Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Low pressure methane solubility in lithium-ion batteries based solvents and electrolytes as a function of temperature. Measurement and prediction

The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate,

Enhancement of ion dynamics in PMMA-based gels with addition of TiO2 nano-particles

Solvent and ion dynamics in PMMA based gels have been investigated as a function of the loading of nanosized TiO₂ particles. The gels have a molar ratio of 46.5:19:4.5:30 of ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate and PMMA, respectively. A series of samples with 0, 4, 6 and 8 wt.% TiO₂ filler were investigated. The diffusion coefficients for the lithium ions and for the two solvents (EC and PC) were investigated by pfg-NMR. It was shown that the addition of filler to the gel electrolytes enhances the diffusion of the cations, while the diffusion of the solvents remains constant. Raman measurements show no significant changes in ion–ion interactions with the addition of fillers, while the ionic conductivity is seen to decrease. However, the sample with 8 wt.% TiO₂ had a conductivity close to that of the unfilled sample.

7Li NMR measurements of polymer gel electrolytes

Ion conducting polymer gels prepared from (ethylene oxide)_n grafted methacrylates, ethylene carbonate (EC), gamma butyrolactone (gBL), and lithium hexafluorophosphate are studied by means of nuclear magnetic resonance spectroscopy. This study shows that there are at least two possible lithium sites with different mobility. The lithium-ions with lower mobility dominate at room temperature, but this is changed as the temperature is increased. The NMR results also show that the ⁷Li spin–spin relaxation time decreases with increasing length of the grafted ethylene oxide side chains, indicating a stronger interaction between the polymer and the Li-ions, and hence, a lower mobility of the Li-ions.

Transport properties of ionic liquid electrolytes with organic diluents

Ionic liquids (ILs) form a novel class of electrolytes with unique properties that make them attractive candidates for electrochemical devices. In the present study a range of electrolytes were prepared based on the IL N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]) and LiNTf2 salt. The traditional organic solvent diluents vinylene carbonate (VC), ethylene carbonate (EC), tetrahydrofuran (THF) and toluene were used as additives at two concentrations, 10 and 20 mol%, leading to a ratio of about 0.6 and 1.3 diluent molecules to lithium ions, respectively. Most promisingly, the lithium ions see the greatest effect in the presence of all the diluents, except toluene, producing a lithium self-diffusion coefficient of almost a factor of 2.5 times greater for THF at 20 mol%. Raman spectroscopy subtly indicates that THF may be effectively breaking up a small portion of the lithium ion–anion interaction. While comparing the measured molar conductivity to that calculated from the self-diffusion coefficients of the constituents indicates that the diluents cause an increase in the overall ion clustering. This study importantly highlights that selective ion transport enhancement is achievable in these materials.

Compositional effects on structure and transport properties in a polyelectrolyte gel

The copolymerization of lithium 2-acrylamido-2-methyl-1-propane sulfonate (LiAMPS) with N,N ′-dimethylacrylamide has yielded polyelectrolyte systems which can be gelled with an ethylene carbonate/N ′,N ′-dimethylacetamide solvent mixture and show high ionic conductivities. 7Li linewidth and relaxation times as well as 1H NMR diffusion coefficients have been used to investigate the effect of copolymer composition as well as copolymer concentration in the gel electrolyte with respect to ionic transport and polyelectrolyte structure. It appears that ion association is likely even in the case of low lithium salt concentration; however a rapid exchange exists between the associated and non-associated lithium species. Beyond 0.2 M of LiAMPS, both the conductivity and solvent diffusion reach a plateau, whilst lithium ion linewidth and spin-spin relaxation are suggestive, on average, of a less mobile species. The thermal analysis data is also supportive of this association effectively leading to a form of phase separation on the nanoscale, which gives a lower overall activity of lithium ions in the solvent rich regions beyond about 0.2 M of LiAMPS, thereby leading to an increase in the final liquidus temperature of the binary liquid solvent from –9 to +5°C.

Enhancement of ion dissociation in polyelectrolyte gels

High conductivity in single ion conducting polymer electrolytes is still the ultimate aim for many electrochemical devices such as secondary lithium batteries. Achieving effective ion dissociation in these cases remains a challenge since the active ion tends to remain in close proximity to the backbone charge as a result of a low degree of ion dissociation. A unique aspect of this dissociation problem in polyelectrolytes is the repulsion between the backbone charges created by dissociation. One way of enhancing ion dissociation in polyelectrolyte systems is to use copolymers in which only a fraction (<20%) of the mer units are charged and where the comonomer is itself chosen to be polar and preferably to be compatible with potential solvents. We have also found that certain dissociation enhancers based on ionic liquids or boroxine ring compounds can lead to high ionic conductivity. In the cases where an ionic liquid is used as the solvent in a polyelectrolyte gel, the viscosity of the ionic liquid and its hydrophilicity are critical to achieving high conductivity. Compounds based on the dicyanamide anion appear to be very effective ionic solvents; polyelectrolyte gels incorporating such ionic liquids exhibit conductivities as high as 10⁻² S/cm at room temperature. In the case of boroxine ring dissociation enhancers, gels based on poly(lithium-2-acrylamido-2-methyl-1-propanesulfonate) and ethylene carbonate produce conductivities approaching 10⁻³ S/cm. This paper will discuss these approaches for achieving higher conductivity in polyelectrolyte materials and suggest future directions to ensure single ion transport.

Gel electrolytes based on lithium modified silica nano-particles

In this work lithium modified silica (Li-SiO₂) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO₂ exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]). Several gel electrolytes based on Li-SiO₂ were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10⁻³ S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.

Boroxine ring compounds as dissociation enhancers in gel polyelectrolytes

In order to combine the advantages of both traditional gel electrolytes and polyelectrolytes, a novel polyelectrolyte which incorporates a boroxine ring-containing anion-trapping agent has been explored. Poly(lithium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPSLi), ethylene carbonate (EC) and tri(methoxyethoxyethoxyethoxy)boroxine (TME₃Bx) were combined to prepare various gel systems. The thermal properties and conductivities of these gels have been investigated. A conductivity of 10^−3.6 S cm⁻¹ at 20 °C has been achieved in a gel polyelectrolyte system with a molar ratio of [EC]:[TME3Bx]:[Li⁺]=24:1.7:1. Temperature-dependent NMR measurements indicated that a significant interaction exists between the boroxine ring and the polyelectrolyte.

The electrochemistry of lithium in ionic liquid/organic diluent mixtures

The electrochemistry of lithium is investigated in a number of electrolytes that consist of a lithium salt dissolved in a combined ionic liquid-organic diluent medium. We find that ethylene carbonate and vinylene carbonate improve electrochemical behaviour, while toluene and tetrahydrofuran are less promising.We also present insights into the electrode passivation caused by these diluents in an ionic liquid electrolyte during lithium cycling. We observe that during lithium cycling those electrolytes with carbonate based diluents are the most able to utilise their previously reported improved lithium ion diffusivities. Conversely, tetrahydrofuran, the most promising diluent of those studied in terms of its known ability to increase lithium ion diffusivity is found not to be as advantageous as a diluent. It appears that the poor electrochemical interfacial properties of the tetrahydrofuran electrolyte prevented the realisation of the benefits of the high solution lithium ion diffusivity.

Effect of flame-retarding additives on surface chemistry in Li-ion batteries

This study examined the properties of 1 wt.% vinylene carbonate, vinyl ethylene carbonate, and diphenyloctyl phosphate additive electrolytes as a promising way of beneficially improving the surface and cell resistance of Li-ion batteries. The additive electrolytes were dominant both in surface formation and internal resistance. In particular, electrochemical impedance spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that diphenyloctyl phosphate is an excellent additive to the electrolyte in the Li-ion batteries due to the improved co-intercalation of the solvent molecules.

Desenvolvimento de redes de polímeros interpenetrantes (IPN) para a aplicação como eletrólito polimérico

Uma nova rede de polímeros interpenetrantes (IPN) baseada em poliuretana de óleo de mamona e poli(etileno glicol) e poli(metacrilato de metila) foi preparada para ser utilizada como eletrólito polimérico. Os seguintes parâmetros de polimerização foram avaliados: massa molecular do poli(etileno glicol) (PEG), concentração de PEG e concentração de metacrilato de metila. As membranas de IPN foram caracterizadas por calorimetria diferencial de varredura (DSC) e espectroscopia de infravermelho por transformada de Fourier (FT-IR). Os eletrólitos de redes de polímeros interpenetrantes (IPNE) foram preparados a partir da dopagem com sal de lítio através do inchamento numa solução de 10% em massa de LiClO4 na mistura de carbonato de etileno e carbonato de propileno na razão mássica de 50:50. As IPNEs foram caracterizadas por espectroscopia de impedância eletroquímica e Raman. As IPNEs foram testadas como eletrólito polimérico em supercapacitores. As células capacitivas foram preparadas utilizando eletrodos de polipirrol (PPy). Os valores de capacitância e eficiência foram calculados por impedância eletroquímica, voltametria cíclica e ciclos galvonostáticos de carga e descarga. Os valores de capacitância obtidos foram em torno de 90 F.g-1 e eficiência variou no intervalo de 88 a 99%. Os valores de densidade de potência foram superiores a 250 W.kg-1 enquanto que a densidade de energia variou de 10 a 33 W.h.kg-1, dependendo da composição da IPNE. As características eletroquímicas do eletrólito formado pela IPN-LiClO4 (IPNE) foram comparadas aos eletrólitos poliméricos convencionais, tais como poli(difluoreto de vinilideno)-(hexafluorpropileno) ((PVDF-HFP/LiClO4) e poliuretana comercial (Bayer desmopan 385) (PU385/LiClO4). As condutividades na temperatura ambiente foram da ordem de 10-3 S.cm-1. A capacitância da célula utilizando eletrodos de PPy com eletrólito de PVDFHFP foi de 115 F.g-1 (30 mF.cm-2) e 110 F.g-1 (25 mF.cm-2) para a célula com PU385 comparadas a 90 F.g-1 (20 mF.cm-2) para a IPNE. Os capacitores preparados com eletrólito de IPNE apresentaram valores de capacitância inferior aos demais, entretanto provaram ser mais estáveis e mais resistentes aos ciclos de carga/descarga. A interpenetração de duas redes poliméricas, PU e PMMA produziu um eletrólito com boa estabilidade mecânica e elétrica. Um protótipo de supercapacitor de estado sólido foi produzindo utilizando eletrodos impressos de carbono ativado (PCE) e o eletrólito polimérico de IPNE. A técnica de impressão de carbono possui várias vantagens em relação aos outros métodos de manufatura de eletrodos de carbono, pois a área do eletrodo, espessura e composição são variáveis que podem ser controladas experimentalmente. As células apresentaram uma larga janela eletroquímica (4V) e valores da capacitância da ordem de 113 mF.cm-2 (16 F.g-1). Métodos alternativos de preparação do PCE investigados incluem o uso de IPNE como polímero de ligação ao carbono ativado, estes eletrodos apresentaram valores de capacitância similares aos produzidos com PVDF. A influência do número de camadas de carbono usadas na produção do PCE também foi alvo de estudo. Em relação ao eletrólito polimérico, o plastificante e o sal de lítio foram adicionados durante a síntese, formando a IPNGel. As células apresentaram alta capacitância e boa estabilidade após 4000 ciclos de carga e descarga. As membranas de IPN foram testadas também como reservatório de medicamento em sistemas de transporte transdérmico por iontoforese. Os filmes, mecanicamente estáveis, formaram géis quando inchado em soluções saturadas de lidocaina.HCl, anestésico local, em propileno glicol (PG), poli(etileno glicol) (PEG400) e suas misturas. O grau de inchamento em PG foi de 15% e 35% em PEG400. Agentes químicos de penetração foram utilizados para diminuir a resistência da barreira causada pela pele, dentre eles o próprio PG, a 2-pirrolidinona (E1) e a 1-dodecil-2-pirrolidinona (E2). Os géis foram caracterizados por espectroscopia de impedância eletroquímica e transporte passivo e por iontoforese através de uma membrana artificial (celofane). O sistema IPN/ lidocaina.HCl apresentou uma correlação linear entre medicamento liberado e a corrente aplicada. Os melhores resultados de transporte de medicamento foram obtidos utilizando o PG como solvente.

Structural and electrochemical properties of LiCoO2 prepared by combustion synthesis

LiCoO2 powders were prepared by combustion synthesis, using metallic nitrates as the oxidant and metal sources and urea as fuel. A small amount of the LiCoO2 phase was obtained directly from the combustion reaction, however, a heat treatment was necessary for the phase crystallization. The heat treatment was performed at the temperature range from 400 up to 700 degreesC for 12 h. The powders were characterized by X-ray diffraction (XRD), X ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and specific surface area values were obtained by BET isotherms. Composite electrodes were prepared using a mixture of LiCoO2, carbon black and poly(vinylidene fluoride) (PVDF) in the 85:10:5% w/w ratio. The electrochemical behavior of these composites was evaluated in ethylene carbonate/dimethylcarbonate solution, using lithium perchlorate as supporting electrolyte. Cyclic voltammograms showed one reversible redox process at 4.0/3.85 V and one irreversible redox process at 3.3 V for the LiCoO2 obtained after a post-heat treatment at 400 and 500 degreesC.Raman spectroscopy showed the possible presence of LiCoO2 with cubic structure for the material obtained at 400 and 500 degreesC. This result is in agreement with X-ray data with structural refinement for the LiCoO2 powders obtained at different temperatures using the Rietveld method. Data from this method showed the coexistence of cubic LiCoO2 (spinel) and rhombohedral (layered) structures when LiCoO2 was obtained at lower temperatures (400 and 500 degreesC). The single rhombohedral structure for LiCoO2 was obtained after post-heat treatment at 600 degreesC. The maximum energy capacity in the first discharge was 136 mA g(-1) for the composite electrode based on LiCoO2 obtained after heat treatment at 700 degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

L'utilizzo di carbonati come reagenti per la sintesi "green" di derivati fenolici: l'esempio del 2-fenossi-1-etanolo

2-Phenoxyethanol (ethylene glycol monophenyl ether) is used as solvent for cellulose acetate, dyes, inks, and resins; it is a synthetic intermediate in the production of plasticizers, pharmaceuticals, and fragrances. Phenoxyethanol is obtained industrially by reaction of phenol with ethylene oxide, in the presence of an homogeneous alkaline catalyst, typically sodium hydroxide. The yield is not higher than 95-96%, because of the formation of polyethoxylated compounds. However, the product obtained may not be acceptable for use in cosmetic preparations and fragrance formulations, due to presence of a pungent “metallic” odor which masks the pleasant odor of the ether, deriving from residual traces of the metallic catalyst. Here we report a study aimed at using ethylene carbonate in place of ethylene oxide as the reactant for phenoxyethanol synthesis; the use of carbonates as green nucleophilic reactants is an important issue in the context of a modern and sustainable chemical industry. Moreover, in the aim of developing a process which might adhere the principles of Green Chemistry, we avoided the use of solvents, and used heterogeneous basic catalysts. We carried out the reaction by using various molar ratios between phenol and ethylene carbonate, at temperatures ranging between 180 and 240°C, with a Na-mordenite catalyst. Under specific conditions, it was possible to obtain total phenol conversion with >99% yield to phenoxyethanol in few hours reaction time, using a moderate excess of ethylene carbonate. Similar results, but with longer reaction times, were obtained using a stoichiometric feed ratio of reactants. One important issue of the research was finding conditions under which the leaching of Na was avoided, and the catalyst could be separated and reused for several reaction batches.