scholarly journals Ion-Conducting Redox-Active Polymer Gels Based on Stable Nitroxide Radicals

Polymers ◽  
2019 ◽  
Vol 11 (8) ◽  
pp. 1322
Author(s):  
Boujioui ◽  
Gohy
Keyword(s):  
Ionic Conductivity ◽  
Polymer Networks ◽  
Ionic Conductivities ◽  
Crosslinking Density ◽  
Organic Radical ◽  
Nitroxide Radicals ◽  
Lithium Ions ◽  
Redox Active ◽  
Ion Conducting ◽  
Stable Nitroxide

Redox-active polymer networks based on stable nitroxide radicals are a very promising class of materials to be used in the so-called organic radical batteries. In order to obtain fast-charging and high power electrodes, however, excellent ionic conductivity inside the electrode material is required to allow easy diffusion of ions and fast redox reactions. In this contribution, we investigated redox-active poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) chains cross-linked through ionic liquid-like 1,2,3-triazolium groups. Different networks were prepared in which the amount of cross-linker and the counter-anion associated to the 1,2,3-triazolium group were varied. The ionic conductivities of the different polymer networks were first measured in the solid state by electrochemical impedance spectroscopy at different temperatures, and an increased ionic conductivity was measured when 1,2,3-triazolium groups were present in the network. The effects of the chemical nature of the counterions associated to the 1,2,3-triazolium groups and of the crosslinking density were then studied. The best ionic conductivities were obtained when bis (trifluoromethane)sulfonamide (TFSI) counter-anions were used, and when the crosslinking density of the TFSI-containing gel was higher. Finally, those ion-conducting gels were loaded with free LiTFSI and the transference number of lithium ions was accordingly measured. The good ionic conductivities and lithium ions transference numbers measured for the investigated redox-active gels make them ideal candidates for application as electrode materials for either organic radical batteries or pseudo-capacitors energy storage devices.

scholarly journals Application of Redox-Responsive Hydrogels Based on 2,2,6,6-Tetramethyl-1-Piperidinyloxy Methacrylate and Oligo(Ethyleneglycol) Methacrylate in Controlled Release and Catalysis

Polymers ◽  
2021 ◽  
Vol 13 (8) ◽  
pp. 1307
Author(s):  
Miriam Khodeir ◽  
He Jia ◽  
Alexandru Vlad ◽  
Jean-François Gohy
Keyword(s):  
Polymer Networks ◽  
Primary Alcohols ◽  
Nitroxide Radicals ◽  
Triggered Release ◽  
Specific Chemical ◽  
Co Catalyst ◽  
Redox Responsive ◽  
Responsive Hydrogels ◽  
Glycol Methyl Ether ◽  
Stable Nitroxide

Hydrogels have reached momentum due to their potential application in a variety of fields including their ability to deliver active molecules upon application of a specific chemical or physical stimulus and to act as easily recyclable catalysts in a green chemistry approach. In this paper, we demonstrate that the same redox-responsive hydrogels based on polymer networks containing 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radicals and oligoethylene glycol methyl ether methacrylate (OEGMA) can be successfully used either for the electrochemically triggered release of aspirin or as catalysts for the oxidation of primary alcohols into aldehydes. For the first application, we take the opportunity of the positive charges present on the oxoammonium groups of oxidized TEMPO to encapsulate negatively charged aspirin molecules. The further electrochemical reduction of oxoammonium groups into nitroxide radicals triggers the release of aspirin molecules. For the second application, our hydrogels are swelled with benzylic alcohol and tert-butyl nitrite as co-catalyst and the temperature is raised to 50 °C to start the oxidation reaction. Interestingly enough, benzaldehyde is not miscible with our hydrogels and phase-separate on top of them allowing the easy recovery of the reaction product and the recyclability of the hydrogel catalyst.

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

2020 ◽  
Author(s):  
Saneyuki Ohno ◽  
Tim Bernges ◽  
Johannes Buchheim ◽  
Marc Duchardt ◽  
Anna-Katharina Hatz ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Ionic Conductivity ◽  
Relative Standard Deviation ◽  
Solid Electrolytes ◽  
Ionic Conductivities ◽  
Ionic Conductors ◽  
Energy Storage Devices ◽  
Activation Barriers ◽  
Storage Devices ◽  
Relative Standard

<p>Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an <i>interlaboratory reproducibility</i> of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm<sup>-1</sup> in the measured total ionic conductivity (1.3 – 5.8 mScm<sup>-1</sup> for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.</p>

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

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

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = 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 Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, 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<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

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

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

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = 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 Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, 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<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

Solid Polymer Electrolytes from Crosslinked PEG and Dilithium N,N'-Bis(trifluoromethanesulfonyl)perfluoroalkane-1,ω-disulfonamide and Lithium Bis(trifluoromethanesulfonyl)imide Salts

2008 ◽  
Vol 73 (12) ◽  
pp. 1777-1798 ◽  
Author(s):  
Olt E. Geiculescu ◽  
Rama V. Rajagopal ◽  
Emilia C. Mladin ◽  
Stephen E. Creager ◽  
Darryl D. Desmarteau
Keyword(s):  
Ionic Conductivity ◽  
Polymer Electrolytes ◽  
Minimum Energy ◽  
Ionic Conductivities ◽  
Solid Polymer Electrolytes ◽  
Solid Polymer ◽  
Segmental Motion ◽  
Concentrated Electrolytes ◽  
Two Factors ◽  
Poly Ethylene

The present work consists of a series of studies with regard to the structure and charge transport in solid polymer electrolytes (SPE) prepared using various new bis(trifluoromethanesulfonyl)imide (TFSI)-based dianionic dilithium salts in crosslinked low-molecular-weight poly(ethylene glycol). Some of the thermal properties (glass transition temperature, differential molar heat capacity) and ionic conductivities were determined for both diluted (EO/Li = 30:1) and concentrated (EO/Li = 10:1) SPEs. Trends in ionic conductivity of the new SPEs with respect to anion structure revealed that while for the dilute electrolytes ionic conductivity is generally rising with increased length of the perfluoroalkylene linking group in the dianions, for the concentrated electrolytes the trend is reversed with respect to dianion length. This behavior could be the result of a combination of two factors: on one hand a decrease in dianion basicity that results in diminished ion pairing and an enhancement in the number of charge carriers with increasing fluorine anion content, thereby increasing ionic conductivity while on the other hand the increasing anion size and concentration produce an increase in the friction/entanglements of the polymeric segments which lowers even more the reduced segmental motion of the crosslinked polymer and decrease the dianion contribution to the overall ionic conductivity. DFT modeling of the same TFSI-based dianionic dilithium salts reveals that the reason for the trend observed is due to the variation in ion dissociation enthalpy, derived from minimum-energy structures, with respect to perfluoroalkylene chain length.

scholarly journals Investigating the Factors Affecting the Ionic Conduction in Nanoconfined NaBH4

Inorganics ◽  
2021 ◽  
Vol 9 (1) ◽  
pp. 2
Author(s):  
Xiaoxuan Luo ◽  
Aditya Rawal ◽  
Kondo-Francois Aguey-Zinsou
Keyword(s):  
Ionic Conductivity ◽  
Ionic Conduction ◽  
Metal Hydrides ◽  
Ionic Conductivities ◽  
Effective Strategy ◽  
Li Ion Batteries ◽  
Large Cage ◽  
Factors Affecting ◽  
Li Ion ◽  
Mcm 41

Nanoconfinement is an effective strategy to tune the properties of the metal hydrides. It has been extensively employed to modify the ionic conductivity of LiBH4 as an electrolyte for Li-ion batteries. However, the approach does not seem to be applicable to other borohydrides such as NaBH4, which is found to reach a limited improvement in ionic conductivity of 10−7 S cm−1 at 115 °C upon nanoconfinement in Mobil Composition of Matter No. 41 (MCM-41) instead of 10−8 S cm−1. In comparison, introducing large cage anions in the form of Na2B12H12 naturally formed upon the nanoconfinement of NaBH4 was found to be more effective in leading to higher ionic conductivities of 10−4 S cm−1 at 110 °C.

scholarly journals Sodium, Silver and Lithium-Ion Conducting β″-Alumina + YSZ Composites, Ionic Conductivity and Stability

Crystals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 293
Author(s):  
Liangzhu Zhu ◽  
Anil V. Virkar
Keyword(s):  
Ion Exchange ◽  
Electrochemical Impedance ◽  
Ionic Conductivities ◽  
Lithium Ion ◽  
Co2 Corrosion ◽  
Ionic Conductors ◽  
Ion Conductor ◽  
Sensor Applications ◽  
Potential Applications ◽  
Ion Conducting

Na-β″-alumina (Na2O.~6Al2O3) is known to be an excellent sodium ion conductor in battery and sensor applications. In this study we report fabrication of Na- β″-alumina + YSZ dual phase composite to mitigate moisture and CO2 corrosion that otherwise can lead to degradation in pure Na-β″-alumina conductor. Subsequently, we heat-treated the samples in molten AgNO3 and LiNO3 to respectively form Ag-β″-alumina + YSZ and Li-β″-alumina + YSZ to investigate their potential applications in silver- and lithium-ion solid state batteries. Ion exchange fronts were captured via SEM and EDS techniques. Their ionic conductivities were measured using electrochemical impedance spectroscopy. Both ion exchange rates and ionic conductivities of these composite ionic conductors were firstly reported here and measured as a function of ion exchange time and temperature.

scholarly journals Performance-tuning of PVA-based gel electrolytes by acid/PVA ratio and PVA molecular weight

2021 ◽  
Vol 3 (3) ◽  
Author(s):  
Saeideh Alipoori ◽  
M. M. Torkzadeh ◽  
Saeedeh Mazinani ◽  
Seyed Hamed Aboutalebi ◽  
Farhad Sharif
Keyword(s):  
Molecular Weight ◽  
Ionic Conductivity ◽  
Charge Carrier Concentration ◽  
Fine Tuning ◽  
Performance Tuning ◽  
Practical Applications ◽  
High Performing ◽  
Flexible Devices ◽  
Gel Electrolytes ◽  
Ion Conducting

AbstractThe significant breakthroughs of flexible gel electrolytes have attracted extensive attention in modern wearable electronic gadgets. The lack of all-around high-performing gels limits the advantages of such devices for practical applications. To this end, developing a multi-functional gel architecture with superior ionic conductivity while enjoying good mechanical flexibility is a bottleneck to overcome. Herein, an architecturally engineered gel, based on PVA and H3PO4 with different molecular weights of PVA for various PVA/H3PO4 ratios, was developed. The results show the dependence of ionic conductivity on molecular weight and also charge carrier concentration. Consequently, fine-tuning of PVA-based gels through a simple yet systematic and well-regulated strategy to achieve highly ion-conducting gels, with the highest ionic conductivity of 14.75 ± 1.39 mS cm-1 have been made to fulfill the requirement of flexible devices. More importantly, gel electrolytes possess good mechanical robustness while exhibiting high-elasticity (%766.66 ± 59.73), making it an appropriate candidate for flexible devices.

Neonatal blood is more resistant to oxidative stress induced by stable nitroxide radicals than adult blood

2007 ◽  
Vol 277 (3) ◽  
pp. 233-237 ◽  
Author(s):  
Tali Silberstein ◽  
David Mankuta ◽  
Alexander I. Shames ◽  
Gertz I. Likhtenshtein ◽  
Dan Meyerstein ◽  
...  
Keyword(s):  
Oxidative Stress ◽  
Nitroxide Radicals ◽  
Neonatal Blood ◽  
Stable Nitroxide
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