Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers

ABSTRACTBlending the biopolymer chitosan (CHI) with poly (aminopropilsiloxane) oligomers (pAPS), and poly (ethylene oxide) (PEO) in the presence of lithium perchlorate lead to ion conducting products whose conductivity depends on the composition of the mixture. A ternary phase diagram for mixtures containing 0.2 M LiClO4 shows a zone in which the physical properties of the products - transparent, flexible, mechanically robust films - indicate a high degree of molecular compatibilization of the components. Comparison of these films with binary CHI-pAPS nanocomposites as well as the microscopic aspect, thermal behavior, and X-ray diffraction pattern of the product with the composition PEO/CHI/pAPS/LiClO4 1:0.5:0.6:0.2 molar ratio indicates that these films may be described as a layered nanocomposite. In this composite, lithium species coordinated by PEO and pAPS should be inserted into chitosan layers. Electrochemical impedance spectroscopy measurements indicate the films are pure ionic conductors with a maximal bulk conductivity of 1.7*10-5 Scm-1 at 40 °C and a sample-electrode interface capacitance of about 1.2*10-9 F.

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Dynamic Emergence of Nanostructure and Transport Properties in Perfluorinated Sulfonic Acid Ionomers

10.26434/chemrxiv.12302693.v1 ◽

2020 ◽

Author(s):

Adlai Katzenberg ◽

Debdyuti Mukherjee ◽

Peter J. Dudenas ◽

Yoshiyuki Okamoto ◽

Ahmet Kusoglu ◽

...

Keyword(s):

Rate Constant ◽

Sulfonic Acid ◽

Mass Fraction ◽

Gas Permeability ◽

Transport Processes ◽

Segmental Mobility ◽

The Matrix ◽

Swelling Rate ◽

Ion Conducting ◽

Perfluorinated Sulfonic Acid

Limitations in fuel cell electrode performance have motivated the development of ion-conducting binders (ionomers) with high gas permeability. Such ionomers have been achieved by copolymerization of perfluorinated sulfonic acid (PFSA) monomers with bulky and asymmetric monomers, leading to a glassy ionomer matrix with chemical and mechanical properties that differ substantially from common PFSA ionomers (e.g., Nafion™). In this study, we use perfluorodioxolane-based ionomers to provide fundamental insights into the role of the matrix chemical structure on the dynamics of structural and transport processes in ion-conducting polymers. Through in-situ water uptake measurements, we demonstrate that ionomer water sorption kinetics depend strongly on the properties and mass fraction of the matrix. As the PFSA mass fraction was increased from 0.26 to 0.57, the Fickian swelling rate constant decreased from 0.8 s-1 to 0.2 s-1, while the relaxation rate constant increased from 3.1×10-3 s-1 to 4.0×10-3. The true swelling rate, in nm s-1, was determined by the chemical nature of the matrix; all dioxolane-containing materials exhibited swelling rates ~1.5 - 2 nm s-1 compared to ~3 nm s-1 for Nafion. Likewise, Nafion underwent relaxation at twice the rate of the fastest-relaxing dioxolane ionomer. Reduced swelling and relaxation kinetics are due to limited matrix segmental mobility of the dioxolane-containing ionomers. We demonstrate that changes in conductivity are strongly tied to the polymer relaxation, revealing the decoupled roles of initial swelling and relaxation on hydration, nanostructure, and ion transport in perfluorinated ionomers.

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Computational Investigation of the Asymmetry in Photosynthetic Reaction Center Models from First Principles

10.26434/chemrxiv.11980119.v1 ◽

2020 ◽

Author(s):

Denis Artiukhin ◽

Patrick Eschenbach ◽

Johannes Neugebauer

Keyword(s):

Spin Density ◽

Reaction Center ◽

Density Functional ◽

Photosynthetic Reaction Center ◽

Chem Phys ◽

Molecular Structures ◽

Error Characteristic ◽

Molecular Systems ◽

Density Distributions ◽

The Asymmetry

We present a computational analysis of the asymmetry in reaction center models of photosystem I, photosystem II, and bacteria from Synechococcus elongatus, Thermococcus vulcanus, and Rhodobacter sphaeroides, respectively. The recently developed FDE-diab methodology [J. Chem. Phys., 148 (2018), 214104] allowed us to effectively avoid the spin-density overdelocalization error characteristic for standard Kohn–Sham Density Functional Theory and to reliably calculate spin-density distributions and electronic couplings for a number of molecular systems ranging from dimeric models in vacuum to large protein including up to about 2000 atoms. The calculated spin densities showed a good agreement with available experimental results and were used to validate reaction center models reported in the literature. We demonstrated that the applied theoretical approach is very sensitive to changes in molecular structures and relative orientation of molecules. This makes FDE-diab a valuable tool for electronic structure calculations of large photosynthetic models effectively complementing the existing experimental techniques.

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Atomic Layer Deposition of LiF and Lithium Ion Conducting (AlF3)(LiF)x Alloys Using Trimethylaluminum, Lithium Hexamethyldisilazide and Hydrogen Fluoride

10.26434/chemrxiv.5459653 ◽

2017 ◽

Author(s):

Younghee Lee ◽

Daniela M. Piper ◽

Andrew S. Cavanagh ◽

Matthias J. Young ◽

Se-Hee Lee ◽

...

Keyword(s):

Lithium Ion ◽

Atomic Layer ◽

Mass Gain ◽

Alloy Film ◽

Ex Situ ◽

X Ray ◽

Layer Deposition ◽

Ion Conducting ◽

Good Agreement

<div>Atomic layer deposition (ALD) of LiF and lithium ion conducting (AlF3)(LiF)x alloys was developed using trimethylaluminum, lithium hexamethyldisilazide (LiHMDS) and hydrogen fluoride derived from HF-pyridine solution. ALD of LiF was studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectrometer (QMS) at reaction temperatures between 125°C and 250°C. A mass gain per cycle of 12 ng/(cm2 cycle) was obtained from QCM measurements at 150°C and decreased at higher temperatures. QMS detected FSi(CH3)3 as a reaction byproduct instead of HMDS at 150°C. LiF ALD showed self-limiting behavior. Ex situ measurements using X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) showed a growth rate of 0.5-0.6 Å/cycle, in good agreement with the in situ QCM measurements.</div><div>ALD of lithium ion conducting (AlF3)(LiF)x alloys was also demonstrated using in situ QCM and in situ QMS at reaction temperatures at 150°C A mass gain per sequence of 22 ng/(cm2 cycle) was obtained from QCM measurements at 150°C. Ex situ measurements using XRR and SE showed a linear growth rate of 0.9 Å/sequence, in good agreement with the in situ QCM measurements. Stoichiometry between AlF3 and LiF by QCM experiment was calculated to 1:2.8. XPS showed LiF film consist of lithium and fluorine. XPS also showed (AlF3)(LiF)x alloy consists of aluminum, lithium and fluorine. Carbon, oxygen, and nitrogen impurities were both below the detection limit of XPS. Grazing incidence X-ray diffraction (GIXRD) observed that LiF and (AlF3)(LiF)x alloy film have crystalline structures. Inductively coupled plasma mass spectrometry (ICP-MS) and ionic chromatography revealed atomic ratio of Li:F=1:1.1 and Al:Li:F=1:2.7: 5.4 for (AlF3)(LiF)x alloy film. These atomic ratios were consistent with the calculation from QCM experiments. Finally, lithium ion conductivity (AlF3)(LiF)x alloy film was measured as σ = 7.5 × 10-6 S/cm.</div>

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Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

10.26434/chemrxiv.9943961.v2 ◽

2019 ◽

Author(s):

Till Fuchs ◽

Sean Culver ◽

Paul Till ◽

Wolfgang Zeier

Keyword(s):

Ionic Conductivity ◽

Vacancy Concentration ◽

Sodium Ion ◽

High Ionic Conductivity ◽

Ionic Conductors ◽

X Ray Diffraction ◽

X Ray ◽

Solid State Batteries ◽

Ion Conducting ◽

Very High

The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solutions with WS42- introduction are explored. The influence of the substitution with WS42- for PS43- and SbS43-, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.

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Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

10.26434/chemrxiv.9943961.v1 ◽

2019 ◽

Author(s):

Till Fuchs ◽

Sean Culver ◽

Paul Till ◽

Wolfgang Zeier

Keyword(s):

Ionic Conductivity ◽

Vacancy Concentration ◽

Sodium Ion ◽

High Ionic Conductivity ◽

Ionic Conductors ◽

X Ray Diffraction ◽

X Ray ◽

Solid State Batteries ◽

Ion Conducting ◽

Very High

The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solutions with WS42- introduction are explored. The influence of the substitution with WS42- for PS43- and SbS43-, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.

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