Stability constraints in the design of galvanic cells using composite electrolytes and auxiliary electrodes

Recent trends in the use of dispersed solid electrolytes and auxiliary electrodes in galvanic cells have increased the need for assessment of materials compatibility. In the design of dispersed solid electrolytes, the potential reactions between the dispersoid and the matrix must be considered. In galvanic cells, possible interactions between the dispersoid and the electrode materials must also be considered in addition to ion exchange between the matrix and the electrode. When auxiliary electrodes, which convert the chemical potential of a component present at the electrode into an equivalent chemical potential of the neutral form of the migrating species in the solid electrolyte are employed, displacement reactions between phases in contact may limit the range of applicability of the cell. Examples of such constraints in the use of oxide dispersoids in fluoride solid electrolytes and NASICON/Na2S couple for measurement of sulphur potential are illustrated with the aid of Ellingham and stability field diagrams.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

Ceramic-polymer interface in composite electrolytes of lithium aluminium titanium phosphate and polyetherurethane polymer electrolyte

Composite electrolytes of the lithium-ion-conducting ceramic Li_1.3Al_0.3Ti_1.7(PO₄)₃ and polyetherurethane/lithium triflate polymer electrolyte have been prepared. Microscopy has shown that adhesion between the ceramic and polymer phases is poor, with gaps up to 1 μm at the interface. When dry, the composites are no more conductive than the pure polymer electrolyte. Exposing the samples to the vapour of solvents such as DMF, acetonitrile or water produces a significant increase in conductivity, over and beyond simple plasticization of the polymer. Pretreating the ceramic with a compatibilizing agent improves adhesion at the interface with the polymer, but decreases overall conductivity in the case investigated.

Thin and flexible solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes for device applications

All solid-state organic ionic plastic crystal–polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10’s lms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material.

Nafion-based composite electrolytes for proton exchange membrane fuel cells operating above 120C with titania nanoparticles and nanotubes as fillers

FAPESP:5150

Enhancement of ion dynamics in organic ionic plastic crystal/PVDF composite electrolytes prepared by co-electrospinning

Electrospun fibers are widely used in composite material design and fabrication due to their high aspect ratio, high surface area and favorable mechanical properties. In this report, novel organic ionic plastic crystal (OIPC) modified poly(vinylidene difluoride) (PVDF) composite fiber membranes were prepared by electrospinning. These composite materials are of interest for application as solid electrolytes in devices including lithium and sodium batteries. The influence of the OIPC, N-ethyl-N-methylpyrrolidinium tetrafluoroborate [C2mpyr][BF4], on the morphology and phase behavior of the composite fibers was investigated by scanning electron microscopy and Fourier transform infrared spectroscopy. Compared with pure electrospun PVDF fibers, which have an electroactive β phase and a small amount of non-polar α phase, the ion-dipole interaction between OIPC and the polymer in the co-electrospun composite system can reduce the non-polar α phase PVDF, resulting in almost entirely electroactive β phase PVDF. Differential scanning calorimetry shows that the ion-dipole interaction between the OIPC and PVDF can also interrupt the crystalline structure of the OIPC. Solid state NMR analysis also reveals different molecular dynamics of the [C2mpyr][BF4] in co-electrospun fibers compared with pure OIPC. Thus, electrospun [C2mpyr][BF4]/PVDF composite fibers that combine both increased ionic conductivity and almost pure β phase PVDF are demonstrated.

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a jelly-like consistency The composite ionic conductivity measured over the range -30 C to 60 C was always lower than that of the neat BMITFSI/BMIPF6 and LiTFSI-BMITFSI/LiTFSI-BMIPF6 electrolytes but still very high (>1 mS/cm at 25 degrees C up to 50 wt% PMMA) While addition of LiTFSI to IL does not influence the glass T-g and T-m melting temperature significantly dispersion of PMMA (especially at higher contents) resulted in increase in T-g and disappearance of T-m In general the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport However for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other Because of the beneficial physico-chemical properties and interesting ion transport mechanism we envisage the present soft matter electrolytes to be promising for application in electrochromic devices (C) 2010 Elsevier Ltd All rights reserved

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

A single ionic conductor based on Nafion and its electrochemical properties used as lithium polymer electrolyte

In an attempt to raise the transport number of Li+ to nearly unity in solid polymer electrolytes, commercial perfluorinated sulfonate acid membrane Nafion 117 was lithiated and codissolved with copolymer poly(vinylidene fluoride)hexafluoropropylene. The effect of fumed silica on the physical and electrochemical properties of the single ion conduction polymer electrolyte was studied with atom force microscopy, fourier transform infrared spectroscopy, differential scanning calorimetry, and electrochemical impedance spectroscopy. It was confirmed that the fumed silica has an obvious effect on the morphology of polymer electrolyte membranes and ionic conductivity. The resulting materials exhibit good film formation, solvent-maintaining capability, and dimensional stability. The lithium polymer electrolyte after gelling with a plasticizer shows a high ionic conductivity of 3.18 x 10(-4) S/cm.

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.

Conductivity in amorphous polyether nanocomposite materials

Using a completely amorphous polyether we have investigated the effect of the inclusion of a nano-particulate filler on a polymer electrolyte. Nano-sized TiO₂ is shown not to significantly affect the conductivity of composite electrolytes containing 1.0 or 1.25 mol/kg LiClO₄ or 1.5 or 2.0 mol/kg LiTFSI. At 1.5 mol/kg LiClO₄ a significant increase in conductivity is observed. Raman spectroscopy experiments have been used to investigate the effect of filler on ion-aggregation. Only one new vibrational mode can be assigned to the composite which is not due to the polymer electrolyte or the filler. From this work, we believe the increased conductivity observed by previous researchers as a result of filler addition may be largely attributed to the effect on the degree of crystallinity along with some disruption of ion-aggregation by the fillers in PEO based electrolytes.

Developing fast ion conductors from nanostructured polymers

- Introduction
- Polymer electrolytes
- Composite electrolytes
- Conclusions
- References

Lithium-ion conducting ceramic/polyether composites

Composites of a lithium ion conducting ceramic with a lithium salt based polymer electrolyte matrix are described. Conductivity measurements as a function of the lithium ion conducting ceramic phase content in the composite show that there is a significant increase in conductivity at approximately 40 vol% of the ceramic. The room temperature conductivity above this ceramic content is enhanced by at least 100% over that of the polymer electrolyte phase alone. It is believed that this additional contribution is substantially lithium ion conduction. The major barrier to ion-motion in these materials appears to be the interface between the polymer and ceramic. This interfacial resistance is strongly moisture-sensitive.

Polymer-ceramic ion-conducting composites

Composites of a Li⁺ ion-conducting ceramic powder in a polyether-based elastomeric electrolyte matrix are described. At 66 wt.% of ceramic the composite can be prepared as a paste and cured into a coherent material having useful elastic and tensile properties. The total conductivity of the composite was found to be (1.9 ± 0.2) × 10⁻⁴ S cm⁻¹ at 40 °C which was approximately 1 order of magnitude higher than the polymer electrolyte component alone. The result was also approximately 1 order of magnitude higher than the total conductivity of the ceramic powders tested in this work.

Effect of morphology and particle size on the ionic conductivities of composite solid electrolytes

A model incorporating the surface conductivity and morphology of the composite solid electrolytes is envisaged to explain their conduction behaviour. The conductivity data on LinX−50 m/o Al2O3 (X = F−, Cl−, Br−, CO32−, SO42−, PO43−) composites prepared by thermal decomposition of LinX·2nAl(OH)3·mH2O salts and Li2SO4−A (A=Al2O3, CeO2, Y2O3, Yb2O3, Zr2O3, ZrO2 and BaTiO3) composites prepared by mechanical mixing of the components are examined in the light of this model. It is surmised that the particle size of both the dispersoids and the hosts not only influence the ionic conductivity of the host matrix but also affect its bulk properties.