic SEI and organic SEI, researchers have proposed a hybrid organic–inorganic SEI, in which the inorganic components offer sufficient mechanical strength to suppress dendrites and the organic components provide a certain flexibility to alleviate the volume expansion. In 2017, Kim et al. presented a free-standing inorganic/organic protective layer composed of mechanically robust Al2O3 and flexible PVDF polymer (FCPL). The FPCL has a high shear modulus, which is critical for dendrite suppression. Nevertheless, the FCPL could not enhance cycling stability due to its low ionic conductivity [114]. In order to further improve the ionic conductivity, Jiao et al., using NaF and PVDF, prepared a similar free-standing and implantable artificial film (FIAPL) to protect Na [115]. In FIAPL, the organic PVDF film could accommodate the volume expansion and thereby maintain the integrity of the interface, while the inorganic NaF particles could improve ionic conductivity and mechanical strength, resulting in uniform Na nucleation and deposition. The same PVDF/NaF layer was also coated on Cu substrate for Na deposition [116]. Inspired by the PVDF/NaF layer, Yu et al. further treated Na with PTFE via in-suit rolling with the formation of NaF/organic carbon species, which function with C=C and C-F groups [117]. They experimentally verified the high mechanical strength, fast ionic kinetics and good sodiophilicity of this protective layer [117,118,119,120]. As reported by Tao et al., the PTFE-derived NaF/carbon layer can be rapidly induced by pressure and a diglyme-induced defluorination reaction, as shown in in Figure 7a. It is explained that the diglyme can bond with Na easily to form chains of O-Na-O, which react with PTFE film rapidly. Benefiting from these merits, the NaF/organic carbon protective layer shows a long life of 1800 h under 3mAh cm−2. The authors also confirmed a similar HnC-O-HnC chain could be obtained using other solvents [121].
The polymer/metal interphases have also been proposed. The polymer film is flexible to accommodate surface expansion, whereas the sodiophilic metal can offer sufficient Na+ ions and high mechanical modulus for dendrite-free plating/stripping. In 2020, Huang et al. reported a well-designed artificial protective layer consisting of PVDF and Sn by coating a Cu collector. [122]. With the PVDF–Sn protective layer, a high average CE of 99.73% can be obtained for 2800 h at 2 mA cm−2. Li et al. also proposed a polyacrylonitrile (PAN) film with a thin Sn layer coated on the bottom. As shown in Figure 7b, benefiting from the low nucleation barrier of Sn seeds, the PAN–Sn protective layer can regulate Na deposition with a controlled location and orientation [123]. More recently, in 2022, Li et al. constructed a similar polymer PVDF and metal Bi layer on Cu substrate (PB@Cu). The cyclic voltammetry and galvanostatic discharge curves in Figure 7c,d confirm the alloying/dealloying of Bi. With Bi metal, the deposition kinetics of Na are increased. At 1 mA cm−2 and 1 mAh cm−2, the PVDF-Bi layer provides a high utilization of Na and a long lifetime of 2500 h, as shown in Figure 7e. The superior electrochemical performance of the PVDF-Bi layer is revealed to originate from flexible PVDF, which could accommodate severe volume change induced by Na+ plating/stripping. Meanwhile, the Bi and/or sodiated Na3Bi can offer high ionic conductivity and sufficient mechanical strength [124].
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Figure 7. (a) Schematic of pressure and diglyme−induced defluorination reaction for preparing PTFE-derived NaF/carbon layer [121]. Copyright 2023, Wiely-VCH. (b) Schematic illustration of PAN−Sn guiding Na deposition with a controlled location and orientation [123]. Copyright 2020, Wiely-VCH. (c) CV curves and (d) the first discharge curves of Na||Cu batteries with bare Cu and PB@Cu. (e) The voltage−time curves of Cu and PB@Cu with Na anode at 1 mA cm−2 and 1 mAh cm−2 [124]. The plating of Na on Cu and Pb@Cu are highlighted with different colors, respectively. Copyright 2022, Elsevier.
Figure 7. (a) Schematic of pressure and diglyme−induced defluorination reaction for preparing PTFE-derived NaF/carbon layer [121]. Copyright 2023, Wiely-VCH. (b) Schematic illustration of PAN−Sn guiding Na deposition with a controlled location and orientation [123]. Copyright 2020, Wiely-VCH. (c) CV curves and (d) the first discharge curves of Na||Cu batteries with bare Cu and PB@Cu. (e) The voltage−time curves of Cu and PB@Cu with Na anode at 1 mA cm−2 and 1 mAh cm−2 [124]. The plating of Na on Cu and Pb@Cu are highlighted with different colors, respectively. Copyright 2022, Elsevier.
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In contrast to stiff and dense inorganic ALD coatings, MLD coatings are confirmed to release volume expansion due to the reduced density and increased flexibility of hybrid organic–inorganic layers [90]. Meanwhile, the hybrid layers provide higher tune ability, since the integration of organic bonds in MLD coatings provides attractive chemical/electrochemical, mechanical and electrical performances. As expected, the MLD technologies show significant improvements in stabilizing Na metal without dendrite growth. As shown in Figure 8a, in 2017, Zhao et al. used trimethylaluminum and ethylene glycol (Alucone) to introduce an organic–inorganic composite layer on the Na anode via MLD at 85 °C. During experimental testing, thicknesses of 10, 25 and 40 MLD cycles were performed. It was proven that 25 MLD cycles of AIEG (Na@25Alucone) were optimal. As reported, the SEI on Na@25Alucone showed higher contents of beneficial NaF and Na2O [125].
The MLD technology is also beneficial for solid Na batteries. In 2020, Sun et al. also coated the same Alucone via MLD between Na and solid Na3SbS3 and Na3PS4 electrolytes, in which the Alucone layer worked as an interfacial stabilizer [126]. As confirmed, the type of artificial SEI layer is dependent on the ALD and MLD depositions cycles. If the deposition cycles of ALD and MLD are small, it will form a nano-alloy interface; if the deposition cycles of ALD and MLD are large, it will form full monolayer. More recently, in 2023, Sun et al. formed nano-hybrid interfaces with nano-alloy and nano-laminated structures (from Al2O3 to Alucone) through ALD-deposited inorganic Al2O3 and MLD-deposited organic Alucone for alkali metal anodes, as shown in Figure 8b [127]. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) results are shown in Figure 8c–e; the Na−, Al−, CAL− and AlO2− are probed on the Na surface, which is realized to be robust and chemically/electrochemically stable upon plating/stripping. In this study, three types of nano-hybrid interfaces are investigated: 1 layer of Al2O3 with 1 layer Alucone (1ALD-1MLD); 2 layers of Al2O3 with 2 layers of Alucone (2ALD-2MLD) and 5 layers of Al2O3 with 5 layers of Alucone (5ALD-5MLD). At the same time, the total thickness of the nano-hybrid interfaces can be controlled by deposited ALD/MLD cycles (mainly including 5, 10 and 25 cycles). The corresponding samples are donated as (1ALD-1MLD)5, (1ALD-1MLD)10 and (1ALD-1MLD)25. Among all samples, the (1ALD-1MLD)10 alloy interface shows the best performance at 3 mA cm−2 and 1 mAh cm−2 for Na metal. The mossy/dendritic Na growth and “dead” Na formation are effectively suppressed, which would account for the improved performance. Finally, the optimal thickness of the Al2O3–Alucone alloy interface for Na metal is 4 nm.
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Figure 8. (a) Na plating/stripping on bare Na and MLD−coated alucone Na [125]. Copyright 2017, American Chemistry Society. (b) Schematic illustration of the fabrication of the nano−alloy and nano−laminated interfacial structures by ALD and MLD deposition. (c) The TOF−SIMS images and depth profiles of Na−, Al−, CAL− and AlO2− ions. (d) The Rutherford backscattering spectrometry and the (e) calculated depth profiles of the (1ALD−1MLD)10 alloy interface [127]. Copyright 2023, Wiely-VCH.
Figure 8. (a) Na plating/stripping on bare Na and MLD−coated alucone Na [125]. Copyright 2017, American Chemistry Society. (b) Schematic illustration of the fabrication of the nano−alloy and nano−laminated interfacial structures by ALD and MLD deposition. (c) The TOF−SIMS images and depth profiles of Na−, Al−, CAL− and AlO2− ions. (d) The Rutherford backscattering spectrometry and the (e) calculated depth profiles of the (1ALD−1MLD)10 alloy interface [127]. Copyright 2023, Wiely-VCH.
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4. Conclusions and Perspectives

In this review, we summarize recent progress on artificial SEI design for Na metal anodes. Some related studies are summarized in Table 1. The configuration of advanced artificial SEI layers has been proposed by several researchers; this includes chemical coating, physical deposition, ex-suit conversion reactions and free-standing films. Based on experimental understanding, the artificial SEI layer can be precisely designed by optimizing the composition, thickness and morphology. Different types of artificial SEI films have their own advantages and disadvantages in suppressing dendrite growth. The inorganic artificial SEI layers usually show high ionic conductivity, good mechanical strength, high Young’s modulus and excellent stability. However, the inorganic artificial SEI is brittle, which makes them rupture easily during huge volume expansion. On the contrary, the organic artificial SEI layers are usually highly elastic, which encourages intimate contact with the Na matrix and the effective maintenance of volume expansion. Meanwhile, the organic artificial SEI can be processed easily. However, the mechanical strength, Young’s modulus and ionic conductivity of organic artificial SEI layers are much lower than those of inorganic artificial SEI layers. As a result, the long-term cycling performance of the Na anode with an organic artificial SEI layer is not very good. For the hybrid organic–inorganic SEI, the inorganic components offer sufficient mechanical strength to suppress dendrites, and the organic components provide a certain flexibility to alleviate the volume expansion. At present, the hybrid artificial SEI layers are mainly prepared via ex-suit coatings, which are limited in controlling the distribution and connection of inorganic–organic components. At the same time, the transport of Na+ in the hybrid interphase is still limited. These protective layers are either highly conductive or demonstrate mechanical stiffness/flexibility. Benefiting from these merits, the protective layers are highly effective in regulating uniform Na+ deposition and suppressing dendritic Na formation.
Despite the advantages mentioned above, some challenges still need to be explored for Na metal: (1) the effect of the physical structure, chemical composition, optimization method and Na+ diffusion mechanism on dendrite suppression should be further investigated; (2) the evolution and failure of artificial SEIs during plating/stripping need to be studied; (3) advanced characterization technologies should be used to reveal the inner relationship between the SEI and Na metal; (4) the design of SEIs should meet practical conditions, especially with limited Na and lean electrolytes; (5) the formation/growth of dendritic Na and the dynamic evolution of the interphase layer need to be fully understood for better SEI configuration.
Table
Table 1. A comparison of the electrochemical performances of various artificial SEI layers for Na metal. In the table, EC, PC, FEC, DMC, DEC, EMC, DME, TEGDME and NaTFSI represent ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, tetraethylene glycol dimethyl ether, and Na bis(trifluoromethanesulfonyl)imide, respectively.
Table 1. A comparison of the electrochemical performances of various artificial SEI layers for Na metal. In the table, EC, PC, FEC, DMC, DEC, EMC, DME, TEGDME and NaTFSI represent ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, tetraethylene glycol dimethyl ether, and Na bis(trifluoromethanesulfonyl)imide, respectively.
InterphaseTechniqueElectrolyteCurrent
(mA cm−2) Capacity
(mAh cm−2)		Lifetime
(h)		Ref.
NaF/Na3SbIn-suit reaction1 M NaClO4 in EC/PC/2%FEC0.5, 0.25650 [54]
NaFIn-suit reaction1 M NaTFSI in DME2, 21000[59]
NaIIn-suit reaction1 M NaClO4 in EC/DEC/5%FEC0.25, 0.75500[65]
NaBrIn-suit reaction1 M NaPF6 in EC/PC1, 1250[66]
NaxMo6S8In-suit sodiation1 M NaPF6 in EC/DMC0.5, /1200[68]
Na3PRolling1 M NaTFSI in FEC/EMC1, 1780[71]
Na2TeRolling1 M NaClO4 in EC/DEC/5%FEC1, 1700[72]
Na3P/NaBrIn-suit reaction1 M NaPF6 in EC/DEC/5%FEC1, 1700[73]
BiIn-suit reaction1 M NaSO3CF3 in Diglyme0.5, 11000[81]
Al2O3ALD1 M NaClO4 in EC/DEC0.25, 0.125450[87]
Of-CNTFree-standing films1 M NaSO3CF3 in Diglyme1, 14500[91]
Poly(DOL)In-suit reaction1 M NaPF6 in TEGDME1, 12800[105]
PhS2Na2Self-activation1 M NaPF6 in EC/PC1, 1800[107]
HCOONaIn-suit reaction1 M NaPF6 in Diglyme2, 12200[108]
NaF/PVDFRolling1 M NaClO4 in EC/DEC/2%FEC1, 1770[117]
PBDF/BiCoating on Cu1 M NaPF6 in Diglyme1, 12700[124]
AluconeMLD1 M NaPF6 in EC/PC1, 1270[125]
Al2O3-AluconeALD-MLD1 M NaPF6 in EC/DEC/FEC3, 11500[127]
Artificial SEI layers with high ionic conductivity, high Young’s modulus and mechanical flexibility are effective for suppressing dendritic Na formation. However, artificial SEIs alone are insufficient to address all the existing issues of Na metal anodes. For these reasons, multiple approaches with specific objectives are necessary for promoting the realization of metal Na. We expect this review will promote a deeper understanding of the SEI of Na.

Author Contributions

P.S. prepared and revised the raw manuscript. X.W. edited the figures. Y.J. and X.C. revised this manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the National Natural Science Foundation of China (No. 52002083) and the start-up grants from Anhui University (No. S020318031/001).

Data Availability Statement

There is no data support for this review.

Conflicts of Interest

The authors declare no competing financial interest.

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Figure 1. Schematic illustration of artificial interface engineering from the aspects of inorganic, organic and hybrid inorganic/organic protective layers. Different colors represent different artificial SEI layers. For each artificial SEI layer, the typical materials are showed correspondingly.
Figure 1. Schematic illustration of artificial interface engineering from the aspects of inorganic, organic and hybrid inorganic/organic protective layers. Different colors represent different artificial SEI layers. For each artificial SEI layer, the typical materials are showed correspondingly.
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Figure 2. (a) Schematic illustration of challenges for Na metal anodes [25]. Copyright 2018, Elsevier. (b) The growth of dendrites and formation of “dead” Na [6]. Copyright 2020, Wiely-VCH.
Figure 2. (a) Schematic illustration of challenges for Na metal anodes [25]. Copyright 2018, Elsevier. (b) The growth of dendrites and formation of “dead” Na [6]. Copyright 2020, Wiely-VCH.
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Figure 3. Schematic illustration of (a) inorganic-enriched SEI and (b) organic-enriched SEI on Na metal [51]. Different colors represent different SEI species. Copyright 2021, Wiely-VCH.
Figure 3. Schematic illustration of (a) inorganic-enriched SEI and (b) organic-enriched SEI on Na metal [51]. Different colors represent different SEI species. Copyright 2021, Wiely-VCH.
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Shi, P.; Wang, X.; Cheng, X.; Jiang, Y. Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes. Batteries 2023, 9, 345. https://doi.org/10.3390/batteries9070345

AMA Style

Shi P, Wang X, Cheng X, Jiang Y. Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes. Batteries. 2023; 9(7):345. https://doi.org/10.3390/batteries9070345

Chicago/Turabian Style

Shi, Pengcheng, Xu Wang, Xiaolong Cheng, and Yu Jiang. 2023. "Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes" Batteries 9, no. 7: 345. https://doi.org/10.3390/batteries9070345

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