Analysis of SEI formed with cyano-containing imidazolium-based ionic liquid electrolyte in lithium secondary batteries

Two kinds of cyano-containing imidazolium-based ionic liquid, 1-cyanopropyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CpMI-TFSI) and 1-cyanomethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CmMI-TFSI), each of which contained 20 wt% dissolved LiTFSI, were used as electrolytes for lithium secondary batteries. Compared with 1-ethyl-3-methylimidazolium-bis(trifluoromethane-sulfonyl)imide (EMI-TFSI) electrolyte, a reversible lithium deposition/dissolution on a stainless-steel working electrode was observed during CV measurements in these cyano-containing electrolytes, which indicated that a passivation layer (solid electrolyte interphase, SEI) was formed during potential scanning. The morphology of the working electrode with each electrolyte system was studied by SEM. Different dentrite forms were found on the electrodes with each electrolyte. The SEI that formed in CpMI-TFSI electrolyte showed the best passivating effect, while the deposited film formed in EMI-TFSI electrolyte showed no passivating effect. The chemical characteristics of the deposited films on the working electrodes were compared by XPS measurements. A component with a cyano group was found in SEIs in CpMI-TFSI and CmMI-TFSI electrolytes. The introduction of a cyano functional group suppressed the decomposition of electrolyte and improved the cathodic stability of the imidazolium-based ionic liquid. The reduction reaction route of imidazolium-based ionic liquid was considered to be different depending on whether or not the molecular structure contained a cyano functional group.     

Density functional theory (DFT) calculations,synthesis and electronic properties of alkoxylated-chalcone additive in enhancing the performance of CMC-based solid biopolymer electrolyte

Alkoxylated-chalcone having push-pull system has been integrated as additive in solid biopolymer electrolyte (SBE) based on carboxymethyl cellulose (CMC) doped with ammonium chloride (NH₄Cl). The structural, optical and thermal stability of the additive were characterized via FT-IR spectroscopy, UV–Vis, 1D NMR and TGA prior film casting as SBE. The optical band gaps (E_g^opt) of alkoxylated-chalcone additive exhibited low range, 3.14 eV which are comparable to that corresponding simulated findings, whereas they lie within the range of organic semiconductor materials. Frontier molecular orbitals (FMO) analysis, chemical reactivity and molecular electrostatic potential (MEP) revealed that the oxygen on alkoxy chain and –NO₂ substituent tuning the energy level of HOMO and LUMO. The investigation of their potential as additive in SBE system has been accomplished by incorporating CMC-NH₄Cl electrolyte using solution-casting method. A various weight ratio (0–8%) of additive was tested and doped with CMC-NH₄Cl as new SBE. The highest ionic conductivity achieved was 2.3 × 10^?2 Scm^?1 at ambient temperature (303K) for the system containing 8 wt.% of chalcone-based additive. The findings imply that the designated chalcone-based moiety has a potential to be employed as additive materials towards the performance enhancement for electrochemical the interests.     

Differential pulse effects of solid electrolyte interface formation for improving performance on high-power lithium ion battery

Solid electrolyte interface (SEI) formation is a key that utilizes to protect the structure of graphite anode and enhances the redox stability of lithium-ion batteries before entering the market. The effect of SEI formation applies a differential pulse (DP) and constant current (CC) charging on charge-discharge performance and cycling behavior into brand new commercial lithium ion batteries is investigated. The morphologies and electrochemical properties on the anode surface are also inspected by employing SEM and EDS. The electrochemical impedance spectra of the anode electrode in both charging protocols shows that the interfacial resistance on graphite anodes whose SEI layer formed by DP charging is smaller than that of CC charging. Moreover, the cycle life result shows that the DP charging SEI formation is more helpful in increasing the long-term stability and maintaining the capacity of batteries even under high power rate charge-discharge cycling. The DP charging method can provide a SEI layer with ameliorated properties to improve the performance of lithium ion batteries.     

Low energy ion beam assisted deposition of controllable solid state electrolyte LiPON with increased mechanical properties and ionic conductivity

Lithium phosphorus oxynitride (LiPON) solid state amorphous film electrolytes were synthesized by ion beam assisted deposition (IBAD) using Li₃PO₄ target under nitrogen reactive plasma. IBAD presents an advantage of controllable nitrogen content of the films by adjusting N₂ and Ar flow ratio. X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), nanoindenter, and profiler were employed to characterize LiPON films. Our results indicate that the film at N₂ and Ar flow ratio of 1:8 showed the best surface morphology and mechanical properties. The highest N atomic percentage of 2.32% was also obtained at this synthesis circumstance, and the resultant LiPON film electrolyte showed higher ionic conductivity of 4.5 × 10⁻⁶ S/cm at room temperature, as well as the highest hardness of 6.8 GPa and the lowest compressive stress of 147.2 MPa. It is believed that as-prepared LiPON solid state electrolyte film optimized can effectively prevent delamination from electrodes, showing some promising application in thin film lithium ion batteries.     

Effect of alumina additions on the anode|electrolyte interface in solid oxide fuel cells

The longevity of a solid oxide fuel cell (SOFC) stack is curtailed by the fragility of its ceramic components. At Ceramic Fuel Cells Limited (CFCL), 15 wt.% alumina is added to the commonly used 10 mol% Y₂O₃–ZrO₂ (YSZ) electrolyte to improve both the fracture toughness and grain-boundary conductivity of the electrolyte. This study investigates the effect of such addition of alumina on the anode|electrolyte interface; more specifically, which reactions occur with the Al₂O₃ at the interface and how these reactions influence fuel cell performance. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to characterize the formation of NiAl₂O₄ in the alumina regions in the electrolyte. The NiAl₂O₄ is observed to grow into the adjacent grain boundaries to form an interconnected NiAl₂O₄ network up to 4 μm deep into the electrolyte. Impedance spectroscopy shows that the formation of NiAl₂O₄ does not affect the grain bulk ionic conductivity. The grain-boundary conductivity is markedly reduced at low temperatures. However, at the high SOFC operating temperature at CFCL (850 °C) the contribution of the grain-boundary conductivity to the total conductivity is diminished, and the NiAl₂O₄ is found not to have an effect on the total electrolyte conductivity and is deemed not to be a detrimental reaction.     

A study on lithium/air secondary batteries—Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions

The stability of the high lithium ion conducting glass ceramics, Li_1+x+yTi_2−xAl_xSi_yP_3−yO₁₂ (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057 M LiOH aqueous solution at 50 °C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50 °C for 3 weeks was observed. The pH value of the LiCl-LiOH-H₂O solution with saturated LiCl was in a range of 7-9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12 and 11.57 M, respectively, by analysis of Li⁺ and OH⁻. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li⁺ and OH⁻ is too low in the solution with a high concentration of Li⁺. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH⁻ ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li + 1/2O₂ + H₂O → 2LiOH, and LTAP is stable under a deep discharge state.     

Effects of Lewis-acid polymer on the electrochemical properties of alkylphosphate-based non-flammable gel electrolyte

Non-flammable polymer gel electrolytes (NPGE) consisting of 1.0 mol dm⁻³ (=M) LiBF₄/EC + DEC + TEP (55:25:20 volume ratio) + PVdF-HFP (EC: ethylene carbonate, DEC: diethyl carbonate, TEP: triethylphosphate, PVdF-HFP: poly(vinyledenefluoride-co-hexafluoropropylene)) have been developed for rechargeable lithium batteries. The effects of addition of Lewis-acid polymer (LAP) with different mole ratio in NPGE have been studied. The addition of LAP improved physico-chemical properties of NPGE, viz ionic conductivity and lithium ion transport number, as well as mechanical and thermal properties. The ionic conductivity of the gel electrolyte containing LAP reached that of the base solution electrolyte (1.0 M LiBF₄/EC + DEC + TEP (55:25:20)) along with better mechanical properties. Interfacial resistance at Li-metal electrode/NPGE was also improved by introducing LAP in the gel.     

Effect of zwitterion on the lithium solid electrolyte interphase in ionic liquid electrolytes

An understanding of the solid electrolyte interphase (SEI) that forms on the lithium-metal surface is essential to the further development of rechargeable lithium-metal batteries. Currently, the formation of dendrites during cycling, which can lead to catastrophic failure of the cell, has mostly halted research on these power sources. The discovery of ionic liquids as electrolytes has rekindled the possibility of safe, rechargeable, lithium-metal batteries. The current limitation of ionic liquid electrolytes, however, is that when compared with conventional non-aqueous electrolytes the device rate capability is limited. Recently, we have shown that the addition of a zwitterion such as N-methyl-N-(butyl sulfonate) pyrrolidinium resulted in enhancement of the achievable current densities by 100%. It was also found that the resistance of the SEI layer in the presence of a zwitterion is 50% lower. In this study, a detailed chemical and electrochemical analysis of the SEI that forms in both the presence and absence of a zwitterion has been conducted. Clear differences in the chemical nature and also the thickness of the SEI are observed and these may account for the enhancement of operating current densities.     

Effect of Cu2O coating on graphite as anode material of lithium ion battery in PC-based electrolyte

Cuprous oxide-coated graphite was synthesized by a polyol reduction process and analyzed by scanning electron microscopy, charge–discharge measurements and cyclic voltammetry. Cu₂O exists at the surface of graphite in the form of nanoparticles and nanorods. The coated cuprous oxide layer acts as a protective layer separating graphite from the propylene carbonate (PC)-based electrolyte solution, and greatly suppresses PC decomposition and graphite exfoliation in PC-based electrolyte systems.     

Favorable combination of positive and negative electrode materials with glyme-Li salt complex electrolytes in lithium ion batteries

Tetraglyme (G4)-lithium bis(trifluoromethanesulfonyl)amide (TFSA) complexes with different G4 ratio were investigated. An increase in the amount of G4 led to the decrease in the viscosity, and increase in the ionic conductivity of the complex, and G4-LiTFSA showed higher thermal stabilities than the conventional organic electrolyte, when the molar ratio of G4 was more than 40 mol%. The increase in the G4 amount improved the rate capabilities of Li/LiCoO₂ cells in the range where the molar ratio of G4 was between 40 mol% and 60 mol%. The stable Li ion intercalation-deintercalation was not observed in the Li/graphite cell of [Li(G4)][TFSA] (G4: 50 mol%) without additives. However, the additives for forming solid electrolyte interface (SEI) film, such as vinylene carbonate, vinylethylene carbonate, and 1,3-propane sultone, led to the charge-discharge performance comparable to that of the conventional organic electrolyte. The adoption of Li₄Ti₅O₁₂ and LiFePO₄ led to excellent reversibilities of the Li half cells using [Li(G4)][TFSA], probably because of the favorable operation voltage. In the case of the LiFePO₄/Li₄Ti₅O₁₂ cell, the cell with [Li(G4)][TFSA] showed the better rate capability than that with the conventional organic electrolyte, when the rate was less than 1 CmA, and it is concluded that [Li(G4)][TFSA] can be the candidate as the alternative of organic electrolytes when the most appropriate electrode-active materials are used.     

Electrospun core-shell nanofibers based on polyethylene oxide reinforced by multiwalled carbon nanotube and silicon dioxide nanofillers: A novel and effective solvent-free electrolyte for lithium ion batteries

Insertion of conductive fillers into solvent-free polymer electrolytes enhances electrochemical behavior of the electrolyte membranes leading to higher ionic conductivity, lower capacity fading, and so on. Although, the presence of the conductive fillers in the polymer matrixes increases the risk of electrical shorting, herein, polyethylene oxide (PEO)-based core-shell nanofibers were prepared via a simple electrospinning method. In the core-shell electrospun fibers, ethylene carbonate (EC) and lithium perchlorate (LiClO₄) were used as a plasticizer and as a lithium salt, respectively. The core component was enwrapped by the PEO/EC/LiClO₄ shell part incorporated with SiO₂ nanoparticles. Various properties of the fabricated membranes were evaluated by changing the ratio of multiwall carbon nanotubes (MWCNTs) in the core part of the nanofibers. The morphology and core-shell structure of the electrospun fibers were studied by FESEM and TEM images. According to FTIR and XRD results, addition of the EC plasticizer and the fillers into the as-spun fibers increased the fraction of free ions and the amorphous regions. From electrochemical impedance spectroscopy studies, the ionic conductivity enhanced by insertion of the plasticizer molecules and the filler particles into the core-shell structures. The highest ionic conductivities of 0.09 and 0.21 mS.cm⁻¹ were obtained for the free-filler and the filler-loaded nanofibrous membranes, respectively. The prepared mats obeyed the Arrhenius behavior ( R²~1 ). Dielectric studies confirmed the obtained data from the ionic conductivities. Furthermore, the capacity residual was enhanced from 69% to 85% by incorporation of the MWCNTs filler into the core component of the electrospun nanofibers. The presented results may facilitate development of versatile nanofibrous membranes embedded with the conductive fillers as solvent-free electrolytes applicable in lithium-ion batteries.     

Effect of fabrication parameters on coating properties of tubular solid oxide fuel cell electrolyte prepared by vacuum slurry coating

The process of vacuum slurry coating for the fabrication of a dense and thin electrolyte film on a porous anode tube is investigated for application in solid oxide fuel cells. 8 mol% yttria stabilized zirconia is coated on an anode tube by vacuum slurry-coating process as a function of pre-sintering temperature of the anode tube, vacuum pressure, slurry concentration, number of coats, and immersion time. A dense electrolyte layer is formed on the anode tube after final sintering at 1400 °C. With decrease in the pre-sintering temperature of the anode tube, the grain size of the coated electrolyte layer increases and the number of surface pores in the coating layer decreases. This is attributed to a reduced difference in the respective shrinkage of the anode tube and the electrolyte layer. The thickness of the coated electrolyte layer increases with the content of solid powder in the slurry, the number of dip-coats, and the immersion time. Although vacuum pressure has no great influence on the electrolyte thickness, higher vacuum produces a denser coating layer, as confirmed by low gas permeability and a reduced number of defects in the coating layer. A single cell with the vacuum slurry coated electrolyte shows a good performance of 620 mW cm⁻² (0.7 V) at 750 °C. These experimental results indicate that the vacuum slurry-coating process is an effective method to fabricate a dense thin film on a porous anode support.     

Simultaneous improvement in ionic conductivity and mechanical properties of multi-functional block-copolymer modified solid polymer electrolytes for lithium ion batteries

Solid polymer electrolytes (SPEs) with high ionic conductivity and acceptable mechanical properties are of particular interest for increasing the performance of batteries. Our previous studies indicated that copolymers could be good candidates for SPE materials due to the variable properties contributed by each block. A series of copolymers applied in this research was poly(ethylene oxide)-block-polyethylene, PEO-b-PE, which contains a conductive block (PEO block) and a reinforcement block (PE block). This study examines the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs. The ternary SPEs were prepared by addition of copolymers into PEO/LiClO₄. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties. The SPEs that contained the highest percentage of PE block, 80 wt%, exhibits the best performances. The results showed an increase of more than two orders in ionic conductivity, about 350% increase in tensile modulus, and about 97% increase in ultimate tensile strength when the PE block increased from 50 wt% to 80 wt%. It was also observed that increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity.     

Influence of silica aerogel on the properties of polyethylene oxide-based nanocomposite polymer electrolytes for lithium battery

In this study, a series of nanocomposite polymer electrolytes (NCPEs) with high conductivity and lithium ion transference number, PEO/LiClO₄/SAP, were prepared from high molecular weight polyethylene oxide (PEO), LiClO₄ and low content of homemade silica aerogel powder (SAP), which had higher surface area and pore volume than the conventional silica particle. From the SEM images it was found that the SAP nanoparticles were well dispersed in the PEO polymer electrolyte matrix. The characterization and interactions in the CPEs were studied by DSC, XRD, FT-IR and ⁷Li NMR analysis. The ac impedance results showed that the ionic conductivity of the CPE was significantly improved by the addition of the as-prepared SAP. The maximum ambient ionic conductivity obtained from the CPE with EO/Li = 6 and 2 wt.% of SAP (O6A2) was about threefold higher than that of the corresponding polymer electrolyte without SAP (O6). In addition, the lithium ion transference number (t⁺) of O6A2 at 70 °C was as high as 0.67, which was also three times higher than that of O6 and has not been previously reported for the PEO–LiX-based polymer electrolytes.     

Effect of covalently bonded polysiloxane multilayers on the electrochemical behavior of graphite electrode in lithium ion batteries

Polysiloxane multilayers were covalently bonded to the surface of natural graphite particles via diazonium chemistry and silylation reaction. The as-prepared graphite exhibited excellent discharge–charge behavior as negative electrode materials in lithium ion batteries. The improvement in the electrochemical performance of the graphite electrodes was attributed to the formation of a stable and flexible passive film on their surfaces. It was also revealed that the chemical compositions of the multilayers exerted influence on the electrochemical behavior of the graphite electrodes. The result of this study presents a new strategy to the formation of elastic and strong passive film on the graphite electrode via molecular design. Owing to the diversity of polysilxoane multilayers, this method also enables researchers to control the surface chemistries of carbonaceous materials with flexibility.     

Electrochemical performance of all-solid-state lithium secondary batteries improved by the coating of Li2O-TiO2 films on LiCoO2 electrode

All-solid-state lithium secondary batteries using LiCoO₂ particles coated with amorphous Li₂O-TiO₂ films as an active material and Li₂S-P₂S₅ glass-ceramics as a solid electrolyte were fabricated; the electrochemical performance of the batteries was investigated. The interfacial resistance between LiCoO₂ and solid electrolyte was decreased by the coating of Li₂O-TiO₂ films on LiCoO₂ particles. The rate capability of the batteries using the LiCoO₂ coated with Li₂Ti₂O₅ (Li₂O·2TiO₂) film was improved because of the decrease of the interfacial resistance of the batteries. The cycle performance of the all-solid-state batteries under a high cutoff voltage of 4.6 V vs. Li was highly improved by using LiCoO₂ coated with Li₂Ti₂O₅ film. The oxide coatings are effective in suppressing the resistance increase between LiCoO₂ and the solid electrolyte during cycling. The battery with the LiCoO₂ coated with Li₂Ti₂O₅ film showed a large initial discharge capacity of 130 mAh/g and good capacity retention without resistance increase after 50 cycles at the current density of 0.13 mA/cm².     

High rate capabilities of all-solid-state lithium secondary batteries using Li4Ti5O12-coated LiNi0.8Co0.15Al0.05O2 and a sulfide-based solid electrolyte

Rate capability of LiNi_0.8Co_0.15Al_0.05O₂ in solid-state cells was investigated with 70Li₂S-30P₂S₅ glass-ceramics as a sulfide solid electrolyte. It showed higher rate capability than LiCoO₂; discharge capacity observed at a current density of 10 mA cm⁻² was ca. 70 mAh g⁻¹. Surface coating with Li₄Ti₅O₁₂ onto the LiNi_0.8Co_0.15Al_0.05O₂ particles further improved the high-rate performance to give ca. 110 mAh g⁻¹. The rate capability promises to realize all-solid-state lithium secondary batteries with very high performance.     

Effect of solvents in liquid electrolyte on the photovoltaic performance of dye-sensitized solar cells

The effect of solvents in liquid electrolyte on the photovoltaic performance of dye-sensitized solar cells was investigated. The solvents with large donor number enhanced the open-circuit voltage but reduced the short-circuit current density. By mixing 30 vol.% NMP with 70 vol.% GBL, the open-circuit voltage increased from 0.55 to 0.632 V and the fill factor increased from 0.607 to 0.613 while the short-circuit current density decreased little. The further addition of 0.4 M pyridine into the above mixed solvent caused a huge increase of overall conversion efficiency from 5.73 to 6.70% under irradiation of 100 mW cm⁻².     

High stability and superior rate capability of three-dimensional hierarchical SnS2 microspheres as anode material in lithium ion batteries

3D hierarchical SnS₂ microspheres have been designed and fabricated via a one-pot biomolecule-assisted hydrothermal method. When used as anode material in rechargeable Li-ion batteries, the as-formed SnS₂ microspheres self-assembled by layered nanosheets, show high lithium storage capacity, long-term cycling stability and superior rate capability. After charge-discharge for 100 cycles, the remaining discharge capacities are kept as high as 570.3, 486.2, and 264 mAh g⁻¹ at 1C (0.65 A g⁻¹), 5C, and 10C rate, respectively. Such outstanding performance of these SnS₂ microspheres is ascribed to their unique 3D hierarchical structures. The new charge-discharge mechanism of 3D SnS₂ microsphere as anode in Li-ion battery is further revealed.     

Electrochemical study of the formation of a solid electrolyte interface on graphite in a LiBC2O4F2-based electrolyte

The formation of a solid electrolyte interface (SEI) on the surface of graphite in a LiBC₂O₄F₂-based electrolyte was studied by galvanostatic cycling and electrochemical impedance spectroscopy (EIS). The results show that a short irreversible plateau at 1.5–1.7 V versus Li⁺/Li was inevitably present in the first cycle of graphite, which is attributed to the reduction of –OCOCOO⁻ pieces as a result of the chemical equilibrium of oxalatoborate ring-opening. This is the inherent property of LiBC₂O₄F₂ and it is independent of the type of electrode. EIS analyses suggest that the reduced products of LiBC₂O₄F₂ at 1.5–1.7 V participate into the formation of a preliminary SEI. Based on the distribution of the initial irreversible capacity and the correlation of the SEI resistance and graphite potential, it was concluded that the SEI formed at potentials below 0.25 V during which the lithiation takes place is most responsible for the long-term operation of the graphite electrode in Li-ion batteries. In addition, the results show that the charge-transfer resistance reflects well the kinetics of the electrode reactions, and that its value is in inverse proportion to the differential capacity of the electrode.