Search results for "electrolyte"

Synthetic approaches to new polymers

1990

A plenary lecture should be an introduction into the main topic of the symposium and a review about the state of art. Therefore, in the first part of this presentation different possibilities for the preparation of new polymers are briefly discussed from a chemical point of view. Some selected examples from the literature show how methods of organic chemistry can be utilized for polymer science: new catalytic systems, new monomers, modification of polymers, new poly-reactions. In the second part, several polyelectrolytes are described: polymers with sec., tert. and quart. N-atoms in the main chain, block copolymers and block polyampholytes. The third part deals with the problems of rod-like…

Proton Conducting Membrane Prepared by Cross-Linking Highly Sulfonated Peek for PEMFC Application

2009

The proton conducting membrane was prepared by cross-linking highly sulfonated and sulfinated poly(etheretherketone) (SsPEEK). The cross-linked membrane is low cost due to its use of non-expensive chemical and simple production procedure. The membrane exhibited high proton conductivity (0.04 S/cm at 60 °C), extremely reduced water uptake, enhanced strength and stability compared with that of non-cross-linked membrane. These results suggested that the cross-linked PEEK membrane is a suitable candidate of proton conducting membranes for polymer electrolyte membrane fuel cell (PEMFC) applications, particularly promising to be used in direct methanol fuel cell (DMFC) due to its lower methanol c…

Competitive Adsorption of Functionalized Polymers

1996

The adsorption and desorption of functionalized polystyrene-block-polybutadiene diblock copolymers from dilute solutions in toluene onto silicon wafers are investigated by means of null ellipsometry. The short polybutadiene block is functionalized by a reaction with 4-(3,5-dioxo-1,2,4-triazolidin-4-yl)benzoic acid. On the average there are six functional groups per chain. The polystyrene block does not adsorb on the surface. The adsorption depends on the length of the polystyrene block, and chains with short polystyrene blocks yield higher surface coverage than larger ones. When short and long chains are put together, the short chains displace the long ones in equilibrium conditions nearly …

Investigation on lithium/polymer electrolyte interface for high performance lithium rechargeable batteries

1997

Abstract Performance data of several linear and cross-linked polymer electrolytes are reported and the electrochemical criteria for the selection of electrolytes to be used in electric vehicle lithium metal batteries are discussed. Further, laboratory lithium cells with LiMn2O4 composite cathode were tested to ascertain the effective viability of these polymer in solid-state batteries and preliminary results are reported. This study clearly demonstrates the importance of a broad-based electrochemical characterization in selecting an electrolyte for lithium metal batteries.

2021

Water-in-salt systems, i.e., super-concentrated aqueous electrolytes, such as lithium bis(trifluoromethanesulfonyl)imide (21 mol/kgwater), have been recently discovered to exhibit unexpectedly large electrochemical windows and high lithium transference numbers, thus paving the way to safe and sustainable charge storage devices. The peculiar transport features in these electrolytes are influenced by their intrinsically nanoseparated morphology, stemming from the anion hydrophobic nature and manifesting as nanosegregation between anions and water domains. The underlying mechanism behind this structure-dynamics correlation is, however, still a matter of strong debate. Here, we enhance the apol…

Polyelectrolytes in dilute solution: viscometric access to coil dimensions and salt effects

2015

Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC), differing in molar masses M (52.3 to 227 kDa) and degrees of charging y (0.2 to 0.6), were studied with respect to their viscometric behavior in dilute aqueous solutions containing variable amounts of NaCl. Complementary measurements were performed on a Brookhaven 90 plus particle size analyzer. M dominates the intrinsic viscosities [η]. For the viscometric interaction parameters B this is only true for large concentrations of extra salt. [η] and B as a function of solvent salinity follow Boltzmann laws. Coil dimensions, determined either via dynamic light scattering or viscometry, agree well. For low salt contents…

Intrinsic Viscosities of Polymer Blends: Sensitive Probes of Specific Interactions between the Counterions of Polyelectrolytes and Uncharged Macromol…

2018

In joint dilute aqueous solutions of pullulan (PUL) and poly(sodium 4-styrenesulfonate) (PSS-Na) the Na+ ions of the polyelectrolyte interact so favorably with the monomeric units of PUL that isolated coils containing both types of macromolecules are formed upon dilution. When water is replaced against a 1 M solution of NaCl, this effect dies out because of the large surplus of Na+ ions. On the other hand, if the water contains increasing amounts of the respective counterpolymer instead of NaCl, the formation of mixed isolated coils is fostered, where a further diminution of the intrinsic viscosities is caused by the lower the solvent quality. The molar mass of PSS-Na plays an important rol…

Viscometry of polyelectrolyte solutions: Star-like versus linear poly[[2-(methacryloyloxy)ethyl] trimethylammonium iodide] and specific salt effects

2017

Abstract The intrinsic viscosities, [η], of the 3-arm star polyelectrolyte in pure water are for a given molar mass considerably lower than for the linear product because of the higher monomer concentration and charge density in isolated coils. These effects are much more pronounced than in the case of uncharged macromolecules. Extra salt (NaCl, NaI, CaCl2) reduces the solution viscosities of the 3-arm star polymer less than of the linear product. The transition of [η] from the value in pure water to the minimum saturation value at high salt concentrations follows a Boltzmann sigmoid. In saline solvents the changes of the viscosities with rising polymer concentration depend strongly on the …

Estimation of pKa shifts in weak polyacids using a simple molecular model: effects of strong polybases, hydrogen bonding and divalent counterion bind…

2004

Abstract The pKa values of ionizable groups in macromolecules can be significantly different than those of the isolated groups in solution. We have estimated theoretically the changes in the dissociation constant of a weak acid (a) in the vicinity of another ionizable group (b) on the basis of the theoretical approach by Hill (J. Am. Chem. Soc. 78 (1956) 3330) for matching pairs of interacting sites on two large molecules. Three cases are considered for group b: the strong base, the same weak acid as group a with hydrogen bonding between them, and the same weak acid as group a with divalent counterion binding. The pKa shifts are evaluated in each case as a function of the interaction energy…

Surface charge regulation of functionalized conical nanopore conductance by divalent cations and anions

2019

Abstract The surface charge regulation in nanoscale volumes is a subject of wide interest to biological and chemical soft matter systems. Also, electrolyte mixtures with monovalent and divalent ions are commonplace in practical applications with micro and nanoporous ion-exchange membranes. We have studied experimentally and theoretically the conductance of conical nanopores functionalized with negative and positive surface charges that are bathed by electrolyte mixtures of the monovalent ions K+ and Cl− and the divalent ions Mg2+, Ba2+, Ca2+, and SO42−. Small concentrations of these ions can modulate the nanopore selectivity and conductance because of their interaction with the charged grou…