Mesoporous Films and Polymer Brushes Helping Each Other To Modulate Ionic Transport in Nanoconfined Environments. An Interesting Example of Synergism in Functional Hybrid Assemblies

2009 ◽  
Vol 131 (31) ◽  
pp. 10866-10868 ◽  
Author(s):  
Alejandra Calvo ◽  
Basit Yameen ◽  
Federico J. Williams ◽  
Galo J.A.A. Soler-Illia ◽  
Omar Azzaroni
Keyword(s):  
Polymer Brushes ◽  
Ionic Transport ◽  
Mesoporous Films ◽  
Hybrid Assemblies

Single Conical Nanopores Displaying pH-Tunable Rectifying Characteristics. Manipulating Ionic Transport With Zwitterionic Polymer Brushes

2009 ◽  
Vol 131 (6) ◽  
pp. 2070-2071 ◽  
Author(s):  
Basit Yameen ◽  
Mubarak Ali ◽  
Reinhard Neumann ◽  
Wolfgang Ensinger ◽  
Wolfgang Knoll ◽  
...  
Keyword(s):  
Polymer Brushes ◽  
Ionic Transport ◽  
Conical Nanopores ◽  
Zwitterionic Polymer

Proton-regulated rectified ionic transport through solid-state conical nanopores modified with phosphate-bearing polymer brushes

2010 ◽  
Vol 46 (11) ◽  
pp. 1908 ◽  
Author(s):  
Basit Yameen ◽  
Mubarak Ali ◽  
Reinhard Neumann ◽  
Wolfgang Ensinger ◽  
Wolfgang Knoll ◽  
...  
Keyword(s):  
Solid State ◽  
Polymer Brushes ◽  
Ionic Transport ◽  
Conical Nanopores

Forces between asymmetric polymer brushes

1990 ◽  
Vol 51 (8) ◽  
pp. 701-707 ◽  
Author(s):  
D.F.K. Shim ◽  
M. E. Cates
Keyword(s):  
Polymer Brushes

Nanostructured Polymer Brushes With Reversibly Changing Properties

2002 ◽  
Vol 727 ◽  
Author(s):  
Denys Usov ◽  
Manfred Stamm ◽  
Sergiy Minko ◽  
Christian Froeck ◽  
Andreas Scholl ◽  
...  
Keyword(s):  
Polymer Brushes ◽  
Phase Segregation ◽  
Water Contact ◽  
Angle Measurements ◽  
Nanostructured Polymer ◽  
Contact Angle Measurements ◽  
Vertical Segregation ◽  
Oxygen Plasma Etching ◽  
Grafting From ◽  
Photoemission Electron

AbstractWe investigated the interplay between different mechanisms of the lateral and vertical segregation in the synthesized via “grafting from” approach symmetric A/B (where A and B are poly(styrene-co-2,3,4,5,6-pentafluorostyrene) and poly(methylmethacrylate), respectively) polymer brushes upon exposure to different solvents. We used X-ray photoemission electron spectroscopy and microscopy (X-PEEM), AFM, water contact angle measurements, and oxygen plasma etching to study morphology of the brushes. The ripple morphology after toluene (nonselective solvent) revealed elongated lamellar-like domains of A and B polymers alternating across the surface. The dimple-A morphology consisting of round clusters of the polymer A was observed after acetone (selective solvent for B). The top layer was enriched with the polymer B showing that the brush underwent both the lateral and vertical phase segregation. A qualitative agreement with predictions of SCF theory was found.

Exploring the Influence of Substitution on the Structure and Transport Properties in the Sodium Superionic Conductor Na11+xSn2+x(Sb1−yPy)1−xS12

2020 ◽  
Author(s):  
Marvin Kraft ◽  
Lara Gronych ◽  
Theodosios Famprikis ◽  
Saneyuki Ohno ◽  
Wolfgang Zeier
Keyword(s):  
Electrochemical Impedance ◽  
Structural Phase ◽  
Ionic Transport ◽  
Sodium Ion ◽  
Ionic Conductors ◽  
Temperature Dependent ◽  
Activation Barriers ◽  
Rietveld Refinements ◽  
High Performing ◽  
The Given

<p>Sulfidic sodium ion conductors are currently investigated for the possible use in all-solid-state sodium ion batteries. The design of high performing electrolytes in terms of temperature-dependent ionic transport is based upon the fundamental understanding of structure – transport relationships within the given structural phase boundaries inherent to the investigated materials class. In this work, the Na<sup>+</sup> superionic structural family of Na<sub>11</sub>Sn<sub>2</sub>PS<sub>12</sub> is explored by using the systematic antimony substitution with phosphorous in Na<sub>11+<i>x</i></sub>Sn<sub>2+<i>x</i></sub>(Sb<sub>1-<i>y</i></sub>P<i><sub>y</sub></i>)<sub>1-<i>x</i></sub>S<sub>12</sub>. A combination of Rietveld refinements against X-ray synchrotron diffraction data with electrochemical impedance spectroscopy is used to monitor the changes in the anionic framework, the Na<sup>+</sup> substructure and the ionic transport. A new simplified descriptor for the average Na<sup>+</sup> diffusion pathways, the average Na<sup>+</sup> polyhedral volume is introduced, which is used to correlate the contraction of the overall lattice and the found activation barriers in the system. This study exemplifies how substitution affects diffusion pathways in ionic conductors and widens the knowledge about the related structural motifs and their influence on the ionic transport in this novel class of ionic conductors.</p>

Multi-Stimuli-Responsive Mesoporous Membranes and Effect of Molecular Architecture on Thermo- and pH-Responsive Behavior of the grafted Block Copolymer brushes

2019 ◽  
Author(s):  
Yanchun Tang ◽  
Kohzo Ito ◽  
Hideaki Yokoyama
Keyword(s):  
Polymer Brushes ◽  
Diblock Copolymers ◽  
Neutron Reflectivity ◽  
Molecular Architecture ◽  
Stimuli Responsive ◽  
Responsive Polymer ◽  
The Matrix ◽  
Stable Part ◽  
Copolymer Brushes ◽  
Mesoporous Membranes

In this study, we prepared ultrafiltration membranes with a decoupled responses of filtration property to temperature and pH. The membrane preparation method was developed based on our previous work. We utilized methanol-supercritical carbon dioxide (methanol-scCO<sub>2</sub>) selective swelling method to introduce nanopores to block copolymers containing poly(diethylene glycol) methyl ether methacrylate (PMEO<sub>2</sub>MA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and polystyrene (PS) blocks. Formation of the mesoporous barrier layer with PS being the mechanically stable part of the matrix was driven by selective swelling of the PMEO<sub>2</sub>MA-b-PDMAEMA domains. Due to the selective swelling of PMEO<sub>2</sub>MA or PDMAEMA domains to introduce pores, the interior of the pores are covered with PMEO<sub>2</sub>MA or PDMAEMA blocks after pore formation. The PMEO<sub>2</sub>MA-b-PDMAEMA polymer brushes are naturally attached on the pore walls and worked as functional gates. PMEO<sub>2</sub>MA is a non-toxic, neutral thermo-responsive polymer with LCST at 26 ᴼC. PDMAEMA is a typical weak polyelectrolyte with pK<sub>a</sub> value at 7.0-7.5 and also a thermo-responsive polymer revealed a LCST of 20-80 °C in aqueous solution. Therefore, these membranes were expected to have multi dimensions as function of the combination of temperature and pH. Moreover, to understand the detail of the temperature and pH depended conformation transitions of PMEO<sub>2</sub>MA-b-PDMAEMA brushes, those diblock copolymers were end-tethered on flat substrates and analyzed via neutron reflectivity (NR).

Changing the Static and Dynamic Lattice Effects for the Improvement of the Ionic Transport Properties Within the Argyrodite Li6PS5-xSexI

2019 ◽  
Author(s):  
Roman Schlem ◽  
Michael Ghidiu ◽  
Sean Culver ◽  
Anna-Lena Hansen ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Activation Barrier ◽  
Parent Compound ◽  
Ionic Transport ◽  
X Ray Diffraction ◽  
X Ray ◽  
Lattice Effects ◽  
Solid State Batteries ◽  
All Solid State Batteries ◽  
Pulse Echo

<p>The lithium argyrodites Li<sub>6</sub>PS<sub>5</sub>X (X = Cl, Br, I) have been gaining momentum as candidates for electrolytes in all-solid-state batteries. While these materials have been well-characterized structurally, the influences of the static and dynamic lattice properties are not fully understood. Recent improvements to the ionic conductivity of Li<sub>6</sub>PS<sub>5</sub>I (which as a parent compound is a poor ionic conductor) via elemental substitutions have shown that a multitude of influences affect the ionic transport in the lithium argyrodites, and that even poor conductors in this class have room left for improvement.</p><p>Here we explore the influence of isoelectronic substitution of sulfur with selenium in Li<sub>6</sub>PS<sub>5-<i>x</i></sub>Se<i><sub>x</sub></i>I. Using a combination of X-ray diffraction, impedance spectroscopy, Raman spectroscopy, and pulse-echo speed of sound measurements,we explore the influence of the static and dynamic lattice on the ionic transport. The substitution of S<sup>2-</sup>with Se<sup>2- </sup>broadens the diffusion pathways and structural bottlenecks, as well as leading to a softer more polarizable lattice, all of which lower the activation barrier and lead to an increase in the ionic conductivity. This work sheds light on ways to systematically understand and improve the functional properties of this exciting material family. </p>

Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li6PS5Br

2019 ◽  
Author(s):  
Ajay Gautam ◽  
Marcel Sadowski ◽  
Nils Prinz ◽  
Henrik Eickhoff ◽  
Nicolo Minafra ◽  
...  
Keyword(s):  
Elevated Temperatures ◽  
Synthesis Method ◽  
Reaction Times ◽  
Ionic Conductivities ◽  
Ionic Transport ◽  
High Energy ◽  
Superionic Conductors ◽  
Rapid Crystallization ◽  
Site Disorder ◽  
Fast Cooling

<p>Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li<sub>6</sub>PS<sub>5</sub>X (X = Cl, Br, I), a site-disorder between the anionsS<sup>2–</sup>and X<sup>–</sup>has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such disorder in Li<sub>6</sub>PS<sub>5</sub>Br can be engineered <i>via</i>the synthesis method. By comparing fast cooling (<i>i.e. </i>quenching) to more slowly cooled samples, we find that anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with <i>ab-initio</i>molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within one minute of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced <i>via</i>quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.</p>

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