An ionic protector to proactively mitigate interfacial degradation induced by electrolyte decomposition in lithium-ion batteries

Abstract

Tetrabutylammonium nonafluorobutanesulfonate (TBNF) is introduced as a capacitive protection electrolyte additive to enhance the performance of high-voltage nickel–cobalt–manganese (NCM) batteries. During charging, the voltage of the positive electrode increases, whereas that of the negative electrode decreases, leading to the migration of cations to the negative electrode and anions to the positive electrode. Based on this principle, an ionic additive for NCM batteries is designed to protect electrodes through capacitive behavior. TBNF suppresses both cathodic and anodic electrolytic decomposition through its extended alkyl chain on the cation and the perfluorinated sulfonate anion. This mitigates the formation of a solid–electrolyte interphase and surface film deposition during cycling. This protection mechanism significantly improves cycling performance, especially under high voltage and temperature conditions. Furthermore, the additive preserves the nominal voltage of the cell, which is essential for energy retention and practical applications. This novel approach can address key challenges in battery design, facilitating the development of more reliable and efficient energy storage systems.

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1 Introduction

Lithium-ion batteries are widely used in mobility and energy storage systems, requiring numerous lithium-ion cells within battery packs.^1–9 Recently, mid-nickel positive electrodes have been adopted in lithium nickel–cobalt–manganese oxide-based (NCM) batteries to reduce the cost per unit energy of lithium-ion batteries. Notably, to achieve an energy density comparable with those of high-nickel NCM-based batteries, the upper cut-off voltage must be increased to enhance the specific capacity of NCM materials.^10–17 In contrast, increasing the cut-off voltage can exacerbate the degradation of the NCM crystal structure and intensify interfacial side reactions during cycling.^18–27 These two degradation phenomena are strongly correlated, and thus interfacial failure must be mitigated to ensure the commercialization of NCM batteries. Film-forming electrolyte additives have been used to reinforce the surface films of NCM materials.^28–42 However, rupture of surface films and electrolytic decomposition of electrolytes remain persistent despite robust film formation.^43–55 Consequently, novel electrolyte additives must be formulated to develop high-voltage NCM batteries and promote the application of lithium-ion batteries.

The decomposition of electrolytes is highly correlated with the charging sequence because oxidation and reduction occur at positive and negative electrodes, respectively. The development of net-current of the positive electrode is the anodic current and vice versa at the negative electrode, and thus the decomposition of electrolytes occurs significantly during the charging period.^56–59 As charging progresses, the positive electrode voltage increases and negative electrode voltage decreases, causing cations to migrate to the negative electrode and anions to migrate to the positive electrode.^50,60 Considering this fundamental closed-loop phenomenon, ionic additives can be designed to protect NCM electrode surfaces through capacitive behavior. The deposited solid electrolyte interphase (SEI) film and the surface film on negative and positive electrodes suppress electrolyte decomposition after the formation of a passivation film; however, mechanical rupture and chemical failure during prolonged cycling ensue by volumetric change of active materials and thermal failure of the electrolyte.^61–67 Hence, sacrificial film-forming additives are not sufficient to perfectly prevent further electrolyte decomposition. Furthermore, the surface film deposited on the NCM surface is highly permeable^68,69 and therefore cannot provide complete protection of NCM from oxidative decomposition of the electrolyte during operation. However, capacitive protection of the electrode surface, which stabilizes the electrode–electrolyte interface, can significantly enhance the cycle life of high-voltage NCM cells by suppressing electrochemical side reactions at the electrode surface.

In this study, tetrabutylammonium nonafluorobutanesulfonate (TBNF, Fig. S1†) was used as a capacitive protection electrolyte additive to improve the cycle performance of NCM cells under high-voltage conditions. The extended alkyl chain of this additive, attached to a nitrogen cation, effectively shields the electrolyte from cathodic decomposition by limiting solvent access during cycling. Instead, the perfluorinated chain-affixed sulfonate anion migrates to the NCM surface during charging, protecting the positive electrode interface. As the lengthened chain is bound at unit charge, both electrode surfaces can be effectively protected through the migration of identical charge during cycling. Although the formation of a distinct compound-based SEI film is not the objective of using TBNF, the additive ensures capacity retention after the initial formation process. Overall, the introduction of TBNF significantly enhances the cell performance under high-voltage conditions by mitigating degradation of the electrolyte species.

2 Results and discussion

Fig. 1 illustrates the conceptual framework of the capacitive protection additive and characterization of the additive effect based on electrochemical and spectroscopic analysis. The morphological features and crystallographic characteristics of the as-synthesized single crystal NCM were systematically investigated using field emission scanning electron microscopy (FE-SEM). The NCM particles demonstrate distinctive single-crystalline characteristics with a tendency to form weak aggregates with a median diameter of approximately 5 μm, as determined by laser diffraction analysis (Fig. S2†). While individual crystals may appear smaller in SEM visualization due to projection effects and the visual emphasis on particle boundaries, the overall size distribution confirms these weakly aggregated single-crystal entities centered around 5 μm, consistent with controlled synthesis conditions. This apparent dimensional variance between volumetric and microscopic analysis is characteristic of single-crystal materials that exhibit weak inter-particle associations driven by high surface energy, which is a typical phenomenon particularly pronounced in single crystal NCM cathodes synthesized at high temperatures, over 900 °C. The crystallographic structure and phase purity of the NCM622 materials were examined through high-resolution X-ray diffraction (XRD) analysis, with the diffraction patterns and corresponding Rietveld refinement results presented in Fig. S3 and Table S1.† The refined diffraction profiles confirm that the samples crystallize in the α-NaFeO₂-type layered structure with R3̄m space group symmetry, characteristic of well-ordered layered oxides. The absence of additional reflections in the diffraction patterns indicates the successful formation of phase-pure materials without detectable impurity phases or secondary structural components. Fig. 1a shows the role of the additive in mitigating interfacial side reactions during cycling. In conventional electrolytes, the deposited SEI and surface films degrade owing to volumetric changes in the active materials and chemical decomposition of the SEI during cycling. Conversely, the capacitive protection additive forms a protective layer over both the positive and negative electrode surfaces, effectively suppressing further electrolytic decomposition. During the charging process, the positive electrode voltage increases, whereas the negative electrode voltage decreases, driving cation migration to the negative electrode and anion movement toward the positive electrode. Based on this fundamental closed-loop mechanism, TBNF is designed and incorporated into NCM batteries to protect the electrode surfaces through capacitive behavior. The extended alkyl chain attached to the nitrogen cation effectively blocks the interaction of solvent molecules, reducing cathodic electrolyte decomposition. Additionally, the perfluorinated chain-attached sulfonate anion migrates toward the NCM surface during charging, thereby protecting the positive electrode interface.

Fig. 1 (a) Scheme for the mechanism of the capacitive protection additive, (b) scan rate-dependent cyclic voltammograms obtained for Li/Cu and Li/Al cells in negative and positive voltage regions, respectively, (c) voltage versus mass change curves obtained from the background and additive-added electrolytes, respectively, and (d) N 1s and S 2p XPS narrow scan spectra from the negative and positive electrodes after formation.

Conventionally, capacitive additives have been utilized as alkali-ion type additives to enhance the reversibility of lithium metal through cation shielding^50,70–72 or to promote uniform formation of the SEI on graphite electrodes.² In contrast, the present study employs the additive as a protective agent for both the positive and negative electrode surfaces. By designing both the cation and anion with bulky structures, the additive is intended to effectively mitigate electrochemical side reactions induced by the continuous contact between the electrode surface and the solvent.

Fig. 1b shows the scan-rate-dependent cyclic voltammograms for both the background and additive-added electrolytes, respectively, in the high- and low-voltage regions. The cyclic voltammetry tests were performed within the electrochemical stability window of typical carbonate electrolytes, ensuring that the observed current arises from double-layer charging of each electrode.^2,48,60 The introduction of TBNF significantly reduces the double-layer charging current at both high and low voltages, indicating that the proximity of the charged species is reduced.

Electrolytic decomposition promotes the deposition of the SEI and surface films on the electrode surface. Thus, electrochemical quartz crystal microbalance (EQCM) measurements were performed for both the background and additive-added electrolytes to compare mass increment during low and high voltage exposure (Fig. 1c). The EQCM analysis was conducted at a cut-off voltage of 4.5 V (vs. Li/Li⁺), consistent with the upper cut-off voltage of NCM (4.45 V vs. Li/Li⁺) required to achieve a specific capacity of 190 mA h g⁻¹ (Fig. S4†), typical of high-nickel-content positive electrodes. The EQCM profiles obtained under continuous exposure to positive and negative voltage show that the final mass of the electrode significantly decreases upon the introduction of TBNF, implying reduced SEI and surface film deposition. In contrast, the background electrolyte results in significant mass increase, indicative of further decomposition.

Fig. 1d shows the X-ray photoelectron spectroscopy (XPS) results for graphite and NCM electrodes after formation, with and without TBNF. N 1s and S 2p narrow-scan XPS spectra were compared to confirm the absence of additive decomposition. The XPS spectra show no evident peaks after formation, indicating that the electrochemical decomposition of the electrolyte additive is inhibited at the electrode surface. Hence, the decrease in the final electrode mass is attributable to the capacitive protective effects of the additive during low- and high-voltage exposures.

Fig. 2 shows the electrochemical characterization results of NCM pouch cells with additive-introduced electrolytes. Cycling was performed under 1.0C, 45 °C conditions as elevated temperature cycling results in severe electrolytic decomposition on the surface of active materials (Fig. 2a). The elevated temperature cycling is generally regarded as the accelerated cycle performance evaluation for LIBs.^73–75 The additive-added cell demonstrates stable cycle performances with increased average coulombic efficiency compared with those of the cells with the background electrolyte, indicating suppressed side reactions. The capacity retention is enhanced by 18.5% in the case of the additive-added electrolyte (Fig. S5†).

Fig. 2 (a) 45 °C, 1.0C cycle performance at 2.5–4.35 V, cycle number dependent (b) charge and discharge nominal voltages, and (c) voltage profiles obtained from background and additive-added electrolyte injected graphite/NCM622 pouch cells.

Fig. 2b compares the nominal voltage of cells with and without the additive. In general, an increase in the nominal voltage degrades the discharge energy of cells. Stable nominal voltage is crucial for preserving the discharge energy, which directly affects the practicality of electric motors and devices powered by batteries. In the cell with the background electrolyte, the charge and discharge nominal voltages increase and decrease, respectively. In contrast, cells with the additive demonstrate stable nominal voltages throughout the cycling process, attributable to the capacitive protection. Hence, the additive helps improve the discharge energy retention and overall energy efficiency of NCM cells (Fig. S6†).

Fig. 2c shows the voltage profile of NCM cells as a function of the cycle number. The introduction of TBNF mitigates the degradation of nominal voltage and discharge capacity, resulting in a more stable voltage profile compared with cells with the background electrolyte.

The 25 °C, 1.0C cycle performance evaluation shows results consistent with elevated temperature cycling (Fig. S7†). The discharge capacity retention is improved with the TNBF additive, and the rate capability is slightly improved with the TNBF additive from less passivation film formation during the formation period. Furthermore, the graphite and NCM electrodes were individually evaluated in coin half-cells to validate the effect of the TNBF additive (Fig. S8†). The results demonstrate that the capacity retention of Li/NCM and Li/graphite cells is improved with additive introduction, implying that the interfacial failure is mitigated with the capacitive additive introduction, individually.

A post-mortem analysis of the cycled negative electrode was performed to investigate the suppression of further SEI deposition by TBNF (Fig. 3). Fig. 3a shows the scanning electron microscopy (SEM) top-view image of the graphite electrode. In the case of the background electrolyte, clogged pores and thick SEI deposition are observed, whereas the additive-added cell retains a clean surface. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) analysis was performed to compare the SEI thickness after cycling (Fig. 3b). Typical SEI components, CH₃O⁻ and P⁻ species,^63,64,76 were explored through three-dimensional ToF-SIMS mapping to investigate the SEI thickness after cycling. Cells with the background electrolyte exhibit intense CH₃O⁻ and P⁻ signals. In contrast, cells with the additive show reduced signals from the SEI species, confirming effective suppression of further SEI film deposition. Ex situ high resolution transmission electron microscopy (HR-TEM) analysis was performed to assess the SEI thickness (Fig. 3c). Substantial SEI film growth is observed on the graphite electrodes cycled with the background electrolyte. Conversely, cells with TBNF display reduced SEI film growth. The mitigation of electrolytic deposition is expected to reduce lithium-ion consumption during cycling. Deposition of the SEI film results in the expansion of the negative electrode after cycling, and a cross-sectional SEM analysis was performed to investigate this phenomenon (Fig. 3d). The electrode thickness for the cell with the background electrode is 74.18 μm, higher than that for the additive-added cells (70.26 μm). Thus, TBNF can suppress cathodic side reactions, preventing volumetric failure of the pouch cell.

Fig. 3 Post-mortem (a) SEM images, (b) three-dimensionally rendered ToF-SIMS maps of CH₃O⁻ and P⁻ anions, and (c) HR-TEM images of graphite electrodes after 300 cycles, (d) cross-sectional SEM images of the graphite electrode after 300 cycles with background and additive-added electrolytes, respectively.

Ex situ characterization of the positive electrode surface was performed to confirm the reduction in anodic decomposition on the NCM surface. The results are shown in Fig. 4. Fig. 4a shows the HR-TEM and corresponding FFT images of background and additive-added electrolytes, respectively. Because the deterioration of the surface layered structure can be performed with the continued oxidation of the electrolyte component, the local structural failure of NCM materials was compared. While the cycled NCM with the background electrolyte shows the degraded surface structure, which is evidenced by rock-salt structure evolution, the additive-added electrolyte mitigates the degradation of the interface by suppressed electrolyte oxidation. The layered structure is well-preserved at the surface of NCM with additive introduction, and hence the resistance growth is retarded at pouch cell evaluation (Fig. 2b). The structural degradation of NCM is coupled with the oxidation of the electrolyte, and thus the deposition of the surface film after cycling was compared. Fig. 4b presents the 3D-ToF-SIMS results of the cycled NCM electrode. Attenuated signals for components resulting from surface film deposition (CO₃⁻ and P⁻) are observed in the presence of the additive. This result demonstrates that TBNF suppresses further surface deposition through its capacitive protective effects. XPS depth-profiling results reveal more pronounced lattice oxygen signals in cells with TBNF compared with those of the background-electrolyte cells, indicating the formation of a thinner surface film after 300 cycles at elevated temperature (Fig. 4c).

Fig. 4 Ex situ (a) HR-TEM images and corresponding FFT images, (b) 3D-rendered ToF-SIMS maps of CO₃⁻ and P⁻ anions and (c) O 1s XPS depth-profiling spectra of NCM622 electrodes with background and additive-added electrolytes after 300 cycles.

For comparison, the conventional film-forming additive vinylene ethylene carbonate (VEC)^77–79 was employed to evaluate the effectiveness of the TNBF additive (Fig. S9†). While the VEC additive enhances the SEI film of the graphite electrode, its ability to sustain interfacial reinforcement diminishes during prolonged cycling due to chemo-mechanical interfacial degradation. In contrast, the TNBF additive provides additional capacitive protection at the electrode surface, which is critical under high-voltage cycling conditions. Thus, reinforcement through further passivation film formation by adding VEC is insufficient. As a consequence, the TNBF additive demonstrates improved cycling performance compared to the conventional VEC additive.

Fig. 5 depicts the working mechanism of the ionic shield in the high-voltage NCM batteries. While typical additives are decomposed to form a robust interphase on the electrode surface, the ionic protector generates a capacitive protection layer that decreases electrochemical side reactions during elevated temperature cycling. On the positive electrode surface, the oxidation of the electrolyte deteriorates the surface of the NCM surface by forming a rock-salt phase, which impedes Li-ion transport at the NCM surface.^80–82 In contrast, the anion shield well protects the NCM surface with the additive, and hence the mitigation of surface structural degradation is conducted.

Fig. 5 Illustration of the detailed working mechanism of the ionic shield-type additive.

On the negative electrode surface, the SEI film on the graphite electrode grows further due to the re-exposure of the electrode surface caused by the rupture of the SEI film in conventional electrolytes. In contrast, the cation shield efficiently protects the interface of graphite–electrolyte, and thus the growth of the SEI film on graphite is suppressed with additive introduction.

This non-sacrificial ionic shield additive can reduce further electrolyte decomposition in the LIBs after formation, significantly mitigating the degradation of cycle performance caused by continued electrolyte decomposition.

3 Conclusions

TBNF is introduced as a capacitive protection electrolyte additive to enhance the cycling performance of high-voltage NCM batteries. This additive mitigates further electrolytic decomposition, contributing to improved cyclability and cell resistance. Electrochemical characterization reveals that TBNF effectively suppresses cathodic and anodic electrolyte decomposition by using its extended alkyl chain on the cation to exclude electrolyte solvents and its perfluorinated sulfonate anion to protect the electrode surface. This protection mechanism mitigates the deposition of the SEI and surface films during cycling, resulting in enhanced cyclability at elevated temperatures. Furthermore, TBNF preserves the nominal voltage stability, crucial for energy retention and practical applications. Surface characterization studies reveal that TBNF reduces the SEI thickness and minimizes pore clogging on the graphite electrode after cycling. On the positive electrode side, surface film deposition and surface structural degradation are reduced, providing evidence for the efficient suppression of anodic decomposition of the electrolyte during high-temperature cycling. These findings highlight the effectiveness of TBNF in stabilizing NCM cells under high-voltage and high-temperature operations. The capacitive protection additive offers a distinct approach to overcoming challenges in LIB design, facilitating the development of more robust and efficient energy storage systems.

Data availability

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

Author contributions

Wontak Kim: methodology, formal analysis, validation, data curation, Joon Ha Chang: methodology, formal analysis, validation, Miseung Kim: methodology, validation, Chihyun Hwang: formal analysis, methodology, validation, Boseong Heo: methodology, Jun Ho Song: formal analysis, Ji-Sang Yu: formal analysis, data curation, Youngjin Kim: formal analysis, writing – review & editing. Hyun-seung Kim: conceptualization, validation, formal analysis, investigation, supervision, writing – original draft, writing – review & editing, funding acquisition.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the Ministry of Trade, Industry & Energy/Korea Evaluation Institute of Industrial Technology (MOTIE/KEIT) (No. 20022514, 20014638, RS-2024-00449746, and RS-2024-00507791), and competitiveness reinforcement project for industrial clusters (HUKB2305) supervised by the Ministry of Trade, Industry and Energy (MOTIE).

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Footnotes

† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d5ta02392k

‡ W. Kim and J. H. Chang contributed equally to this work.

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