In situ high‐quality LiF/Li3N inorganic and phenyl‐based organic solid electrolyte interphases for advanced lithium–oxygen batteries

Abstract

Lithium metal shows a great advantage as the most promising anode for its unparalleled theoretical specific capacity and extremely low electrochemical potential. However, uncontrolled lithium dendrite growth and severe side reactions of the reactive intermediates and organic electrolytes still limit the broad application of lithium metal batteries. Herein, we propose 4‐nitrobenzenesulfonyl fluoride (NBSF) as an electrolyte additive for forming a stable organic–inorganic hybrid solid electrolyte interphase (SEI) layer on the lithium surface. The abundance of lithium fluoride and lithium nitride can guarantee the SEI layer's toughness and high ionic conductivity, achieving dendrite‐free lithium deposition. Meanwhile, the phenyl group of NBSF significantly contributes to both the chemical stability of the SEI layer and the good adaptation to volume changes of the lithium anode. The lithium–oxygen batteries with NBSF exhibit prolonged cycle lives and excellent cycling stability. This simple approach is hoped to improve the development of the organic–inorganic SEI layer to stabilize the lithium anodes for lithium–oxygen batteries.

INTRODUCTION

Lithium metal has garnered considerable attention because of its low density, high theoretical capacity, and lowest electrochemical potential (−3.040 V vs. standard hydrogen electrode).^1–4 Among the next-generation rechargeable batteries, lithium–oxygen batteries, owing to their high theoretical energy density (up to 3500 W h kg⁻¹), have been one of the most promising candidates.⁵ However, several scientific challenges urgently need to be overcome. Especially, highly reactive oxygen species are inevitable to attack the lithium anodes in lithium–oxygen batteries, which play a crucial role in irreversible side reactions during cycling.⁶ Meanwhile, due to its highly reactive nature, lithium metal reacts spontaneously with most organic electrolyte solvents and lithium salts, resulting in the spontaneous formation of pristine solid electrolyte interphase (SEI) layer on the lithium surface.^7,8 During the repeated electrodeposition and precipitation, the fragile and heterogenous SEI layer is broken and lithium dendrites are then easily generated on the lithium surface. Amounts of fresh lithium metal are exposed to the organic electrolyte, consuming both lithium and electrolyte.⁹ Besides, the constantly generated SEI forms a thick and porous surface layer on lithium metal, resulting in largely increased interfacial resistance.¹⁰

Numerous efforts have been devoted to inhibiting lithium dendrite growth and enhancing the stability of anodes, such as using modified separators,¹¹ nanostructured anodes,¹² electrolyte additives,¹³ surface coating,¹⁴ and so on. Among these approaches, developing appropriate electrolyte additives is one of the most effective and economical strategies to improve the electrochemical performance and energy efficiency of lithium–oxygen batteries.¹⁵ A variety of electrolyte additives, such as lithium fluoride (LiF),¹⁶ polydimethylsiloxane,¹⁷ fluoroethylene carbonate,¹⁸ tris(2,2,2-trifluoroethyl) borate,¹⁹ LiNO₃,²⁰ trace-amount water,²¹ and nitrocellulose,²² have been researched to form firm SEI layers in situ. The additives that can form dense LiF-rich SEI layers with high interfacial energy are increasingly popular. Unfortunately, its low elastic modulus is unsatisfactory for lithium metal anodes to undergo dendrite growth and drastic volume fluctuations.²³ Recently, the phenyl group has been known to endow the SEI layers with excellent chemical reversibility and electrochemical stability against associated side reactions in batteries.²⁴ Meanwhile, the flexibility of the formed SEI layer can be significantly improved due to π–π bonds in the benzene ring.²⁵ Therefore, developing new additives to form the organic–inorganic hybrid SEI layer is vital to guaranteeing rapid ionic conductivity, high mechanical strength, favorable flexibility, and electrochemical stability with excellent electronic insulation.^26–29

In this contribution, 4-nitrobenzenesulfonyl fluoride (NBSF) is introduced as a novel electrolyte additive. It is found that NBSF can react with the natural LiOH on the lithium metal to form a LiF-rich and lithium nitride (Li₃N)-rich SEI layer, which effectively inhibits lithium dendrite growth as a rigid barrier and realizes uniform lithium deposition as an ionic conductor. Besides, the flexibility of the SEI layer is improved to fit the volume change of the lithium anode and inhibit the attacks of the oxygen species through the benzene ring. With the trifunctional properties of the LiF-rich and Li₃N-rich phenyl-based organic–inorganic protective SEI layer, lithium–oxygen batteries with NBSF exhibit high round-trip efficiency and improved cycling performance up to 286 cycles. This work lays the groundwork for further development of practical lithium metal batteries.

RESULTS AND DISCUSSION

The porous and thick LiOH layer is naturally present on the lithium metal surface. However, in practical lithium metal batteries, the native film may locally enhance lithium ionic flux and exacerbate the decomposition of the electrolyte, thereby aggravating battery performance. Therefore, forming a stable SEI layer to replace the unstable native film is essential. We introduce 4-NBSF (Figure S1) as a novel electrolyte additive into lithium–oxygen batteries. The pristine lithium anodes were soaked in 1,2-diethoxyethane (DME) solvent for 5 min to produce a thin layer of LiOH (Figure S2). To confirm whether NBSF can form a protective layer and avoid the effects of lithium salts, we immersed the lithium anodes after soaking in DME directly in NBSF/tetraethylene glycol dimethyl ether (TEGDME) solution for 12 h. Figure 1A schematically depicts the reaction on the lithium surface: NBSF reacts spontaneously with LiOH to form a LiF-rich and phenyl-based protective layer on the lithium anode.³⁰

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Figure 2 shows the treated lithium anodes' energy-dispersive spectroscopy (EDS). The uniform distributions of C, F, and N elements are observed, which show the SEI layer is generated by the reactions of NBSF and LiOH (Figure 2A–C). X-ray photoelectron spectroscopy (XPS) was also conducted to detail the composition of the formed SEI layer. In the spectra of C 1s (Figure 2D), the peak at 284.4 eV is assigned to the C═C bond, which directly shows the presence of phenyl.^31,32 The peaks at 284.8, 285.7, 288.7, and 289.9 eV that correspond to C–C/C–H, C–S, ROCO₂Li, and Li₂CO₃, respectively.^33–36 Particularly, the C–N bond corresponds to the peak of 286.5 eV. The C–N bond, which is the typical feature of NBSF, indicates that NBSF can form a protective layer on the lithium anode. The F 1s XPS spectra show the peaks of 684.4 and 688.4 eV correspond to LiF and S–F bonds, respectively (Figure 2E).³⁷ The existence of LiF confirms that NBSF can react with LiOH, proving the reaction mentioned in Figure 1. As known to us, due to its strong chemical stability and mechanical strength, LiF can effectively block the direct contact between electrolyte and lithium metal. Moreover, LiF favors enhancing the lithium ionic diffusion during electrodeposition, contributing to uniform and dendrite-free morphology.³⁸ Moreover, the peaks located at 54.5, 55.2, 55.4, and 55.7 eV correspond to ROCO₂Li, Li₃N, Li₂CO₃, and LiF, respectively.³⁹ It is known that fast ion conductor Li₃N can facilitate lithium ion transmission (Figure 2F).⁴⁰ The N 1s and O 1s XPS spectra of the treated lithium anodes are given to show more detailed information (Figure S3). Moreover, the surface morphology of the bare lithium anodes is observed to be slightly rough, and it seems that a thin layer of LiOH is overlaid on the lithium surface (Figure S4). A smooth surface is obtained after DME and NBSF treatment, which can contribute to the NBSF's positive effect on improving lithium metal morphology. All the results confirm that NBSF can, in situ, form a stable SEI layer on the lithium anode.

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The cycling performances of lithium–oxygen batteries were carried with the discharge capacity limited to 1000 mA h g⁻¹ in LiTFSI/TEGDME electrolytes with and without NBSF. As shown in Figure 3A, the batteries without NBSF exhibit a sharp increase in charging overpotential within only 20 cycles. In contrast, lithium–oxygen batteries with NBSF can stabilize the charging overpotential below 4.5 V in 286 cycles, presenting improved cycling performance (Figure 3B). Besides, more details concerning the charging curves with NBSF are shown to prove the small voltage interval during cycling (Figure S5). The comparison of the terminal voltages of the lithium–oxygen batteries with and without NBSF is shown (Figure 3C). The enhanced electrochemical performance and prolonged cycle life directly indicate the well-protective effect of the LiF-rich and Li₃N-rich phenyl-based organic–inorganic layer in alleviating the side reactions in batteries. Even compared with other reported electrolytes (Table S1), NBSF still shows superior cycle life at a high current density. As the electrochemical impedance spectra (EIS) show, the lithium–oxygen batteries with NBSF exhibit markedly lower interfacial resistance than the batteries without NBSF (Figure S6), indicating the positive effect of the LiF and Li₃N in facilitating the lithium ionic diffusion. Besides, EIS spectra for the lithium–oxygen batteries after different cycles are shown (Figure S7). At the first 20 cycles, the impedance of batteries with NBSF remains stable. After 30 cycles, there is a slight decrease in impedance. We explain this via the reaction of NBSF to form the SEI with high lithium-ion conductivity. All the results prove that the SEI layer derived from NBSF plays a critical role in promoting uniform lithium ionic deposition, which also protects the lithium anode from side reactions.

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The morphologies of anodes in lithium–oxygen batteries after cycling are investigated using a scanning electron microscope (SEM) to examine the effect of NBSF. The SEM image of batteries without NBSF was uneven and rough after 20 cycles, and many lithium dendrites were observed (Figure 4A). On the contrary, the lithium anode surface with NBSF remained smooth after cycling (Figure 4B). The cross-section SEM images were also obtained to better understand the stability of the formed SEI layer (Figure S8). The thickness of the fluffy structure in lithium anodes without NBSF is around 131 μm after the first cycle, and after 20 cycles, it is 245 μm, growing about 114 μm. However, in the batteries with NBSF, the thickness of the fluffy structure is around 127 μm after the first cycle and 136 μm after 20 cycles, growing only 9 μm. The differences in lithium surface morphologies suggest that NBSF can prevent lithium dendrite growth due to excellent electron blocking effect and suppress the side reactions with electrolytes. Meanwhile, this result also indicates that the protective SEI layer on the anode surface with NBSF can suppress the attack of reactive oxygen species, greatly enhancing cycling stability.

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The Fourier transform infrared spectroscopy (FTIR) spectra of lithium anodes for the batteries with NBSF after 20 cycles were obtained (Figure S9). The vibration at 1428−1620 cm⁻¹ corresponds to the benzene skeleton, which indicates that benzene exists on the lithium surface as a part of the protective layer. The peaks at 1351 and 874 cm⁻¹ arise from –NO₂ group stretching, and the characteristic peak at 1194 cm⁻¹ corresponds to the C–N bond.⁴¹ All these results suggest that the organic–inorganic protective layer produced by NBSF is stable during cycling. XPS measurements were employed to investigate the composition of the SEI layer. Obviously, after cycling, the content of F and N on the lithium anode with NBSF was enhanced compared with the lithium anode without NBSF (Figure S10). The specific fitting results are shown (Figure 5). C═C, C–C/C–H, C–S, and C–N are represented by the peaks at 284.4, 284.8, 285.7, and 286.5 eV, respectively. The existence of C═C bonds confirms the protective effect of the benzene ring on the lithium anodes. Besides, the peaks at 286.6, 288.7, and 289.9 eV are attributed to CH₃COOLi, ROCO₂Li, and Li₂CO₃, respectively (Figure 5A,B). The peak at 684.8 eV in F 1s XPS spectra is assigned to LiF, which is a reduction product of LiTFSI (Figure 5C,D).⁴² Obviously, the batteries with NBSF show a higher content of LiF, which is attributed to the reaction of NBSF and LiOH. Besides, the higher content of LiF on the lithium anode surface is beneficial for suppressing the thickening of the SEI layer during cycling and preventing lithium dendrite growth.⁴³ The peaks of ROCO₂Li and Li₂CO₃ are at 54.4 and 55.4 eV, respectively (Figure 5E,F). And importantly, the peaks at 55.2 and 55.7 eV correspond to Li₃N and LiF, respectively. The N 1s and O 1s XPS spectra are also given to show more details about the composition (Figure S11). The peak at 399.7 eV in N 1s spectra corresponds to LiTFSI, and the peaks at 398.4, 400.1, and 403.5 eV are assigned to the Li₃N, C–N bond, and –NO₂ group, respectively (Figure S11A,C).^44,45 Since the C–N bond and –NO₂ group are both characteristic features of NBSF, it can be confirmed that the protective SEI layer is derived from NBSF. The peaks in O 1s spectra at 530.8, 531.5, and 532.7 eV correspond to CH₃COOLi, Li₂CO₃, and ROCO₂Li, respectively. In particular, the peak at 532.17 eV corresponds to the –NO₂ group (Figure S11B,D). Besides, the uniform C, F, and N element distribution of the lithium anodes with NBSF also guarantees that NBSF participates in forming the SEI layer (Figure S12). Therefore, these findings further suggest that adding NBSF can create a LiF-rich and Li₃N-rich phenyl-based organic–inorganic SEI layer, further increasing the stability of lithium anodes.

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To evaluate the electrochemical stability of the lithium metal anode during long-term cycling, Li–Li symmetric cells were employed. Figure 6 shows the voltage profile of cells with and without NBSF at a current density of 1 mA cm⁻². Due to the severe side reactions and lithium dendrite growth, the cell without NBSF shows a larger overpotential with irregular fluctuations in 1100 h (Figure 6A). Notably, the cell with NBSF displays a stable lithium plating/stripping process with negligible overpotential over 1900 h, indicating that the SEI layer derived from NBSF can protect lithium from the corrosion of electrolytes. EIS measurement was also applied to examine the interphase stability of the protective layer on the lithium anode (Figure S13). Compared with the battery with NBSF, the pristine resistance of the interphase between the electrode and electrolyte of the battery without NSBF is slightly bigger. After five cycles, the impedance of the battery without NBSF increases sharply, which can be attributed to the side reactions between lithium anode and electrolyte. Surprisingly, the impedance of the battery with NBSF is significantly reduced. To further illustrate the impedance-changing behavior, we fit the Nyquist plots of Li–Li symmetric batteries using the equivalent circuit (Figure S14). Notably, the pristine and fifth charge-transfer resistance of batteries without NBSF is 155.0 and 115.3 Ω, respectively. However, the pristine and fifth charge-transfer resistance of batteries with NBSF is 59.97 and 27.20 Ω, respectively. We attribute this to the protective effect and improvement of lithium ionic conductivity of the SEI layer formed by NBSF. Apparently, the addition of NBSF can effectively create a highly conductive lithium-ion protective layer on the lithium anode, benefiting the electrochemical stability.

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The possible formation mechanism of the organic–inorganic SEI layer is also proposed (Figure S15). The –SO₂F group on NBSF reacts with LiOH to form LiF, and then the –NO₂ group reacts with lithium metal to produce LiNO₂ on lithium anodes, which turns to Li₃N to facilitate ion conduction. Meanwhile, lithium benzenesulfonate is formed to increase the flexibility of the SEI layer. Above all, a uniform and firm protective SEI layer is formed.

CONCLUSION

In summary, we report NBSF as a new electrolyte additive in lithium–oxygen batteries for the first time. XPS and FTIR spectra confirmed that NBSF can form an SEI layer with high-quality and abundant LiF and Li₃N on the lithium surface by reaction with LiOH to facilitate uniform deposition of lithium ions and inhibit dendrite growth. Meanwhile, the phenyl-based SEI component can stabilize the lithium anodes. Thanks to the organic–inorganic hybrid SEI layer, lithium–oxygen batteries can steadily cycle 286 times. This strategy represents promising progress in protecting lithium anode for practical lithium–oxygen batteries.

EXPERIMENTAL SECTION

Preparation of multiwalled carbon nanotube (MWCNT) cathode

To prepare the MWCNT cathode, MWCNT (8−15 nm; XFNANO), single-layer graphene (0.8−1.2 nm; XFNANO) and poly(vinylidene fluoride) (Sigma-Aldrich) were used at a weight ratio of 8:1:1. N-methyl-2-pyrrolidinone was the solvent. The mixture was subsequently subjected to ultrasonic treatment for 30 min and magnetic stirring for 24 h. Afterward, the slurry was applied to carbon papers and placed in a vacuum oven to dry at 80°C for 24 h. The cathode's total mass loading amounts to approximately 0.1 mg.

Preparation of electrolytes

A total of 1 M LiTFSI/TEGDME and 1 M LiTFSI/EC/DMC (volume ratio 1:1) are pure electrolytes for the lithium–oxygen battery and Li–Li symmetric battery; 50 mM 4-NBSF (97%+; Alfa) was added as an additive for the electrolyte with NBSF.

Battery assembly

All batteries were assembled in the glove box filled with argon gas, with O₂ and H₂O content kept below 0.5 ppm. The CR2032 coin-type model with holes for O₂ was employed for lithium–oxygen batteries. The working electrodes were the lithium foil (15.6 mm in diameter) and MWCNT cathode separated by a Whatman GF/B glass fiber separator. The electrolyte volume was ∼120 µL. The electrochemical measurements of lithium–oxygen batteries were conducted in a 1.0 mbar pure O₂ environment. The Li–Li symmetric batteries were assembled with the standard CR2032 coin-type model with two lithium foils separated by a Whatman GF/C glass fiber separator. The electrolyte volume was ∼60 µL.

Electrochemical analysis

All lithium–oxygen batteries were tested using a LAND electrochemical testing system within a voltage window of 2.3–4.5 V (vs. Li⁺/Li). The capacity was limited to 1000 mAh g⁻¹ with a constant current density of 1000 mA g⁻¹. The Li–Li symmetric batteries were tested with voltage limits of −0.8 and 0.8 V (vs. Li⁺/Li) at 25°C after a 3 h rest period. EIS was conducted on a Gamry Interface 5000E system with a frequency range spanning from 10⁶ to 10⁻¹ Hz and a voltage amplitude of 10 mV.

Electrochemical characterization

After cycling, the anodes were disassembled from the batteries and washed in 1,2-DME for 30 min. They were then dried in the argon-filled glove box for 2 h. Note that all the samples were transferred to the analysis system without air exposure. X-ray diffraction was acquired to analyze the crystal structure on Panalytical at 40 kV with Cu Kα radiation. The XPS results were obtained to analyze the surface composition on a Thermo Scientific K-Alpha TM+ with Al Kα radiation. The microstructure and morphologies of the lithium anodes were observed using field emission SEM (Apreo 2C). The element mapping information for lithium anodes was obtained by coupling EDS with SEM. For FTIR, Thermo Fisher Nicolet Is10 was utilized with a wave number range from 4000 to 400 cm⁻¹.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the support of the National Natural Science Foundation (Grant No. 22109131, 52077180), Sichuan Province Innovative Talent Funding Project for Postdoctoral Fellows, Young Elite Scientists Sponsorship Program (CAST, 2022QNRC001), the Natural Science Foundation of Sichuan Province (No. 2022NSFSC0247), and Southwest Jiaotong University's New Interdisciplinary Cultivation Fund (No. 2682022KJ028).

CONFLICT OF INTEREST STATEMENT

The authors declare that there are no conflicts of interests.

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