A Novel Approach for Robust Solid/electrolyte Interface Formation in Lithium-Ion Batteries using Methyl p-toluenesulfonate Additive

doi:10.21203/rs.3.rs-3233577/v1

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A Novel Approach for Robust Solid/electrolyte Interface Formation in Lithium-Ion Batteries using Methyl p-toluenesulfonate Additive

https://doi.org/10.21203/rs.3.rs-3233577/v1

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In this study, a novel S-based compound, methyl p-toluene sulfonate (MPTS) has been investigated as film forming additive in Li/graphite cells. According to the density functional theory (DFT) investigation of electron affinity energy of MPTS and carbonate solvents, MPTS has more negative electron affinity energy of -2.17 eV, whilst it is only − 1.03 eV for ethylene carbonate (EC) and − 0.73 eV for dimethyl carbonate (DMC). It confirms the highest reductive activity of MPTS, which was consistent with the CV test result. The physicochemical features of the graphite electrode were studied using Fourier-transform infrared (FTIR) spectroscopy, field-emission scanning microscopy (FESEM), X-ray photoelectron spectroscopy (XPS) analysis, transmission electron microscopy (TEM), The electrochemical tests results showed that the battery with 1.5% wt% MPTS exhibited a low impedance on the electrode interface and remarkable cyclability, maintaining 93.17% of its initial capacity at 0.2 C after 100 cycles, approximately 11% more than the conventional electrolyte. These outstanding performances are ascribed to the preferential absorption of MPTS and the as-created interface. TEM and XPS analysis confirmed that MPTS forms a thinner SEI layer containing sulfur on the graphite electrode, predicted by recommended mechanism via theoretical calculations. This protective sulfur-containing film promotes faster lithium intercalation/deintercalation kinetics via declining the charge transfer resistance.

Solid electrolyte interface

Lithium-ion battery

Film forming additives

Density functional theory

Sulfur-containing films

Cycle life

Capacity.

Lithium-ion batteries (LIBs) have received much consideration as energy sources in various energy-storage and electronic systems due to multiple benefits over other batteries, including long cycling life, environmental friendliness, and high energy density [1–6]. A typical lithium-ion battery comprises graphite as an anode electrode, a transition metal oxide as a cathode electrode, and an electrolyte consisting of carbonate-based solvents and lithium salt [7–9]. Today, graphite is more widely applied as an anode electrode for advanced commercial LIBs owing to its superior electrical conductivity, substantial theoretical capacity (372 mAh g^− 1), and cost-effectiveness[10–12]. One of the most critical challenges of using graphite as an anode electrode is the exfoliation of the graphite structure during cycling. This is because of the co-intercalation of solvents and dissolved transition-metal (TM) cations originating from the cathode, leading to fading of the capacitance [13, 14]. An SEI is initiated on the exterior of an anode through the initial few LIB cycles by reducing carbonate-based electrolyte, which is lithium-ion conduction but electrical insulation. It should be noted that the SEI consisting of the inorganic and organic components is vital to the excellent operation of LIBs[15]. It affects its rate capability, safety, charge cycle, specific capacity, and initial capacity loss [16, 17]. However, capacity fading within the first charging process of the LIBs is unavoidable, and a gradually reducing capacity may occur as the SEI layer thickens with time. The high coulombic efficiency and long cycle life are achieved by batteries with excellent SEI films, which shield the graphite electrode's surface from deterioration or peeling while allowing selective metal ion migration and preventing further electrolyte degradation [18, 19]. The SEI films formed through the reduction of additives act as a practical electrochemical obstacle that prevents further destructive reactions between the electrolyte and electrode [20, 21]. Generally, one of the most cost-effective and easy strategies to optimize electrolyte formulation to create a high-quality SEI film is the proper use of reduction-type additives in carbonate electrolytes [22–24]. Electrolyte additives preferentially reduce and hinder further decomposition of the electrolyte by forming a thin, compact, and robust layer [25–27]. From this perspective, many studies have been done on film-forming additives, for example, compounds including unsaturated hydrocarbons (e.g., vinyl ethylene carbonate (VEC)) [28–30], sulfur organic additives (e.g., 3-sulfolene (3SF) [31], and diphenyl disulfide (DPDS)[32], nitrogen-containing compound (e.g., 3-(phenylsulfonyl)propionitrile (PSPN), 3-Methyl-1,4,2-dioxazol-5-one (MDO)) [33, 34], and silicon-containing compounds (e.g., tris(trimethylsilyl) phosphate (TMSP)) [35], and so on. Among the additives usually utilized for lithium-ion batteries, sulfur-containing compounds are notable due to the tremendous effect they have on the electrochemical efficiency of LIBs by enhancing their interfacial properties [36]. Some common sulfur-containing additives are ethylene sulfite (ES) [37], 1, 3-propane sultone (PS), vinyl ethylene sulfite (VES), 3-Hydroxypropane-1-sulfonic acid, and 1-Propene 1,3-Sultone (PES) [38], 1,3,2-dioxathiolane-2,2-dioxide (DTD)[39]. The reduction decomposition of the sulfur-containing compounds was investigated, and the formation of Li₂SO₃ and (RSO₃Li) ₂ was proved. Wang et al. [31] found that 3SF additive for 1,2-Propanediol cyclic carbonate (PC)-based electrolytes can create a uniform and thin SEI on the graphite electrode, repressing the gradual co-insertion and reduction of PC-based electrolytes. Yang et al. [40] introduced dioxathiolane-2,2,5,5-tetraoxide (D-DTD) into the electrolyte to stabilize the electrode-electrolyte interfacial (EEI) on both electrodes (cathode and anode) and decrease parasitic interfacial reactions of LIBs at moderate and ambient conditions. In other research, Wang et al. [41] introduced p-Toluenesulfonyl isocyanate (PTSI) as an additive to the ethylene carbonate (EC)-based electrolyte, which increased the cycle capacity of Li/graphite cells and lowered the impedance, particularly at high current densities owing to the creation of an SEI layer, preventing continuous reductive decomposition procedures through the cycling.

In this work, the common electrolyte 1.0 M lithium hexafluorophosphate (LiPF₆) in EC: DMC (50:50, by volume) was applied to evaluate the effect of methyl p-toluene sulfonate (MPTS) as a new sulfur-containing additive on the electrochemical properties of graphite electrode. Density functional theory calculation, along with cyclic voltammetry, showed that MPTS could preferably be reduced. Therefore, it is expected that the MPTS will be effective in producing the protective film. The impact of MPTS on the graphite electrode was evaluated utilizing electrochemical examinations, for instance, electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), rate capability, and cycling stability. The results indicated that adding 1.5% of MPTS into the baseline electrolyte greatly enhanced the capacity and cyclability of the graphite by creating an SEI on the electrode. Moreover, many studies have examined the properties of electrolyte additives of film-forming and their effect on the behavior of lithium-ion batteries. However, the exact mechanism of desired SEI film formation by reductive-type additives is unclear. Therefore, the realization of the mechanism of film formation will be beneficial in the development of efficient additives. We also tried to scrutinize the impact of MPTS on the modification of solid electrolyte interface via density functional theory calculations.

Theoretical computations

DFT computations were performed to assess the MPTS's reduction ability and the mechanism of SEI formation [42]. The lowest unoccupied and highest occupied molecular orbital (LUMO and HUMO) energies of the MPTS additive compared to EC and DMC were calculated. The determined structures were optimized in the Gaussian 09 package applying the B3PW91 exchange-correlation energy functional with 6–311G (d, p)[31]. Moreover, the influence of implicit solvent on the MPTS reduction procedures was demonstrated by the polarized continuum model (PCM), as conducted in Gaussian 09. The dielectric constant of EC/DMC 50/50 (51.4) was used for all PCM calculations. To better understand the reduction activity of MPTS, the electron affinity energy (EAE) was also calculated. The EAE is the amount of energy released when an electron attaches to the molecule to create an anion, which is calculated via the following expression (EAE = G _{optimized anion}-G _{optimized neut}) [7]. ΔG of reactions was utilized as a criterion for determining the dominant reaction so that in each step, the Gibbs free energy of the reactions is compared with each other, and any reaction with the most negative value is considered as the desired reaction.

Materials

Dimethyl carbonate (DMC), the functional additive Methyl p-toluenesulfonate (MPTS), and Ethylene carbonate (EC), were purchased from Sigma Aldrich. Battery Grade Lithium hexafluorophosphate (LiPF₆) purchased from Exir Gmbh. All reagents were applied with no additional refinement.

Preparation of electrolyte and electrode

The blank electrolyte was supplied through the dissolution of 1.0 M LiPF₆ in the mixed solvents of EC/DMC (50/50, by volume). The research electrolyte with MPTS was attained by dissolving MPTS in the base electrolyte and stirring for 10 min. The electrolyte solutions were prepared in an Ar-filled glove box (H₂O < 5 ppm). A Karl Fischer 831 Coulometer (Metrohm, Swiss) was used to distinguish the H₂O level in the electrolyte samples and set to be less than five ppm. The graphite electrode material was prepared by a combination of 10 wt.% PVDF, 10 wt.% carbon black, and 80 wt.% graphite in NMP encased on cupper (Cu) foil and then dried for 12 h in a vacuum oven at 120°C. Finally, the graphite/Li half-cell was prepared using Celgard 2400 divider and Li metal reference/counter electrodes in an Ar-filled glove box.

Physical instruments

A Galvanostat/Potentiostat Autolab (PGSTAT 302N) was used to record electrochemical impedance spectroscopies (EIS) with amplitude of voltage of 5.0 mV and frequency varied 0.1–100 kHz and after 5 and 100 cycles at OCV. Cyclic voltammetry (CV) was conducted on Galvanostat/Potentiostat Autolab (PGSTAT 302N). Charge/discharge experiments were performed at room temperature on a Netware eight-channel battery tester to explore the MPTS influence on the cyclic stability of graphite electrodes. For the first three cycles, the graphite/Li half cells were discharged and charged to 0.005 V and 2.5 V, respectively, at 0.1 C (1 C = 372 mA h g^− 1), and for the following cycles, they were discharged/charged at 0.2 C within the equal operating voltage. The capacity retention after representative cycles was computed according to the fourth cycle capacity after the formation process. The C-rate capabilities were appraised by varying the charge and discharge current densities from 0.1 to 0.2, 0.5, and 1.0 C and finally returned to 0.1 C. The cycled electrodes were dissected inside a glove box, rinsed three times with DMC to eliminate residues, and dried before being ready for physical characterizations. The electrode morphology and structure have been observed using a FESEM (MIRA3), TEM (Carl Zeiss-EM10C-100Kv-Germany) and an X-ray diffractometer (XRD, EQUINOX3000, Intel) was used to study the crystalline structure of the electrode. The surface composition of cycled electrodes was examined by EDX spectroscopy, FTIR (BRUKER-ALPHA), and XPS (Bes Tec, Germany).

DFT outcomes

Theoretical calculations were executed to investigate the electrochemical reaction activity of MPTS. The molecular structure and FT-IR spectra of MPTS are shown in Figure. 1a, which shows the S-containing functional group. Based on the molecular orbital theory, the LUMO and HOMO energy levels can describe the capability to gain and lose electrons [43, 44]. It is believed that a low LUMO level leads to increased reduction potential [45, 46]. Figure. 1b shows the molecular structures of DMC, EC, MPTS, and corresponding HOMO and LUMO energy. MPTS has a lower LUMO energy (-1.51 eV) than EC (0.71 eV) and DMC (0.31 eV), indicating that MPTS preferentially involves in the generation of the SEI film on the anode electrode. It matches well with the higher reduction potential of MPTS seen in the CV results. Moreover, the lower the electron affinity energy (EAE), the higher the molecule's reductive activity. As seen in Figure. 2, MPTS has the lowest EAE of -2.17 eV, indicating that it has the highest electrochemical activity, which would form a protective film to prevent the degradation of the electrolyte.

The possible reaction path is investigated by Gibbs free energy changes via DFT calculations to understand the film-forming process of MPTS. First, the most stable reduction state of the MPTS molecule was confirmed. Then, the interaction of the molecule with products in electrolyte media such as lithium-ion and EC, DMC, and itself was investigated. When MPTS additive is added to the electrolyte, as LUMO energies and electron affinity results show, its reduction is preferable to the reduction of carbonate solvents, so the reaction of MPTS reduction product with electrolyte components such as lithium-ion (Li⁺) from LiPF₆ salt, EC and DMC was investigated. Figure. 3a shows the results of optimized structures after reactions. In the first step, the reaction of MPTS^− 1 with EC, DMC, and Li⁺ was investigated, and the optimal product structures were obtained for EC (MPTS)⁻¹, DMC (MPTS)⁻¹, and Li⁺ (MPTS)⁻¹ with ΔG = + 0.63 eV, ΔG = + 0.27 eV, and ΔG= -0.04 eV values, respectively. Comparing ΔG values, it is clear that the negative ΔG value for Li⁺ (MPTS)⁻¹ shows that the MPTS^− 1 tends to react with lithium-ion because of the oxygen existence as a good site for Li ions. While the positive value of ΔG for EC (MPTS)⁻¹ and DMC (MPTS)⁻¹ shows that MPTS^− 1 has less tendency to react with EC and DMC. On the other hand, the ability of MPTS^− 1 to gain an extra electron was also evaluated, and the more negative value of EAE₂= -3.88 eV compared with ΔG for Li⁺ (MPTS)⁻¹ indicates that MPTS^− 1 is more inclined to accept an electron and reduce for the second time. With the reduction of MPTS^− 1, the cleavage of the S–O bond happens, and the reduction products of MPTS^− 1 decomposed into two parts, which are OCH₃ ^− 1 and PTS^− 1. Through natural bond orbital (NBO) analysis, the same negative charge for both products was obtained. In the next step, the reaction between OCH₃ ^− 1 as a reactant with EC, DMC, Li⁺, and MPTS produces EC(OCH₃)⁻¹, DMC(OCH₃)⁻¹, Li^+ 1(OCH₃)⁻¹, MPTS(OCH₃)⁻¹, products with Gibbs free energy values of + 0.004, + 0.12, -0.50 and + 0.06 eV respectively. As it can be understood, due to the negative ΔG value, forming Li⁺ (OCH₃)⁻¹ has the highest possibility.

The reaction possibility of PTS^− 1 with environment compounds was also investigated. The reaction of PTS^− 1 with EC, DMC, and Li⁺ was investigated, and the optimal product structures were obtained for EC(PTS)⁻¹, DMC(PTS)⁻¹, and Li⁺ (PTS)⁻¹ with ΔG = + 0.11, + 0.35, and − 0.52 eV, respectively. Comparing ΔG values, it is clear that the negative ΔG value of Li⁺ (PTS)⁻¹ shows that the PTS^− 1 tends to react with lithium-ion because of the oxygen existence as favorable sites for Li ions and the distance between Li⁺ and two oxygen atoms is 2.03 Å. While the positive value of ΔG for EC (PTS)⁻¹ and DMC (PTS)⁻¹ shows, PTS^− 1 has less tendency to react with EC and DMC. Briefly, as shown in Figure. 3b, the two-electron reduction of MPTS is also possible beside one-electron reduction path, where the presence of Li-ion from lithium salt results in the formation of the lithiated sulfur-containing ingredients such as C₇H₇SO₂Li (two electron reduction) and C₈H₁₀SO₃Li (one electron reduction), which agrees with the literature where Che et al. [47] reported p-toluene sulfonyl fluoride (pTSF) as film forming additive for both cathode and anode. They investigated the reduction mechanism of the pTSF additive that by acquiring an electron, the cleavage of the S-F bond happened when creating the reductive product of C₇H₇SO₂Li.

Practical outcomes

Influence of MPTS on the graphite electrode

The MPTS reduction behavior on the graphite electrode was assessed using cyclic voltammogram (CV). The first and second cycles' CV curves for the graphite electrodes in 1.0 M LiPF₆-EC: DMC (50:50, by volume) without and with MPTS are illustrated in Figure. 4a, b. In the first sweep of cathodic potential for baseline electrolyte, there is a reduction current peak approximately at 0.6 V (vs. Li/Li), which is ascribed to the EC reduction in the electrolyte[48]. On the other hand, the cathodic performance of the cell with the MPTS-added electrolyte is changed, and an additional peak are noticed at approximately 2.20 V in the CV curve. This peak can be interpreted as the electrochemical pre-reduction of MPTS on the graphite electrode to create SEI film. The reduction peak of MPTS vanished from the second cycle.

The cycle performance along with EIS analysis of Graphite/Li half-cells containing different quantities of MPTS were recorded to optimize the amount of MPTS in the electrolyte. The capacity retention was obtained after 50 cycles in 0%, 0.5%, 1%, 1.5%, and 2% of MPTS for Graphite/Li cells at 0.5 C. As can be understood from Figure. S1 the inclusion of MPTS leads to increase in capacity retention and the electrolyte containing 1.5% MPTS possesses the highest value. But with the extra addition of MPTS the capacity retention decreased. The observed phenomenon can be attributed to the construction of a thicker solid electrolyte interface on the surface of the electrode and the subsequent increase in interfacial impedance, as evidenced by EIS analysis depicted in Figure. S2. Therefore, the electrolyte with 1.5% MPTS was determined to be the optimal amount of additive.

The charge/discharge test of cells without and with MPTS was conducted to realize the impact of MPTS on the cycle durability of Li/graphite half-cells (Figure. 5). The cells were cycled at 0.1 C during the initial three cycles (formation process), then at 0.2 C for the next 100 cycles. Graphite/Li half cells with initial charge-discharge curves with and without 1.5 wt% of MPTS are shown in Figure. 5a at a low current density of 0.1 C. The graphite electrode demonstrated first charge-discharge capacities of 340.64 mAhg^− 1 and 370.70 mAhg^− 1, respectively, with irreversible capacity (C_irr) loss of 30.05 mAhg^− 1 and initial coulombic efficiency (ICE) of 91.90% in the additive-free cell. On the other hand, the MPTS-containing cell delivered a precise capacity in the first charge (353.94 mAhg^− 1) and discharge (373.53mAhg^− 1) with C_irr of 19.60 mAhg^− 1 and ICE of 94.75%. These improvements in ICE and C_irr are due to the presence of the MPTS, which can reduce prior to electrolyte and shield the active sites on the graphite substrate and preserve it considerably from the carbonate electrolyte decomposition [49]. Generally, the Li ion intercalation occurs below 0.5 V vs. Li/Li⁺, exhibiting a long plateau ranging from 0.2 to 0.01 V in both cells. The cycling behavior and coulombic efficiency of Li/graphite cells are depicted in Figure. 5b, c. The outcomes revealed that the cell with MPTS has excellent cycle-life and higher coulombic efficiency compared with the cell without this additive. The specific charge capacities in the initial cycle at 0.2 C rate for the base electrolyte and the electrolyte with additive are 351.12 and 360.40 mAhg^− 1 respectively. The initial capacity at 0.2 C rate is improved because the MPTS has been preferentially reduced to construct an efficient SEI film to protect against further electrolyte solvent decomposition. At the 100th cycle, the capacity in the MPTS-free electrolyte decreased from 351.12 to 286.60 mA h g^− 1. The capacity retention was 85.38% after 50 cycles and 81.62% after 100 cycles relative to the first cycle at a 0.2 C rate. According to the cyclability of the graphite electrode cycled in MPTS containing electrolyte, the cyclic performance was enhanced, and the capacity retention was 93.17% after 100 cycles.

Figure. 5d shows the rate capability of Li/graphite cells without and with MPTS at various C-rates. As can be seen, the MPTS-containing cell represents a higher rate capability than the blank electrolyte. The related charge capacities for MPTS containing electrolytes at C-rates of 0.1 C, 0.2 C, 0.5 C, and 1 C are ~ 375, 353, 266, and 146 mAhg^− 1, respectively. These values are greater than those of the blank in similar conditions (~ 350, 318, 244, and 97 mAhg^− 1). Furthermore, the capacity retention of ~ 95% in MPTS containing and ~ 89% in the baseline electrolyte was achieved once the current density was reverted to the first 0.1 C. This is because the MPTS-derived interface film enhances the conductivity of lithium ions, boosts the fast transfer of Li ions, and diminishes the charge-transfer resistance (R_CT) at different current densities, which is further proved by EIS characterization. Hereupon, introducing MPTS in the electrolyte noticeably improved the rate performance and cycle life. This can be explained by the fact that adding MPTS to the electrolyte favored the reduction reaction at a higher potential with the generation of a stable, denser, and thinner solid electrolyte interface. Hence the electron tunneling through the interfacial film is hindered, and subsequent decomposition of the electrolyte could be eliminated.

The graphite/Li half-cell's AC impedance in MPTS-containing and blank electrolytes after 2 and 100 cycles was measured for further investigation. As observed in Figure. 6a, b, there are two semicircles in the Nyquist plots. A semicircle at a middle-frequency (R_ct) illustrates the electrode charge transfer impedance, a semicircle at a high frequency (interlayer resistance, R_f) corresponds to the impedance of migration of Li⁺ from the electrolyte to the electrode, and the Warburg (W_o) impedance, which is relevant for Li ions diffusion in the solid [49]. Obviously, after two cycles, the R_ct and R_f of the cell with and without MPTS are comparable and almost close to each other, as shown in Figure. 6a, c. Nevertheless, after 100 cycles the resistance of the blank electrolyte displays a remarkable growth as indicated in Figure. 6b, d. It becomes noticeably higher than that of the MPTS-containing electrolyte, demonstrating the drastic consumption of the blank electrolyte, as a result of degradation products, enveloping the graphite electrode surface. On the other hand, the R_f and R_ct of the cell with MPTS prominently reduced after 100 cycles, which is

consistent with the achieved higher cycle stability compared to the blank. Such interfacial resistance reduction during the consecutive charge and discharge can also be perceived in other studies. Decreasing the interfacial and charge transfer resistance can diminish the ohmic and activation polarization happening during the insertion/disinsertion of Li⁺ ions into the graphite electrode, leading to the significant cyclic performance of the electrode [50]. It should be noted that it is essential to do more detailed studies on realizing the interfacial ingredients that make such changes in impedance in future research. The EIS data are used to determine the diffusion coefficients of Li ions (D_Li+) and the exchange current density (J₀)[51] according to Eqs. (1) and (2):

D = T²R²/2A²F⁴n⁴C²σ² (1)

J₀ = RT/nFR_ctA (2)

Where T = thermodynamic temperature (298 K), R = gas coefficient (8.314 Jk^− 1mol^− 1), A = area of the electrode (A = πr²) [52], F = Faraday coefficient (96500 Cmol^− 1 ), n = transferred electron number through insertion/de-insertion of Li ion (for Li⁺ n = 1), and C = Li⁺ ion concentration in solid, and σ = the slope of the linear part in Z′ ∼ ω^−1/2 (Warburg factor) [53]. σ (Ω·s^− 1/2) can be achieved from the equation [54] (3):

Z′ = R_S + R_ct + σω^−1/2 (3)

Figure. 6e, f displays the Warburg factor (σ) by fitting line slopes for the blank and MPTS-containing electrolytes. The D_Li+ of the cell with MPTS is 1.42 × 10^− 11 cm²s^− 1 and 2 × 10^− 11 cm²s^− 1 after 2 and 100 cycles, respectively, which is greater than D_Li+ of the cell without additive after 2 and 100 cycles (1.25 × 10^− 11 cm² s^− 1and 0.41 × 10^− 11 cm² s^− 1). Moreover, the exchange current density (J₀) of MPTS containing electrolyte after 100 cycles is 8.18×10^− 4 A cm^− 2, which is approximately 3 times greater than that of base electrolyte (2.82×10^− 4 A cm^− 2) suggesting that the cell with MPTS possesses much better kinetics[52].

The morphology of graphite electrodes was also studied. Figure. 7a-f represents the FESEM and TEM micrographs of the fresh graphite electrode before and after 100 cycling in the electrolyte with and without MPTS. As can be seen, there is no covering on the fresh graphite electrode surface, while deposits are created on both cycled graphite electrodes, which shows that the formation of SEI layer happened after contact with the electrolyte. In the MPTS-free electrolyte, the surface of the graphite is covered with spherical particles, which suggests that a secondary reaction takes place between the electrolyte and electrode surface during the cycle[55]. Consequently, the film may cause an increase in the electrode’s impedance value. However, the homogenous, smooth and compact morphology is seen on the graphite surface with the MPTS containing electrolyte, which diminishes the direct contact between the electrolyte and electrode surface. The TEM images of samples without and with additive in Figure. 7e, f shows that a better quality layer with MPTS is formed than the sample without additives. This illustrates that adding MPTS makes it easier to create a better SEI film. Figure. 7g, h represents the EDX elemental mapping of cycled graphite electrodes in additive-free electrolyte and MPTS-containing electrolyte, respectively, which proved the presence of the S element on the surface of graphite in the electrolyte with MPTS.

The X-ray diffraction patterns of the graphite electrodes before as fresh and after cycling in the electrolytes with and without MPTS were indicated in Figure. S3. Each of the electrodes was made under equal circumstances. As shown in figure S3, there are two peaks at approximately 26 and 55 related to the graphite structure. The findings suggest that the structure of the graphite electrode remains unchanged throughout cycling in the electrolyte with or without MPTS. Hence, the alteration in the morphology of graphite surface isn’t caused by phase transition of the electrode, but rather by the incorporation of MPTS into the base electrolyte. This implies that a protective film originating from MPTS forms on the graphite surface, leading to an enhancement in the performance of the cell.

Figure. 8 represents the FT-IR spectra of the cycled and pure graphite electrodes in the presence and absence of MPTS. The peaks at 2926 and 2849 cm^− 1 in the fresh electrode represent the asymmetric and symmetric vibrations of the CH₂ groups, respectively. The C = C and C-O bands originating from chemisorbed oxygen groups are a result of the peaks at 1641 and 1089 cm^− 1, respectively [49, 56]. According to studies, the chemical composition of the layer of SEI can be ascertained by the electrolyte ingredients [57]. The construction of the SEI layer by EC happens via two mechanisms. In the first mechanism, lithium carbonate (Li₂CO₃) and gaseous compounds are the main products of the electrochemically-induced reduction of EC[58]. In the second path, the main component of SEI is lithium ethylene dicarbonate (LEDC), which are substantially insoluble in the electrolyte [59]. The reduction of DMC causes the formation of lithium methyl carbonate (LMC) [57]. The pronounced peaks at 1633 cm^− 1 (C = O) and 1052 cm^− 1 (C‒O) are correlated to ROCO₂Li species. The characteristic peak at 1448 cm^− 1 shows the existence of Li₂CO₃ [31]. The bands at 1106 and 1245 cm^− 1 exist in the FT-IR spectrum of the cycled graphite in the electrolyte with 1.5% MPTS. To determine these peaks, we checked the FT-IR of the pure MPTS. In the region from 1100 to 1400 cm^− 1, two bands at 1175 and 1350 cm^− 1 are detected, which are associated with the symmetrical stretching and asymmetrical stretching of SO₂, respectively[49, 60]. Hence, the peaks at 1106 and 1245 cm^− 1 were ascribed to the symmetric and asymmetric SO₂ stretching, respectively, shifted to the lower frequency and proved the MPTS reduction products incorporation in the construction of SEI layer. In addition, the peaks related to the C = O, and C-O are also observed, creating a stable SEI layer.

The XPS of graphite electrodes without and with MPTS was conducted after 100 cycles to determine the chemistry of the layer of SEI. As can be seen in Figure. 9, the C 1s spectrum has two maxima at 284.2 and 285.5 eV, referring to C‒C and C‒O covalent bonding due to carbon black and lithium alkyl carbonates (R-CH₂OCO₂-Li), respectively. In addition, the bands at 291.2, 289.9, and 287.7 eV are related to the PVDF, Li₂CO_3, and C = O bond, respectively[47]. As depicted in Figure. 9, the peak intensity of C = O decreases by adding MPTS, elucidating that MPTS could prevent solvent degradation. Moreover, the inclusion of MPTS reduces the intensity of Li₂CO₃, one of the major degradation derivatives of carbonate-based electrolytes, in O 1s and C 1s spectra, demonstrating the positive effect of MPTS in suppressing the electrolyte decomposition. Furthermore, three characteristic peaks assigned to LiF, LiP_xF_y, and LiP_xO_yF_z can be seen, which are related to the decomposition products of LiPF₆[61]. It should be noted that by increasing the electrolyte decomposition products, the interfacial impedance would increase and lead to poor cycling behavior of the graphite electrode. The intensity of these peaks decreases in the presence of MPTS, indicating that the MPTS-derivative SEI film limits the degradation of LiPF₆. The XPS results support the EIS data. After 100 cycles, the cell with MPTS added electrolyte has a much lower impedance than the cell with baseline electrolyte. As shown in C 1s and F1s, the peak of PVDF almost vanished after 100 cycles in electrolyte with 1.5 wt% MPTS, elucidating that the uniform SEI layer covers the graphite electrode, being consistent with the TEM result. As seen in EDX elemental mapping characterization and XPS spectrum of graphite after cycling with MPTS-containing electrolyte, S-containing products can also be observed in S 2p spectra of the surface of the electrode after cycling in 1.5 wt% MPTS electrolyte at 166.6 eV and 168.5eV related to R-SO₂Li (two-electron reduction) and RSO₃Li (one-electron reduction) respectively, which are assigned to the reduction reaction of MPTS, as discussed in Figure. 3.

In this study, methyl p-toluene sulfonate (MPTS), a new S-based additive, was investigated as an electrolyte additive that formed film on the graphite electrode. DFT computation showed that the electron affinity energy of MPTS is more negative than the reference electrolyte, which can be reduced prior to the base electrolyte. The study of the reduction mechanism with the help of the DFT thermodynamic study recommended the one electron and two-electron reduction mechanisms, which finally showed that the lithiated sulfur-containing compounds take part in SEI formation, which was in good agreement with XPS and EDX results. The rate capability and cycle behavior of graphite/Li cells were enhanced applying a small dosage of 1.5 wt % MPTS. The capacity retention was also enhanced from 81.62–93.17% after 100 cycles, which is connected to modified SEI layer created on the graphite in the existence of MPTS, that can protect the graphite electrode from co-intercalation of the solvated Li ions, meliorate the structural stability of graphite electrode, suppress the electrolyte destructive reactions, and lower the charge transfer resistance. The protective SEI film is compact and thin according to SEM and TEM micrographs. Theoretical and practical outcomes proved that the MPTS additive was involved in constructing an SEI on the graphite electrode. These results lead to a more profound understanding of SEI film stability and propose a new electrolyte design and development for secondary lithium-ion batteries.

Acknowledgment

The authors appreciate the Renewable Energy Research Center (RERC) and Amirkabir University of Technology (AUT) for technical assistance.

Ethical Approval

This declaration is not applicable

Competing interests

The authors declare they have no financial interests

Authors' contributions

Susan Hamidi: Investigation, Conceptualization Writing – original draft, Visualization; Mehran Javanbakht: Supervision, and Conceptualization, Resources Mohammad Hassan Mousazadeh: Supervision; Saeedeh Sarabadani Tafreshi: Conceptualization, Writing – review & editing.

Funding

No funds, grants, or other support was received

Availability of data and materials

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files.

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A Novel Approach for Robust Solid/electrolyte Interface Formation in Lithium-Ion Batteries using Methyl p-toluenesulfonate Additive

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