Solvation of AgTFSI in 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid investigated by vibrational spectroscopy and DFT calculations

In this paper we investigate the solvation of silver bis(trifluoromethylsulfonyl)imide salt (AgTFSI) in 1‐ethyl‐3‐methylimidazolium TFSI [EMI][TFSI] ionic liquid by combining Raman and infrared (IR) spectroscopies with density functional theory (DFT) calculations. The IR and Raman spectra were measured in the 200–4000 cm⁻¹ spectral region for AgTFSI/[EMI][TFSI] solutions with different concentrations ([AgTFSI] <0.2 mole fraction). The analysis of the spectra shows that the spectral features observed by dissolution of AgTFSI in [EMI][TFSI] solution originate from interactions between the Ag⁺ cation and the first neighboring TFSI anions to form relatively stable Ag complexes. The ‘gas phase’ interaction energy of a type [Ag(TFSI)₃]²⁻ complex was evaluated by DFT calculations and compared with other interionic interaction energy contributions. The predicted spectral signatures because of the [Ag(TFSI)₃]²⁻ complex were assessed in order to interpret the main IR and Raman spectral features observed. The formation of such complexes leads to the appearance of new interaction‐induced bands situated at 753 cm⁻¹ in Raman and at 1015 and 1371 cm⁻¹ in IR, respectively. These specific spectral signatures are associated with the ‘breathing’ mode and the S–N–S and S–O stretching modes of the TFSI anions engaged in the complex. Finally, all these findings are discussed in terms of interaction mechanisms enabling the electrodeposition characteristics of silver from AgTFSI/[EMI][TFSI] IL‐based electrolytic solutions. Copyright © 2015 John Wiley & Sons, Ltd.     

Lithium solvation and diffusion in the 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid

The Raman spectra of (1 − x)(BMITFSI), xLiTFSI ionic liquids, where 1‐butyl‐3‐methylimidazolium cation (BMI⁺) and bis(trifluoromethane‐sulfonyl)imide anion (TFSI⁻) are analyzed for LiTFSI mole fractions x < 0.4. As expected from previous studies on similar TFSI‐based systems, most lithium ions are shown to be coordinated within [Li(TFSI)₂]⁻ anionic clusters. The variation of the self‐diffusion coefficients of the ¹H, ¹⁹F, and ⁷Li nuclei, measured by pulsed‐gradient spin‐echo NMR (PGSE‐NMR) as a function of x, can be rationalized in terms of the weighted contribution of BMI⁺ cations, TFSI⁻ ‘free’ anions, and [Li(TFSI)₂]⁻ anionic clusters. This implies a negative transference number for lithium. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray Raman spectroscopy of lithium‐ion battery electrolyte solutions in a flow cell

The effects of varying LiPF₆ salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium‐ion battery electrolyte solvents (ethylene carbonate–dimethyl carbonate and propylene carbonate) have been investigated. X‐ray Raman scattering spectroscopy (a non‐resonant inelastic X‐ray scattering method) was utilized together with a closed‐circle flow cell. Carbon and oxygen K‐edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li⁺ ion concentration in the solvent manifests itself as a blue‐shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K‐edge results agree with previous soft X‐ray absorption studies on LiBF₄ salt concentration in propylene carbonate, carbon K‐edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.     

Lithium solvation in a PMMA membrane plasticized by a lithium‐conducting ionic liquid based on 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide

The Raman and Infrared (IR) spectra of poly(methyl methacrylate) (PMMA) membranes plasticized by ionic liquids of the (1 − x)[1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)],xLiTFSI type, where BMI⁺ is the 1‐butyl‐3‐methylimidazolium cation and TFSI⁻ the bis(trifluoromethanesulfonyl)imide anion, are analyzed for a lithium bis(trifluoromethane sulfone)imide (LiTFSI) mole fraction x = 0.23 and PMMA contents from 0 to 50 wt%. The lithium is found to have an average coordination of about three CO groups and less than one TFSI⁻ anion. It plays the role of a cross‐linker between the ester groups of PMMA and the nonvolatile ionic liquid. Addition of PMMA to the (1 − x)(BMITFSI),xLiTFSI ionic liquid lowers the conductivity but might improve the lithium transference number by transforming the [Li(TFSI)₂]⁻ anionic clusters present in the pure ionic liquid into a mixed coordination by ester groups and TFSI⁻ anions. Copyright © 2008 John Wiley & Sons, Ltd.     

一种新型锂离子电池聚合物电解质的光谱学研究

本文主要利用Raman光谱对由丙烯碳酸酯(PC)/聚丙烯腈(PAN)/双三氟甲基碘酸酰亚胺锂(LiTFSI)组成的锂离子电池聚合物电解质进行了研究,通过研究发现:Li+离子与PC的缔合和PC对TFSI-阴离子结构的影响导致了Li+-PC-TFSI-离子团的生成。而在所有的PC分子和盐发生缔合之前,PAN却不能溶到PC中。一旦PAN开始溶于PC,电解质内与PC相关的微观结构将不再随盐的浓度的增加而改变。但Li+离子与PAN之间的作用却显得异常激烈。     

Cerussite,PbCO3 – a new Stimulated Raman Scattering (SRS)‐active crystal with high‐order Stokes and anti‐Stokes lasing

Orthorhombic PbCO₃, known as natural crystal cerussite, is presented as a new Stimulated Raman Scattering (SRS)‐active crystal. With picosecond laser pumping high‐order Raman‐induced χ⁽³⁾ generation is observed. All registered Stokes and anti‐Stokes sidebands in the visible and near‐IR are identified and attributed to the SRS‐promoting phonon mode A_1g of the carbonate group, with ω_SRS ≈ 1054 cm⁻¹. The first Stokes steady‐state Raman gain coefficient in the visible spectral range is estimated as well to a value not less than 4.6 cm·GW⁻¹.     

CH3NH3PbI3/poly‐3‐hexylthiophen perovskite mesoscopic solar cells: Performance enhancement by Li‐assisted hole conduction

To address if the non‐triphenylamine derivative hole transporting materials such as P3HT (poly‐3‐hexylthiophene) could also exhibit high device efficiency in mesoscopic MAPbI₃ perovskite solar cells, we examined the effect of Li‐TFSI (Li‐bis(trifluoromethanesulfonyl) imide) and t‐BP (4‐tert‐butylpyridine) additives added in P3HT on device performance. Unlike the triphenylamine HTMs, the P3HT thiophene HTM without amine moiety was not doped by the additives but its conductivity was significantly improved by the Li‐TFSI/t‐BP mediated additional hole conduction. By inclusion of Li‐TFSI/t‐BP additive, we could fabricate more efficient mesoscopic MAPbI₃ perovskite solar cells with smaller hysteresis with respect to scan direction due to Li mediated additional hole conduction. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

离子液体凝胶聚合物电解质PP13TFSI-LiTFSI-P(VdF-HFP)的电化学性能 (cited: 1)

采用溶液浇铸法将N-甲基-N-丙基哌啶二(三氟甲基磺)亚胺(PP13TFSI)、二(三氟甲基磺)亚胺锂与偏氟乙烯-六氟丙烯共聚物(P(VdF-HFP))混合制备离子液体凝胶聚合物电解质(ILGPEs). 通过扫描电子显微镜观察发现,这种离子液体凝胶聚合物电解质由于液体相的均匀分布而具有疏松的结构. 采用电化学阻抗、计时电流法、线性扫描伏安法测试了电解质的离子电导率、锂离子迁移数和电化学窗口. 室温下离子液体凝胶聚合物电解质的离子电导率和锂离子迁移数分别是0.79 mS/cm和0.71,电化学窗口为0～5.1 Vvs. Li⁺/Li. 电池性能测试表明,这种离子液体凝胶聚合物电解质在Li/LiFePO₄电池中是稳定的,放电容量在30、75和150mA/g倍率下分别为135、117和100 mAh/g,电池经100个循环后容量保持在100%而几乎没有衰减.     

Synthesis and Raman spectroscopic characterisation of hydrotalcite with CO32− and VO3− anions in the interlayer

Infrared and Raman spectroscopy were used to characterise synthetic mixed carbonate and vanadate hydrotalcites of formula Mg₆Al₂(OH)₁₆(CO₃)²⁻, (VO₄)³⁻·4H₂ O. The spectra were used to assess the molecular assembly of the cations and anions in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features based on (1) the carbonate anion (2) the hydroxyl units and (3) water units. Bands were assigned to the hydroxyl stretching vibrations of water. Three types of carbonate anions were identified: (1) carbonate hydrogen‐bonded to water in the interlayer, (2) carbonate hydrogen‐bonded to the hydrotalcite hydroxyl surface and (3) free carbonate anions. It is proposed that the water is highly structured in the hydrotalcite, as it is hydrogen‐bonded to both the carbonate and the hydroxyl surface. The spectra were used to assess the contamination of carbonate in an open reacting vessel in the synthesis of vanadate hydrotalcites of formula Mg₆Al₂(OH)₁₆(CO₃)²⁻, (VO₄)³⁻·4H₂ O. Bands have been assigned to vanadate anions in the infrared and Raman spectra associated with V O bonds. Copyright © 2007 John Wiley & Sons, Ltd.     

A novel and shortcut method to prepare ionic liquid gel polymer electrolyte membranes for lithium-ion battery

The ionic liquid polymer electrolyte (IL-PE) membrane is prepared by ultraviolet (UV) cross-linking technology with polyurethane acrylate (PUA), methyl methacrylate (MMA), ionic liquid (Py₁₃TFSI), lithium salt (LiTFSI), ethylene glycol dimethacrylate (EGDMA), and benzoyl peroxide (BPO). N-methyl-N-propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py₁₃TFSI) ionic liquid is synthesized by mixing N-methyl-N-propyl pyrrolidinium bromide (Py₁₃Br) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The addition of Py₁₃TFSI to polymer electrolyte membranes leads to network structures by the chain cross-linking. The resultant electrolyte membranes display the room temperature ionic conductivity of 1.37 × 10^?3 S cm^?1 and the lithium ions transference number of 0.22. The electrochemical stability window of IL-PE is about 4.8 V (vs. Li⁺/Li), indicating sufficient electrochemical stability. The interfacial resistances between the IL-PE and the electrodes have the less change after 10 cycles than before 10 cycles. IL-PE has better compatibility with the LiFePO₄ electrode and the Li electrode after 10 cycles. The first discharge performance of Li/IL-PE/LiFePO₄ half-cell shows a capacity of 151.9 mAh g^?1 and coulombic efficiency of 87.9%. The discharge capacity is 131.9 mAh g^?1 with 95.5% coulombic efficiency after 80 cycles. Therefore, the battery using the IL-PE exhibits a good cycle and rate performance.     

A piperidinium-based ester-functionalized ionic liquid as electrolytes in Li/LiFePO<Subscript>4</Subscript> batteries

A new functionalized ionic liquid (IL) based on cyclic quaternary ammonium cations with ester group and bis(trifluoromethanesulfonyl)imide ([TFSI]^?) anion, namely, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized and characterized. Physical and electrochemical properties, including Li-ion transference number, ionic conductivity, and electrochemical stability, were investigated. The electrochemical window of [MMOCPip][TFSI] was 6 V, which was wide enough to be used as a common electrolyte material. The Li-ion transference number of this IL electrolyte containing 0.1 M LiTFSI was 0.56. The half-cell tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of a Li/LiFePO₄ cell. For the Li/LiFePO₄ half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh g^?1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte for lithium-ion batteries.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

Laser‐induced phase changes in olivine FePO4: a warning on characterizing LiFePO4‐based cathodes with Raman spectroscopy

Raman spectroscopy is an excellent technique for probing lithium intercalation reactions of many diverse lithium ion battery electrode materials. The technique is especially useful for probing LiFePO₄‐based cathodes because the intramolecular vibrational modes of the PO₄³⁻ anions yield intense bands in the Raman spectrum, which are sensitive to the presence of Li⁺ ions. However, the high power lasers typically used in Raman spectroscopy can induce phase transitions in solid‐state materials. These phase transitions may appear as changes in the spectroscopic data and could lead to erroneous conclusions concerning the delithiation mechanism of LiFePO₄. Therefore, we examine the effect of exposing olivine FePO₄ to a range of power settings of a 532‐nm laser. Laser power settings higher than 1.3 W/mm² are sufficient to destroy the FePO₄ crystal structure and result in the formation of disordered FePO₄. After the laser is turned off, the amorphous FePO₄ compound crystallizes in the electrochemically inactive α‐FePO₄ phase. The present experimental results strongly suggest that the power setting of the excitation laser should be carefully controlled when using Raman spectroscopy to characterize fundamental lithium ion intercalation processes of olivine materials. In addition, Raman spectra of the amorphous intermediate might provide insight into the α‐FePO₄ to olivine FePO₄ phase transition that is known to occur at temperatures higher than 450 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the magnesium‐carbonate minerals—artinite and dypingite

Magnesium minerals are important in the understanding of the concept of geosequestration. The two hydrated hydroxy magnesium‐carbonate minerals artinite and dypingite were studied by Raman spectroscopy. Intense bands are observed at 1092 cm⁻¹ for artinite and at 1120 cm⁻¹ for dypingite, attributed ν₁ symmetric stretching mode of CO₃²⁻. The ν₃ antisymmetric stretching vibrations of CO₃²⁻ are extremely weak and are observed at 1412 and 1465 cm⁻¹ for artinite and at 1366, 1447 and 1524 cm⁻¹ for dypingite. Very weak Raman bands at 790 cm⁻¹ for artinite and 800 cm⁻¹ for dypingite are assigned to the CO₃²⁻ν₂ out‐of‐plane bend. The Raman band at 700 cm⁻¹ of artinite and at 725 and 760 cm⁻¹ of dypingite are ascribed to CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum of artinite in the OH stretching region is characterised by two sets of bands: (1) an intense band at 3593 cm⁻¹ assigned to the MgOH stretching vibrations and (2) the broad profile of overlapping bands at 3030 and 3229 cm⁻¹ attributed to water stretching vibrations. X‐ray diffraction studies show that the minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality, and explains why the Raman spectra of these minerals have not been previously or sufficiently described. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Raman spectroscopic characterisation of hydrotalcite with CO32− and (MoO4)2− anions in the interlayer

Raman spectroscopy has been used to characterise synthetic mixed carbonate and molybdate hydrotalcites of formula Mg₆Al₂(OH)₁₆((CO₃)²⁻,(MoO₄)²⁻)·4H₂O. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features on the basis of the carbonate anion, the molybdate anion, the hydroxyl units and water units. Bands are assigned to the hydroxyl stretching vibrations of water. Three types of carbonate anions are identified: (1) carbonate hydrogen‐bonded to water in the interlayer, (2) carbonate hydrogen‐bonded to the hydrotalcite hydroxyl surface, (3) free carbonate anions. It is proposed that the water is highly structured in the hydrotalcite, as it is hydrogen bonded to both the carbonate and the hydroxyl surface. The spectra have been used to assess the contamination of carbonate in an open reaction vessel in the synthesis of a molybdate hydrotalcite of formula Mg₆Al₂(OH)₁₆((CO₃)²⁻, (MoO₄)²⁻)·4H₂O. Bands are assigned to carbonate and molybdate anions in the Raman spectra. Importantly, the synthesis of hydrotalcites from solutions containing molybdate provides a mechanism for the removal of this oxy‐anion. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopy of gallium‐ and zinc‐based hydrotalcites

Insight into the unique structure of hydrotalcites (HTs) has been obtained using Raman spectroscopy. Gallium‐containing HTs of formula Zn₄ Ga₂(CO₃)(OH)₁₂ · xH₂O (2:1 ZnGa‐HT), Zn₆ Ga₂(CO₃)(OH)₁₆ · xH₂O (3:1 ZnGa‐HT) and Zn₈ Ga₂(CO₃)(OH)₁₈ · xH₂O (4:1 ZnGa‐HT) have been successfully synthesised and characterised by X‐ray diffraction (XRD) and Raman spectroscopy. The d(003) spacing varies from 7.62 Å for the 2:1 ZnGa‐HT to 7.64 Å for the 3:1 ZnGa‐HT. The 4:1 ZnGa‐HT showed a decrease in the d(003) spacing, compared to the 2:1 and 3:1 compounds. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised gallium‐containing HTs. Raman bands observed at around 1050, 1060 and 1067 cm⁻¹ are attributed to the symmetric stretching modes of the (CO₃²⁻) units. Multiple ν₃ (CO₃²⁻) antisymmetric stretching modes are found between 1350 and 1520 cm⁻¹, confirming multiple carbonate species in the HT structure. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands observed at 710 and 717 cm⁻¹ and assigned to the ν₄ (CO₃²⁻) modes support the concept of multiple carbonate species in the interlayer. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of novel benzotriazole based zwitterionic salt as electrolyte additive for lithium ion batteries

A novel zwitterionic lithium-benzotriazole sulfobetaine is fabricated by grafting 1,3– propanesultone onto benzotriazole and then lithiating it. The resultant lithium-benzotriazole-sulfobetaine additive is used as an electrolyte additive in lithium ion batteries in 1 M LiPF₆ (ethylene carbonate/dimethyl carbonate = 1:1). The electrolytes with the lithium-benzotriazole sulfobetaine shows higher ionic conductivities (2.18 $\times$ 10⁻² S cm⁻¹) compared to the bare electrolyte (1.07 $\times$ 10⁻² S cm⁻¹) and greater electrochemical stability (anodic limit at ~5.5 V vs. Li/Li⁺) than the pure electrolyte (anodic limit at ~4.6 V vs. Li/Li⁺). The discharge capacity of the lithium cobalt oxide/graphite cells is improved at higher C-rates with the addition of lithium-benzotriazole sulfobetaine due to increased ionic conductivity. The lithium cobalt oxide/graphite cells with the lithium-benzotriazole sulfobetaine additive also show stable cycling performance. These findings warrant the use of lithium-benzotriazole sulfobetaine as an electrolyte additive in lithium ion batteries.     

Evolution of excess electron binding motifs under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects in endohedral metallofullerenes with endo C–F bonds

How does the endo C–F bond influence the excess electron binding motif? For lithium‐doped endohedral perfluorofullerenes with endo C–F bonds, under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects, the singly occupied molecular orbital electron cloud of the sphere‐like Li···F₈@C₆₀F₅₂ (D₂) is partially dispersed within the σ_p–s antibonding orbital of endo C–F bonds and the space between C^δ+–F_endo^δ– double electric layers, which makes Li···F₈@C₆₀F₅₂ have partial excess electron (electride characteristics) and partial lithium salt characteristics, while in the tube‐like Li···F₂@C₆₀F₅₈ (C_s), as the Li is changing from approaching F to keeping away from F and to approaching another one, the singly occupied molecular orbital electron cloud is mainly dispersed from within the p orbital of the short endo C–F bond to within the middle of the two F atoms and again to within the p orbital of the short endo C–F bond, which indicates an evolution from lithium salt characteristic to excess electron characteristic, and again to lithium salt characteristic. Copyright © 2012 John Wiley & Sons, Ltd.     

Carbon‐Coated Supraballs of Randomly Packed LiFePO4 Nanoplates for High Rate and Stable Cycling of Li‐Ion Batteries

One of the key strategies used to obtain high‐rate Li‐ion battery is the reduction of the Li‐ion path length inside the active materials and the enhancement of the ionic diffusion outside the active materials. It is demonstrated that electrochemical performance can be improved significantly at high C‐rates using carbon‐coated spherical aggregates or “supraballs” of randomly packed olivine LiFePO₄ (LFP) nanoplates as cathode active materials. 258 nm LFP nanoplates with 30 nm thickness are synthesized through a high‐temperature solvothermal method, in which short lithium‐ion channels are formed perpendicular to the top or bottom planes. These thin nanoplates are formed into carbon‐coated “supraballs” through a spray‐drying and thermal annealing process, in which nanoplates are not stacked but randomly packed due to relatively fast drying. Internal and external nanoplate ion diffusion is therefore enhanced simultaneously due to the optimal molecular crystalline structure and interparticle pore structures of the nanoplates. Indeed, the initial capacity of the carbon‐coated supraballs is 162 mAh g^?1 (173.34 mAh cm^?3) at 0.1 C and more than 80% is retained (≈130.91 mAh g^?1) at 50 C. Furthermore, they offer durable cycling stability (>500 cycles) at 1 C without compromising their capacity.     

Dissociation of C6F5SO3Li in two organic solvents with different dielectric constants: a Raman spectroscopic study

Organic solutions of lithium pentafluorobenzene sulfonate (C₆F₅SO₃Li) with varying molalities in N,N‐dimethyl formamide (DMF) and triethyleneglycol dimethylether (triglyme) were investigated by Raman spectroscopy. Spectral decomposition in the ν_s(SO₃) stretching region showed bands characteristic of free anions, ion pairs and various aggregates. The relative fraction of each species has been followed as a function of salt molality. In DMF, free anions dominate, while in triglyme ion pairs dominate, in accordance with the solvent dielectric constant. Copyright © 2007 John Wiley & Sons, Ltd.