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.

Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts

Mixed salts of Ionic Liquids (ILs) and alkali metal salts, developed as electrolytes for lithium and sodium batteries, have shown a remarkable ability to facilitate high rate capability for lithium and sodium electrochemical cycling. It has been suggested that this may be due to a high alkali metal ion transference number at concentrations approaching 50 mol% Li(+) or Na(+), relative to lower concentrations. Computational investigations for two IL systems illustrate the formation of extended alkali-anion aggregates as the alkali metal ion concentration increases. This tends to favor the diffusion of alkali metal ions compared with other ionic species in electrolyte solutions; behavior that has recently been reported for Li(+) in a phosphonium ionic liquid, thus an increasing alkali transference number. The mechanism of alkali metal ion diffusion via this extended coordination environment present at high concentrations is explained and compared to the dynamics at lower concentrations. Heterogeneous alkali metal ion dynamics are also evident and, somewhat counter-intuitively, it appears that the faster ions are those that are generally found clustered with the anions. Furthermore these fast alkali metal ions appear to correlate with fastest ionic liquid solvent ions.

Ionic liquid electrolytes in mg-air batteries

 This study investigated ionic liquid electrolytes for Mg-air batteries and proposed a promising electrolyte material for this battery system. Mg-air batteries employing the proposed material has also shown its promise in energy storage applications.

Study of lithium conducting single ion conductor based on polystyrene sulfonate for lithium battery application

The effect of processing history and morphology is of particular importance for lithium-ion electrolytes for achieving higher ionic conductivities. In this study, single ion conducting poly (4-lithium styrene sulfonic acid) was synthesized by neutralization reaction from polystyrene sulfonic acid, and the effect of morphology and processing method was studied by comparing pelletized, electrospun and gel samples. The PSSLi gels displayed best ionic conductivity, while the pelletized samples showed the worst ionic conductivity. Although electrospinning led to a free standing electrolyte, the lower amount of solvent phase led to lower ionic conductivity when compared to the PSSLi gel. The ionic conductivity at room temperature improved from 6.6 × 10−5 S/cm to 1.4 × 10−3 S/cm by optimizing the processing methodology and the lithium ion concentration. The results show that PSSLi based single ion conducting lithium (SICL) gels are a promising candidate for lithium ion battery application.

Molecular dynamics study of a dual-cation ionomer electrolyte

The poly(N1222)xLi1-x[AMPS] ionomer system with dual cations has previously shown decoupled Li ion dynamics from polymer segmental motions, characterized by the glass transition temperature, which can result in a conductive electrolyte material whilst retaining an appropriate modulus (ie. stiffness) so that it can suppress dendrite formation, thereby improving safety when used in lithium metal batteries. To understand this ion dynamics behavior, molecular dynamics techniques have been used in this work to simulate structure and dynamics in these materials. These simulations confirm that the Li ion transport is decoupled from the polymer particularly at intermediate N1222+ concentrations. At 50 mol% N1222+ concentration the polymer backbone is more rigid than for higher N1222+ concentrations, but with increasing temperature Li ion transport is more significant than polymer or quaternary ammonium cation motions. Here we suggest an ion hopping mechanism for Li+, arising from structural rearrangement of ionic clusters that could explain its decoupled behavior. Higher temperatures favor an aggregated ionic structure as well as enhancing these hopping motions. The simulations discussed here provide an atomic-level understanding of ion dynamics that could contribute to designing an improved ionomer with fast ion transport and mechanical robustness.