Novel SEI formation of maleimide-based additives and its improvement of capability and cyclicability in lithium ion batteries

This investigation elucidates three maleimide (MI)-based aromatic molecules as additives in electrolyte that is used in lithium ion batteries. The 1.1 M LiPF₆ in ethylene carbonate (EC):propylene carbonate (PC):diethylene carbonate (DEC) (3:2:5 in volume) containing MI-based additives can prompt the formation of a solid electrolyte interface (SEI); and inhibit the entering into the irreversible state during lithium intercalation and co-intercalation. The reduction potential is 0.71-0.98 V versus Li/Li⁺ as determined by cyclic voltammetry (CV). The morphology and element analysis of the positive and negative electrode after the 100th charge-discharge cycle are examined by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). Moreover, the MI was used in lithium ion batteries and provided 4.9% capacity increase and 16.7% capacity retention increase when cycled at 1C/1C. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries. MI is decomposed electrochemically to form a long winding narrow SEI strip on the graphite surface. This novel SEI strip not only prevents exfoliation on the graphite electrode but also stabilizes the electrolyte. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries.     

On the difference in cycling behaviors of lithium-ion battery cell between the ethylene carbonate- and propylene carbonate-based electrolytes

Density functional theory (DFT) calculations and classical molecular dynamics (MD) simulations have been performed to gain insight into the difference in cycling behaviors between the ethylene carbonate (EC)-based and the propylene carbonate (PC)-based electrolytes in lithium-ion battery cells. DFT calculations of the lithium solvation, Li⁺(S)_i (S = EC or PC; i = 1–4) with and without the presence of the counter anion showed that the desolvation energy to remove one solvent molecule from the first solvation shell of the lithium ion was significantly reduced by as much as 70 kcal mol⁻¹ (293.08 kJ mol⁻¹) in the presence of the counter anion, suggesting the lithium ion is more likely to be desolvated at high salt concentrations. The thermodynamic stability of the ternary graphite intercalation compounds, Li⁺(S)_iC₇₂, in which Li⁺(S)_i was inserted into a graphite cell, was also examined by DFT calculations. The results suggested that Li⁺(EC)_iC₇₂ was more stable than Li⁺(PC)_iC₇₂ for a given i. Furthermore, some of Li⁺(PC)_iC₇₂ were found to be energetically unfavorable, while all of Li⁺(EC)_i=1–4C₇₂ were stable, relative to their corresponding Li⁺(S)_i in the bulk electrolyte. In addition, the interlayer distances of Li⁺(PC)_iC₇₂ were more than 0.1 nm longer than those of Li⁺(EC)_iC₇₂. MD simulations were also carried out to examine the solvation structures at a high salt concentration of LiPF₆: 2.45 mol kg⁻¹. The results showed that the solvation structure was significantly interrupted by the counter anions, having a smaller solvation number than that at a lower salt concentration (0.83 mol kg⁻¹). We propose that at high salt concentrations, the lithium desolvation may be facilitated due to the increased contact ion pairs so as to form a stable ternary GIC with less solvent molecules without destruction of graphite particles, followed by solid–electrolyte-interface film formation reactions. The results from both DFT calculations and MD simulations are consistent with the recent experimental observations.     

Behaviour of highly crystalline graphitic materials in lithium-ion cells with propylene carbonate containing electrolytes: An in situ Raman and SEM study

The microcrystalline flaked graphites SFG6 and SFG44 were evaluated with regard to their compatibility with propylene carbonate (PC) by in situ Raman microscopy and postmortem scanning electron microscopy (SEM) study. PC is employed as electrolyte component in lithium-ion batteries. However, when used with certain types of graphitic materials, exfoliation occurs. To compare the effects of exfoliation, the first lithium insertion properties of these graphitic materials were measured with in situ Raman microscopy. Lithium half-cells containing either 1 M LiClO₄ 1:1 (w/w) ethylene carbonate (EC):dimethyl carbonate (DMC) or 1:1 (w/w) EC:PC were investigated. The commencement of the exfoliation process was detected in SFG44 EC:PC by the appearance of a shoulder band at 1597 cm⁻¹ on the G-band (1584 cm⁻¹) below 0.9 V versus Li/Li⁺. The band (assigned as the exfoliation or E-band) at higher wavenumbers (1597 cm⁻¹) corresponded to solvated lithium ions intercalated into graphite. The in situ Raman spectra of SFG6 in EC:DMC or EC:PC and SFG44 in EC:DMC did not show the E-band and instead displayed regular lithium intercalation spectra.In situ Raman microscopy and SEM were further employed to study the exfoliation process observed for SFG44 in 1:1 (w/w) EC:PC, when the potential was held under steady-state conditions at 0.8, 0.6 and 0.3 V, respectively. A blue-shift in the E-band from 1597 to 1607 cm⁻¹ was observed as the potential was lowered. SEM images showed dissimilar degrees of exfoliation at these three potentials.     

The function of vinylene carbonate as a thermal additive to electrolyte in lithium batteries

The role of vinylene carbonate (VC) as a thermal additive to electrolytes in lithium ion batteries is studied in two aspects: the protection of liquid electrolyte species and the thermal stability of the solid electrolyte interphase (SEI) formed from VC on graphite electrodes at elevated temperatures. The nuclear magnetic resonance (NMR) spectra indicate that VC can not protect LiPF₆ salt from thermal decomposition. However, the function of VC on SEI can be observed via impedance and electron spectroscopy for chemical analysis (ESCA). These results clearly show VC-induced SEI comprises polymeric species and is sufficiently stable to resist thermal damage. It has been confirmed that VC can suppress the formation of resistive LiF, and thus reduce the interfacial resistance.     

The effect of electrolyte temperature on the passivity of solid electrolyte interphase formed on a graphite electrode

The effect of electrolyte temperature on the passivity of solid electrolyte interphase (SEI) was investigated in 1 M LiPF₆-ethylene carbonate/diethyl carbonate (50:50 vol.%) electrolyte, using galvanostatic charge-discharge experiment, and ac-impedance spectroscopy combined with Fourier transform infra-red spectroscopy, and high resolution transmission electron microscopy (HRTEM). The galvanostatic charge-discharge curves at 20 °C evidenced that the irreversible capacity loss during electrochemical cycling was markedly increased with rising SEI formation temperature from 0 to 40 °C. This implies that the higher the SEI formation temperature, the more were the graphite electrodes exposed to structural damages. From both increase of the relative amount of Li₂CO₃ to ROCO₂Li and decrease of resistance to the lithium transport through the SEI layer with increasing SEI formation temperature, it is reasonable to claim that, due to the enhanced gas evolution reactions during transformation of ROCO₂Li to Li₂CO₃, the rising SEI formation temperature increased the number of defect sites in the SEI layer. From the analysis of HRTEM images, no significant structural destruction in bulk graphite layer was observed after charge-discharge cycles. This means that solvated lithium ions were intercalated through the defect sites in the SEI, at most, into the surface region of the graphite layer.     

Electrochemical intercalation of lithium into a natural graphite anode in quaternary ammonium-based ionic liquid electrolytes

Electrochemical intercalation of lithium into a natural graphite anode was investigated in electrolytes based on a room temperature ionic liquid consisting of trimethyl-n-hexylammonium (TMHA) cation and bis(trifluoromethanesulfone) imide (TFSI) anion. Graphite electrode was less prone to forming effective passivation film in 1 M LiTFSI/TMHA-TFSI ionic electrolyte. Reversible intercalation/de-intercalation of TMHA cations into/from the graphene interlayer was confirmed by using cyclic voltammetry, galvanostatic measurements, and ex situ X-ray diffraction technique. Addition of 20 vol% chloroethylenene carbonate (Cl-EC), ethylene carbonate (EC), vinyl carbonate (VC), or ethylene sulfite (ES) into the ionic electrolyte resulted in the formation of solid electrolyte interface (SEI) film prior to TMHA intercalation and allowed the formation of Li-C₆ graphite interlayer compound. In the ionic electrolyte containing 20 vol% Cl-EC, the natural graphite anode exhibited excellent electrochemical behavior with 352.9 mAh/g discharge capacity and 87.1% coulombic efficiency at the first cycle. A stable reversible capacity of around 360 mAh/g was obtained in the initial 20 cycles without any noticeable capacity loss. Mechanisms concerning the significant electrochemical improvement of the graphite anode were discussed. Ac impedance and SEM studies demonstrated the formation of a thin, homogenous, compact and more conductive SEI layer on the graphite electrode surface.     

Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF₆ and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO₄ lithium-ion battery. Charging/discharging capacity of the LiFePO₄ electrode was ca. 150 mAh g⁻¹ (VC content 5 wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350 mAh g⁻¹ (C/10 rate). In the case of the full graphite |1 M LiPF₆ + TMS + VC 10 wt% |LiFePO₄ cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120 mAh g⁻¹. Exchange current density for Li⁺ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j_o(Li/Li⁺) = 8.15 × 10⁻⁴ A cm⁻². Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO₄ electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF₆ + TMS + VC electrolyte (TG/DTA experiment) was present at ca. 275 °C. The LiFePO₄(solid) + 1 M LiPF₆ + TMS + 10 wt% VC system shows a flash point of ca. 150 °C. This was much higher in comparison to that characteristic of a classical LiFePO₄ (solid) + 1 M LiPF₆ + 50 wt% EC + 50 wt% DMC system (T_f ≈ 37 °C).     

Electrolyte additives for enhanced thermal stability of the graphite anode interface in a Li-ion battery

The influence of electrolyte additives on the thermal stability of graphite anodes in a Li-ion battery has been investigated. The selected additives are: ethyltriacetoxysilane, 1,3-benzoldioxole, tetra(ethylene glycol)dimethylether and vinylene carbonate. These compounds were added in 4% to an electrolyte consisting of 1M LiBF₄ ethylene carbonate (EC)/diethyl carbonate (DEC) solvent mixture. Differential scanning calorimetry (DSC) was used to investigate the thermal stability. The electrochemical performance was investigated by galvanostatic cycling and the formed solid electrolyte interphase (SEI) was characterised by photoelectron spectroscopy (PES) using Al Kα and synchrotron radiation (SR). The onset temperature for the thermally activated reactions was found to increase for all electrodes cycled with additives compared to electrodes cycled without additives. The onset temperature increased in the order: no additive < tetra(ethylene glycol)dimethyl ether < 1,3-benzoldioxole < ethyl-triacetoxysilane < vinylene carbonate. Features in the PES spectra found to be associated with high onset temperatures for thermally activated reactions are: (i) no discernible graphite peak, (ii) small amount of salt species of the type LiF and Li_xBF_yO_z and (iii) larger amounts of organic compounds preferably with a high oxygen content.     

Triethyl orthoformate as a new film-forming electrolytes solvent for lithium-ion batteries with graphite anodes

Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0 M LiPF₆ in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO₂Li, ROLi, Li₂CO₃, etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes.     

Effect of fluoroethylene carbonate on high temperature capacity retention of LiMn2O4/graphite Li-ion cells

In order to overcome severe capacity fading of LiMn₂O₄/graphite Li-ion cells at high temperature at 60 °C, fluoroethylene carbonate (FEC) was newly evaluated as an electrolyte additive. With 2 wt.% FEC addition into the electrolyte (EC/DEC/PC with 1 M LiPF₆), the capacity retention at 60 °C after 130 cycles was significantly improved by about 20%. To understand the underlying principle on the capacity retention enhancement, the electrochemical properties of the cells including cell performance, impedance behavior as well as the characteristics of the interfacial properties were examined. Based on these results, it is suggested that the improved capacity retention of LiMn₂O₄/graphite Li-ion cells with addition of FEC especially at high temperature is mainly originated from the thin and stable SEI layer formed on the graphite anode surface.     

Ethylene carbonate—propylene carbonate mixed electrolytes for lithium batteries

Electrolytic characteristics of propylene carbonate (PC)ethylene carbonate (EC) mixed electrolytes were studied, compared with those in PC electrolytes. Conductivity and Li charge—discharge efficiency values increased with EC contents increasing. For example, 1 M LiClO₄ECPC (EC mixing molar ratio; [EC]/[PC] = 4) showed the conductivity of 8.5 ohm^?1 cm^?1, which value was 40% higher than that in PC. Also, 1 M LiClO₄ECPC([EC]/[PC] = 5) showed the Li charge—discharge efficiency of 90.5% at 0.5 mA cm^?2, 0.6 C cm^?2, which value was ca. 25% higher than that in PC. ECPC mixed electrolytes were considered to be practically available for ambient lithium batteries in regard to the high Li⁺ ion conductivity and also high Li charge—discharge efficiency.     

Interfacial structural stabilization on amorphous silicon anode for improved cycling performance in lithium-ion batteries

Interfacial structures of electrode-current collector and electrode-electrolyte have been designed to be stabilized for improved cycling performance of amorphous silicon (Si) that is considered as an alternative anode material to graphite for lithium-ion batteries. Interfacial structural stabilization involves the interdigitation of Si electrode-Cu current collector substrate by anodic Cu etching with thiol-induced self-assembly, and the formation of self-assembled siloxane on the surface of Si electrode using silane. The novel interfacial architecture possesses promoted interfacial contact area between Si and Cu, and a surface protective layer of siloxane that suppresses interfacial reactions with the electrolyte of 1 M LiPF₆/ethylene carbonate (EC):diethylene carbondate (DEC). FTIR spectroscopic analyses revealed that a stable solid electrolyte interphase (SEI) layer composed of lithium carbonate, organic compounds with carboxylate metal salt and ester functionalities, and PF-containing species formed when having siloxane on Si electrode. Interfacially stabilized Si electrode exhibited a high capacity retention 80% of the maximum discharge capacity after 200 cycles between 0.1 and 1.5 V vs. Li/Li⁺. The data contribute to a basic understanding of interfacial structural causes responsible for the cycling performance of Si-based alloy anodes in lithium-ion batteries.     

Surface chemistry of intermetallic AlSb-anodes for Li-ion batteries

The solid electrolyte interphase (SEI) layer on AlSb electrodes has been studied in Li/AlSb cells containing a LiPF₆ EC/DEC electrolyte using X-ray photoelectron spectroscopy (XPS). Data were collected before SEI-formation, during formation, and after formation at 0.01 V versus Li⁰/Li⁺, and at full delithiation in cycled cells at 1.20 V. The thickness of the SEI layer increases during lithiation and decreases during delithiation. This dynamic behaviour occurs continuously on cycling the cells. The growth of the SEI layer can be attributed predominantly to the deposition of carbonaceous species below 0.50 V versus Li⁰/Li⁺; these species disappear almost completely during delithiation. The extra surface-layer formation is a consequence of the additional charge that is needed to lithiate the remaining Sb component of the micrometer-sized AlSb particles at low potentials as seen by synchrotron-based X-ray diffraction. Aluminium is not reactive to lithium alloying in this electrolyte. Relatively small amounts of LiF were detected in the AlSb SEI layers compared to that commonly found in the SEI layers on graphite electrodes.     

Phenomenologically modeling the formation and evolution of the solid electrolyte interface on the graphite electrode for lithium-ion batteries

The formation and evolution of the solid electrolyte interface (SEI) film during the first electrochemical intercalation of lithium into graphite were modeled as a special precipitation process including a nucleation phase of the SEI film's solid deposition, and followed by a growth phase involving the precipitation of new solids on previously formed solid nuclei. It was shown that the solid species can nucleate in the electrolyte solution, directly on the graphite surface, or adjacent to an already present particle on the graphite surface when precipitating from the electrolyte solution. Within the framework of classical nucleation theory (CNT), we can qualitatively explain the origin of the two-layer structure of SEI films, which consists of a thin, compact polycrystalline or heteromicrophase layer rich in inorganic species (e.g., LiF, Li₂O) close to the electrode, and a thicker porous and amorphous layer composed mainly of organic compounds (e.g., ROLi, ROCO₂Li) that is farther from the graphite.     

Effect of vinylene carbonate as additive to electrolyte for lithium metal anode

The cycling efficiencies and cycling performance of a lithium metal anode in a vinylene carbonate (VC)-containing electrolyte were evaluated using Li/Ni and LiCoO₂/Li coin type cells. The cycling efficiencies of deposited lithium on a nickel substrate in an EC + DMC (1:1) electrolyte containing LiPF₆, LiBF₄, LiN(SO₂CF₃)₂ (LiTFSI), or LiN(SO₂C₂F₅) (LiBETI) at 25 and 50 °C were improved by presence of VC. However, the lithium cycling efficiencies at low temperature (0 °C) decreased by adding VC to the EC+DMC (1:1) electrolyte. The deposited lithium at low temperature exhibited a dendritic morphology and a thicker surface film. The lithium ion conductivity of the VC derived surface film was lower than that of the VC-free surface film at low temperature. Therefore, we concluded that the cycling efficiency decreased with decreasing temperature. On the other hand, the cell containing VC additive has excellent performance at elevated temperature. The deposited lithium at 50 °C in the VC-containing electrolyte exhibited a particulate morphology and formed a thinner surface film. The VC derived surface film, which consists of polymeric species, suppressed the deleterious reaction between the deposited lithium and the electrolyte.     

Electrochemical cycling behaviour of lithium carbonate (Li2CO3) pre-treated graphite anodes – SEI formation and graphite damage mechanisms

Graphite electrode surfaces were treated using a simple process of sedimentation in aqueous solutions containing 0.5 and 1.0 wt.% Li₂CO₃ with particle sizes of ∼1–2 μm. During the first cycle of voltammetry tests (vs. Li/Li⁺), the graphite surface was subjected to electrochemical degradation as a result of fracture and removal of near-surface graphite particles. Surface degradation was accompanied by a 0.4% strain in the graphite lattice as determined by in situ Raman spectroscopy. Pre-treated electrodes experienced a capacity drop of 3% in the first cycle, compared to a 40% drop observed in case of untreated graphite electrodes. After testing for 100 cycles, a capacity of 0.54 mAh cm⁻² was recorded for the pre-treated electrodes as opposed to a significant drop to 0.11 mAh cm⁻² for the untreated graphite. Cross-sectional HR-TEM indicated that the SEI formed on the pre-treated electrodes primarily consisted of Li₂CO₃ crystals of 14.6 ± 6.9 nm in size distributed within an amorphous matrix. The results suggested that the Li₂CO₃ enriched SEI formed on the pre-treated electrodes reduced the intensity of solvent co-intercalation induced surface damage. It is proposed that the Li₂CO₃ enriched SEI facilitated Li⁺ diffusion and hence improved the capacity retention during long-term cycling.     

Synthesis of organic carbonates from alcoholysis of urea: A review

Organic carbonates are green compounds with a wide range of applications. They are widely used for the synthesis of important industrial compounds including monomers, polymers, surfactants, plasticizers, and also used as fuel additives. They can be divided into two main classes: cyclic and linear carbonates. Dimethyl carbonate (DMC) and diethyl carbonate (DEC) are the important linear carbonates. Carbonyl and alkyl groups present in DMC and DEC make them reactive and versatile for synthesizing various other important compounds. Ethylene carbonate (EC), glycerol carbonate (GC) and propylene carbonate (PC) are well-known cyclic organic carbonates. Phosgenation of alcohols was widely used for synthesis of organic carbonates; however, toxicity of raw materials restricted use of phosgenation method. A number of new non-phosgene methods including alcoholysis of urea, carbonylation of alcohols using CO₂, oxy-carbonylation of alcohols, and trans-esterfication of alcohols and carbonates have been developed for synthesizing organic carbonates. Carbonylation of alcohols is preferred as it helps in utilization and sequestration of CO₂, however, poor thermodynamics due to high stability of CO₂ is the major obstacle in its large scale commercialization. Oxy-carbonylation of alcohols offers high selectivity but presence of oxygen poisons the catalyst. Recently, alcoholysis of urea has received more attention because of its inexpensive abundant raw materials, favorable thermodynamics, and no water-alcohol azeotrope formation. Also, ammonia evolved in this synthesis route can be recycled back to urea by reacting it with CO₂. In other words, this method is a step towards utilization of CO₂ as well. This article reviews synthesis of DMC, DEC, GC, PC, and EC from urea by critically examining various catalysts used and their performances. Mechanisms have been reviewed in order to give an insight of the synthesis routes. Research challenges along with future perspectives have also been discussed.     

On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries

Vinylene carbonate (VC) was tested as an additive to electrolyte solutions for Li-ion batteries. For the model electrodes, synthetic graphite was chosen as the anode material, while LiMn₂O₄ spinel and LiNiO₂ were chosen as the cathode materials. The test solution was 1 M LiAsF₆ in a 1:1 mixture of ethylene and dimethyl carbonates (EC-DMC). Cyclic voltammetry (CV), chronopotentiometry, impedance spectroscopy, electrochemical quartz crystal microbalance (EQCM), FTIR and X-ray photoelectron spectroscopies have been used in this study. It was found that VC is a reactive additive that reacts on both the anode and the cathode surfaces. The influence of this additive on the behavior of Li-graphite anodes is very positive, since it improves their cyclability, especially at elevated temperatures, and reduces the irreversible capacity. The spectroscopic studies indicate that VC polymerizes on the lithiated graphite surfaces, thus forming poly alkyl Li-carbonate species that suppress both solvent and salt anion reduction. The presence of VC in solutions reduces the impedance of the LiMn₂O₄ and LiNiO₂ cathodes at room temperature. However, we have not yet found any pronounced impact of VC on the cycling behavior of the cathodes, either at room temperature or at elevated temperatures. Thus, VC can be considered as a desirable additive for the anode side in Li-ion batteries, one which has no adverse effect on the cathode side.     

Effects of particle size on the thermal stability of lithiated graphite anode

The thermal behavior of fully lithiated natural graphite flakes with different particle sizes has been investigated using differential scanning calorimetry (DSC). For DSC measurements, a fully lithiated graphite anode was heated in a hermetically sealed high pressure pan with a poly vinylidene diflouride (PVdF) binder and 1 M LiPF₆ solution in ethylene carbonate (EC)-diethyl carbonate (DEC) mixture. It has been founded that the particle size has a strong influence on the thermal stability of the lithiated graphite anode. The heat generation due to the solid electrolyte interface (SEI) decomposition increases with decreasing the particle size. The onset temperatures for exothermic reactions after initial SEI decomposition appear to be lower for graphite electrodes with smaller particle sizes. This is attributed to a thermal induced delithiation facilitated by reduced diffusion path and higher surface area in smaller graphites. The structural changes in graphites during DSC scan have been investigated by ex situ X-ray diffraction (XRD) and Raman spectrometer.     

In situ FTIR spectra at the Cu electrode/propylene carbonate solution interface

In situ Fourier transform infrared spectroscopy (FTIR) spectra measurements were obtained for a Cu electrode/solution of lithium perchlorate in propylene carbonate (PC). The dependence of potential on the concentration of PC in the vicinity of the electrode was investigated. The bands due to free PC and PC solvated to lithium ions in the solution were distinguished by the single reflection attenuated total reflection (ATR) spectra. In the FTIR spectra, the reversible change in the concentration of free PC and solvated PC in the diffuse double layer was observed to be accompanied by a change in potential. As the potential decreased, the free PC concentration increased, while the concentration of the PC solvated to lithium ions decreased. Thus, it can be concluded that the equilibrium shifts from Li⁺(PC)₄ to Li⁺(PC)₃ + PC as the potential decreases. Furthermore, Li⁺(PC)₃ orientates itself so that it is parallel to the electrode surface.