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Journal articles on the topic 'Glassy Electrolytes'

Author: Grafiati

Published: 7 September 2023

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1

Morales, Daniel J., and Steven Greenbaum. "NMR Investigations of Crystalline and Glassy Solid Electrolytes for Lithium Batteries: A Brief Review." International Journal of Molecular Sciences 21, no. 9 (May 11, 2020): 3402. http://dx.doi.org/10.3390/ijms21093402.

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The widespread use of energy storage for commercial products and services have led to great advancements in the field of lithium-based battery research. In particular, solid state lithium batteries show great promise for future commercial use, as solid electrolytes safely allow for the use of lithium-metal anodes, which can significantly increase the total energy density. Of the solid electrolytes, inorganic glass-ceramics and Li-based garnet electrolytes have received much attention in the past few years due to the high ionic conductivity achieved compared to polymer-based electrolytes. This review covers recent work on novel glassy and crystalline electrolyte materials, with a particular focus on the use of solid-state nuclear magnetic resonance spectroscopy for structural characterization and transport measurements.

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2

Wheaton, Jacob, and Steve Martin. "Electrochemical Characterization of a Drawn Thin-Film Mixed Oxy-Sulfide Glassy Electrolyte Material for Solid-State Battery Applications." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 489. http://dx.doi.org/10.1149/ma2022-024489mtgabs.

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Solid-state batteries are a promising avenue for next-generation lithium-ion batteries due to their enabling of the lithium metal anode, while simultaneously removing the flammable organic electrolyte. Glassy materials are particularly interesting as solid-state electrolytes due to their intrinsic lack of grain boundaries, their low temperature forming capabilities, and their highly tunable chemistries. Much work has been done to study the electrochemical properties of glasses in the Li2S – SiS2 – LixMOy phase space, and several compositions have shown high ionic conductivities (~ 10-3 S/cm), large electrochemical stability windows (0-5 V vs. Li/Li+), and good glass forming ability. These glasses, however, have not been well studied at thicknesses that are viable for commercialization of solid electrolytes (< 100 μm). Utilizing a glass working method known as the redraw process, a rectangular preform of glass can be reheated and drawn from ~ 5 mm in thickness to thin films of less than 100 μm. The electrochemical behavior of thin-film glasses in the Li2S – SiS2 – LiPO3 phase space created through the glass redraw process are studied utilizing electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic symmetric cell cycling. These results show that thin-film glassy solid electrolytes made through the glass redraw method are a viable new research direction for generation of highly conducting thin-film solid-state electrolytes.

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3

TSIULYANU, D., I. STRATAN, and M. CIOBANU. "INFLUENCE OF GLASSY BACKBONE ON THE PHOTOFORMATION AND PROPERTIES OF SOLID ELECTROLYTES Ag : As-S-Ge." Chalcogenide Letters 17, no. 1 (January 2020): 9–14. http://dx.doi.org/10.15251/cl.2020.171.9.

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The effect of the glassy backbone on the process of fabrication and some properties of solid electrolytes obtained via photodissolution (PD) of Ag into chalcogenide glasses (ChG) of the system As-S-Ge have been studied with respect to XRD and far IR spectroscopy analyses. The compositional tie – line (GeS4)x (AsS3)1-x has been chosen to realize the monotonic transition of the structural units of glassy backbone from trigonal to tetragonal configuration. It is shown that the process of solid electrolyte formation occurs in three steps, but the last two steps, as well as the electrical properties of the finally fabricated electrolyte, are strongly influenced by chemical composition and microstructure of the used ChG backbone. The rate of solid electrolyte formation exhibit a maximum around of glassy backbone composition (GeS4)0.33(AsS3)0.67 but the electrical resistivity of fabricated solid electrolytes reaches a minimum at this composition. Based on IR transmission spectra analyses, it is assumed that these peculiarities are due to glass homogenization, which results from building in this alloyed composition of an amalgamation of tetrahedral and trigonal structural units connected in a random network, without clustering. Such homogenization promotes the transport of both electrons and ions involved in photoreaction because of lack of phase boundaries and additional defects.

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4

Okkema, Mary, Madison Martin, and Steve Martin. "Electrochemical Characterization of a Drawn Thin-Film Glassy Mixed Oxy-Sulfide-Nitride Phosphate Electrolyte Material for Applications in Solid-State Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 414. http://dx.doi.org/10.1149/ma2022-024414mtgabs.

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Thin-film glassy solid-state electrolytes are often considered for applications in energy storage devices; fully-dense thin-film glassy electrolyte materials are able to minimize power loss while suppressing dendrite growth. The glass with the composition Na4P2S5.8O0.92N0.18 (NaPSON) was chosen because it balances the high conductivity of a sulfide chemistry with the high processability and electrochemical stability of an oxy-nitride chemistry. NaPSON thin-film glassy solid-state electrolyte ribbons with thicknesses that range from 75 to 600 μm were drawn using a process of softening and drawing of a cast and annealed preform. Raman spectroscopy was run on the thin-film samples to ensure the material was structurally similar after processing across different thicknesses and remelts. Electrochemical impedance spectroscopy (EIS) was used on varying thicknesses of thin-film to investigate and compare the ionic conductivity of Na+ in the thin film compared to the bulk sample. Area specific resistance models as a function of time were created to compare the trend of bulk and interfacial resistances of different thicknesses. Thin-film samples were made into symmetric cells and cycled. The cycling of the symmetric cells gave insight into the behavior and durability of the electrolyte under applied voltage and sustained current. These results show that drawn thin-film electrolytes are a solid research direction.

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5

Martin, Madison, Mary Okkema, and Steve Martin. "Electrochemical Characterization of a Drawn Thin-Film Glassy Mixed Oxy-Sulfide-Nitride Phosphate Electrolyte for Applications in Solid-State Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 530. http://dx.doi.org/10.1149/ma2022-024530mtgabs.

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Thin-film glassy solid-state electrolytes (GSEs) are being considered for applications in energy storage devices; fully-dense thin-film glassy electrolyte materials are able to minimize power loss while suppressing dendrite growth. The glass with the composition Na4P2S5.8O0.92N0.18 (NaPSON) was chosen because it balances the high conductivity of a sulfide chemistry with the high processability and electrochemical stability of an oxy-nitride chemistry. NaPSON thin-film GSE ribbons with thicknesses that range from 50 to 150 μm were drawn using a process of softening and drawing of a cast and annealed preform. Electrochemical impedance spectroscopy (EIS) was used on varying thicknesses of thin-film to investigate and compare the ionic conductivity of Na+ in the thin film compared to the bulk sample. Area specific resistance models as a function of time were created to compare the trend of bulk and interfacial resistances of different thicknesses. Thin-film samples were made into symmetric cells and cycled. The cycling of the symmetric cells gave insight into the behavior and durability of the electrolyte under applied voltage and sustained current. These results show that drawn thin-film electrolytes are a viable research direction for all solid-state batteries.

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6

Bin, Wu, and Fan Chun. "Summary of Lithium-Ion Battery Polymer Electrolytes." Advanced Materials Research 535-537 (June 2012): 2092–99. http://dx.doi.org/10.4028/www.scientific.net/amr.535-537.2092.

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Polymer electrolyte is a good ion conductor in lithium-ion battery with an excellent performance in conductivity, ion mobility and ion transport number. Some researches show strengthening mechanisms of polymer electrolyte membranes correlated with macromolecules group weight of PEGDME such as concentration of compounded Li+ salt. Ion transport in glassy polymer electrolytes including polymer backbones with same mesogenic chains can affect amorphous structure and relaxation at ambient temperature. In addition, singe crystal structure polymer electrolytes have various internal microstructures and external properties such as conductivity and charge or discharge stability in electrochemical that correlating with layers of ion diffusion and forming.

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7

Ingram, M. "Ion transport in glassy electrolytes." Solid State Ionics 94, no. 1-4 (February 1, 1997): 49–54. http://dx.doi.org/10.1016/s0167-2738(96)00610-8.

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8

Choi, H., H. K. Kim, Y. W. Koo, K. H. Nam, S. M. Koo, W. J. Cho, and H. B. Chung. "Investigation of Electrical Properties in Chalcogenide Thin Film According to Wave Length." Advanced Materials Research 31 (November 2007): 135–37. http://dx.doi.org/10.4028/www.scientific.net/amr.31.135.

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Programmable metallization cell (PMC) memory is based on the electrochemical control of nanoscale quantities of metal in thin films of solid electrolyte. We investigate the nature of thin films formed by the photo-dissolution of Ag into Ge-Se-Te glasses for use in programmable metallization cell devices. Glassy alloys of a-Ge25Se75-xTex(x = 0, 25) are prepared by well known melt-quenching technique. Thin films of a-Ge25Se75-xTex(x = 0, 25) glassy alloys are evaporated by vacuum evaporation technique at ~10-6 torr on glass substrate at room temperature. Optical properties in this study concerns photo-diffusion of Ag on Ag-doped Ge-Se-Te electrolytes. With these promising properties, the composition a-Ge25Se75-xTex(x = 0, 25) is recommended as a potential candidate for PMC-RAM.

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9

Vukicevic, Natasa, Vesna Cvetkovic, Nebojsa Nikolic, Goran Brankovic, Tanja Barudzija, and Jovan Jovicevic. "Formation of the honeycomb-like MgO/Mg(OH)2 structures with controlled shape and size of holes by molten salt electrolysis." Journal of the Serbian Chemical Society 83, no. 12 (2018): 1351–62. http://dx.doi.org/10.2298/jsc180913084v.

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Synthesis of the honeycomb-like MgO/Mg(OH)2 structures, with controlled shape and size of holes, by the electrolysis from magnesium nitrate hexahydrate melt onto glassy carbon is presented. The honeycomb-like structures were made up of holes, formed from detached hydrogen bubbles, surrounded by walls, built up of thin intertwined needles. For the first time, it was shown that the honeycomb-like structures can be obtained by molten salt electrolysis and not exclusively by electrolysis from aqueous electrolytes. Analogies with the processes of the honeycomb-like metal structures formation from aqueous electrolytes are presented and discussed. Rules established for the formation of these structures from aqueous electrolytes, such as the increase of number of holes, the decrease of holes size and coalescence of neighbouring hydrogen bubbles observed with increasing cathodic potential, appeared to be valid for the electrolysis of the molten salt used.

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10

Fettkether, Will, Steve Martin, and Jacob Wheaton. "Development and Optimization of Composite Cathode Materials for Use with Thin-Film Glassy Solid Electrolytes in Solid-State Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 515. http://dx.doi.org/10.1149/ma2022-024515mtgabs.

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The electrochemical properties and thermal behavior of thin-film glassy solid electrolytes (GSE) in the [Li2S - SiS2 - LiPO3] system make them viable candidates for inclusion in solid-state batteries. To properly assess these electrolytes in the full-cell format, compatible composite cathode materials must be developed. These materials must be electronically and ionically conductive, and form a stable interface in contact with the GSE. A composite blend of redox-active lithium iron phosphate (LiFePO4), a mixed-oxy-sulfide glassy electrolyte, carbon nanotubes, a lithium solvate ionic liquid (SIL), and styrene butadiene rubber binder (SBR) was utilized to create the cathode material. Mixing time and order of component mixing were controlled in order to optimize for ionic and electronic conductivities within the bulk composite powder. With the addition of the SIL and SBR, a composite cathode blend capable of stably cycling in contact with the GSE was created.

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11

Imrie, C. T., M. D. Ingram, and G. S. McHattie. "Ion Transport in Glassy Polymer Electrolytes." Journal of Physical Chemistry B 103, no. 20 (May 1999): 4132–38. http://dx.doi.org/10.1021/jp983968e.

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12

Bunde, A. "Anomalous ionic transport in glassy electrolytes." Il Nuovo Cimento D 16, no. 8 (August 1994): 1053–63. http://dx.doi.org/10.1007/bf02458787.

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13

Mena, Silvia, Jesus Bernad, and Gonzalo Guirado. "Electrochemical Incorporation of Carbon Dioxide into Fluorotoluene Derivatives under Mild Conditions." Catalysts 11, no. 8 (July 22, 2021): 880. http://dx.doi.org/10.3390/catal11080880.

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One of the main challenges to combat climate change is to eliminate or reuse Carbon dioxide (CO2), the largest contributor to the greenhouse gases that cause global warming. It is also important to synthesize compounds through greener technologies in order to obtain more environmentally friendly solutions. This study describes the electrocarboxylation process of α,α,α-trifluorotoluene using different working electrodes (glassy carbon, silver and copper) and electrolytes (polar aprotic solvent and ionic liquid). Carboxylated compounds were obtained in the same way in both electrolytic medias with more than 80% conversion rates, high yields, good selectivity, and moderate efficiencies using silver and copper as cathodes in organic electrolytes and ionic liquids.

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14

E.A., Il'ina, Raskovalov A.A., Saetova N.S., Antonov B.D., and Reznitskikh O.G. "Composite electrolytes Li7La3Zr2O12–glassy Li2O–B2O3–SiO2." Solid State Ionics 296 (November 2016): 26–30. http://dx.doi.org/10.1016/j.ssi.2016.09.003.

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15

Deshpande, V. K. "Science and technology of glassy solid electrolytes." IOP Conference Series: Materials Science and Engineering 2 (July 1, 2009): 012011. http://dx.doi.org/10.1088/1757-899x/2/1/012011.

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16

Hona, Ram Krishna, Mandy Guinn, Uttam S. Phuyal, S’Nya Sanchez, and Gurjot S. Dhaliwal. "Alkali Ionic Conductivity in Inorganic Glassy Electrolytes." Journal of Materials Science and Chemical Engineering 11, no. 07 (2023): 31–72. http://dx.doi.org/10.4236/msce.2023.117004.

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17

Hester, Gavin, Tom Heitmann, Madhusudan Tyagi, Munesh Rathore, Anshuman Dalvi, and Saibal Mitra. "Neutron Scattering Studies of Lithium-Ion Diffusion in Ternary Phosphate Glasses." MRS Advances 1, no. 45 (2016): 3057–62. http://dx.doi.org/10.1557/adv.2016.492.

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ABSTRACTWe have studied the diffusion mechanism of lithium ions in glassy oxide-based solid state electrolytes using elastic and quasielastic neutron scattering. Samples of xLi2SO4-(1-x)(Li2O-P2O5) were prepared using conventional melt techniques. Elastic and inelastic scattering measurements were performed using the triple-axis spectrometer (TRIAX) at Missouri University Research Reactor at University of Missouri and High Flux Backscattering Spectrometer (HFBS) at NIST Center for Neutron Research, respectively. These compounds have a base glass compound of P2O5 which is modified with Li2O. Addition of Li2SO4 leads to the modification of the structure and to an increase lithium ion (Li+) conduction. We find that an increase of Li2SO4 in the compounds leads to an increase in the Lorentzian width of the fit for the quasielastic data, which corresponds to an increase in Li+ diffusion until an over-saturation point is reached (< 60% Li2SO4). We find that the hopping mechanism is best described by the vacancy mediated Chudley-Elliot model. A fundamental understanding of the diffusion process for these glassy compounds can help lead to the development of a highly efficient solid electrolyte and improve the viability of clean energy technologies.

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18

Chandra, Angesh, Alok Bhatt, and Archana Chandra. "Ion Conduction in Superionic Glassy Electrolytes: An Overview." Journal of Materials Science & Technology 29, no. 3 (March 2013): 193–208. http://dx.doi.org/10.1016/j.jmst.2013.01.005.

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19

Knödler, D., W. Dieterich, and J. Petersen. "Coulombic traps and ion conduction in glassy electrolytes." Solid State Ionics 53-56 (July 1992): 1135–40. http://dx.doi.org/10.1016/0167-2738(92)90302-6.

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20

Braga, M. H., J. A. Ferreira, V. Stockhausen, J. E. Oliveira, and A. El-Azab. "Novel Li3ClO based glasses with superionic properties for lithium batteries." J. Mater. Chem. A 2, no. 15 (2014): 5470–80. http://dx.doi.org/10.1039/c3ta15087a.

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21

Springer, Renaldo E., Tawanda J. Zimudzi, and Derek M. Hall. "Examining the Impact of Solution and Surface Composition on Positive Electrode Kinetics for the All-Iron Redox Flow Battery." ECS Meeting Abstracts MA2022-02, no. 54 (October 9, 2022): 2054. http://dx.doi.org/10.1149/ma2022-02542054mtgabs.

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Efforts to reduce the cost of long-duration energy storage systems have drawn increased interest in all-iron redox flow battery systems due to their inexpensive electrolytes. Previous studies have shown that the kinetics of the positive electrode for the Fe(II, III) reaction in these systems are sluggish on carbon surfaces and require significant overpotentials. Here, we identify how changes to the electrode surface and electrolyte composition can influence the electrochemical rate constants to reduce required overpotentials using a rotating disc electrode (RDE) assembly. The impacts of solution composition in terms of pH, chloride content, and cation species were investigated using a range of electrolyte compositions reported for all-iron flow battery systems. The electrode materials studied were glassy carbon, pyrolytic graphite basal plane, and pyrolytic graphite edge plane. Untreated and electrochemically oxidized electrode materials were quantified using X-ray photoelectron spectroscopy (XPS), and the reaction rate constants were quantified using electron impedance spectroscopy (EIS). Rate constants of the Fe(II, III) reaction on untreated electrode materials were largest on platinum and lowest on glassy carbon with pyrolytic materials providing comparable results. For the materials examined, increases electrolyte chloride content generally decreased the obtained rate constant.

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22

Munoz, Stephen, and Steven Greenbaum. "Review of Recent Nuclear Magnetic Resonance Studies of Ion Transport in Polymer Electrolytes." Membranes 8, no. 4 (November 30, 2018): 120. http://dx.doi.org/10.3390/membranes8040120.

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Current and future demands for increasing the energy density of batteries without sacrificing safety has led to intensive worldwide research on all solid state Li-based batteries. Given the physical limitations on inorganic ceramic or glassy solid electrolytes, development of polymer electrolytes continues to be a high priority. This brief review covers several recent alternative approaches to polymer electrolytes based solely on poly(ethylene oxide) (PEO) and the use of nuclear magnetic resonance (NMR) to elucidate structure and ion transport properties in these materials.

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23

Balogun, Sheriff A., and Omolola E. Fayemi. "Effects of Electrolytes on the Electrochemical Impedance Properties of NiPcMWCNTs-Modified Glassy Carbon Electrode." Nanomaterials 12, no. 11 (May 30, 2022): 1876. http://dx.doi.org/10.3390/nano12111876.

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The supercapacitive properties of synthesized nickel phthalocyanine multiwalled carbon nanotubes nanocomposite on a glassy carbon electrode (NiPcMWCNTs-GCE) in four different electrolytes were investigated. The successful synthesis of the NiPcMWCNTs nanocomposite was confirmed by UV/vis electrode spectroscopy, SEM, TEM, EDX, and XRD techniques. The supercapacitive behaviors of the modified electrodes were examined in PBS, H2SO4, Na2SO4, and SAB electrolytes via CV and EIS techniques. The highest specific capacitance of 6.80 F g−1 was achieved for the GCE-NiPcMWCNTs electrode in 5 mM [Fe(CN)6]4−/3− prepared in 0.1 M PBS (pH 7). Charge transfer resistance Rct values of 0.06, 0.36, 0.61, and 1.98 kΩ were obtained for the GCE-NiPcMWCNTs in H2SO4, SAB, Na2SO4, and PBS electrolytes, respectively. Power density values, otherwise known as the “knee” frequency f°, of 21.2, 6.87, 2.22, and 1.68 Hz were also obtained for GCE-NiPcMWCNTs in H2SO4, Na2SO4, PBS, and SAB electrolytes, respectively. GCE-NiPcMWCNTs demonstrated the fastest electron transport capability and the highest power density in H2SO4 compared to the other electrolytes. Hence, GCE-NiPcMWCNTs-modified electrodes had high stability, high energy and power densities, and a large specific capacitance.

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24

Baskaran, N. "Conductivity relaxation and ion transport processes in glassy electrolytes." Journal of Applied Physics 92, no. 2 (July 15, 2002): 825–33. http://dx.doi.org/10.1063/1.1487456.

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25

Chandra, Angesh, Alok Bhatt, and Archana Chandra. "Synthesis and characterization of Ag+ion conducting glassy electrolytes." European Physical Journal Applied Physics 63, no. 1 (July 2013): 10904. http://dx.doi.org/10.1051/epjap/2013120299.

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26

Chan, Chin Han, and Hans-Werner Kammer. "Low Frequency Dielectric Relaxation and Conductance of Solid Polymer Electrolytes with PEO and Blends of PEO and PMMA." Polymers 12, no. 5 (April 27, 2020): 1009. http://dx.doi.org/10.3390/polym12051009.

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Solid polymer electrolytes are mixtures of polymer and inorganic salt. There are quite a number of studies dealing with the relationship between electric conductivity and structural relaxation in solid polymer electrolytes. We present a phenomenological approach based on fluctuation-dissipation processes. Phase heterogeneity appears in poly(ethylene oxide) (PEO) of high molecular mass and its blends due to crystallization and accompanying phase segregation. Addition of salt hampers crystallization, causing dynamic heterogeneity of the salt mixtures. Conductivity is bound to amorphous phase; the conductivity mechanism does not depend on content of added salt. One observes dispersion of conductivity relaxation only at low frequency. This is also true for blends with poly(methyl methacrylate) (PMMA). In blends, the dynamics of relaxation depend on glass transition of the system. Glassy PMMA hampers relaxation at room temperature. Relaxation can only be observed when salt content is sufficiently high. As long as blends are in rubbery state at room temperature, they behave PEO-like. Blends turn into glassy state when PMMA is in excess. Decoupling of long-ranging and dielectric short-ranging relaxation can be observed. Conductivity mechanism in PEO, as well as in blends with PMMA were analyzed in terms of complex impedance Z*, complex permittivity, tangent loss spectra and complex conductivity.

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27

Protsenko, V. S., and L. S. Bobrova. "Electrode processes in a deep eutectic solvent containing dissolved chromium(III) chloride." Voprosy Khimii i Khimicheskoi Tekhnologii, no. 5 (October 2022): 84–93. http://dx.doi.org/10.32434/0321-4095-2022-144-5-84-93.

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We considered the kinetics of electrochemical processes occurring during electrodeposition of coatings from a low-temperature ionic liquid based on a eutectic mixture of choline chloride and ethylene glycol, in which a trivalent chromium salt is dissolved. Irreversible current waves of Cr(III) ions discharge on a glassy carbon electrode in the electrolytes of studied compositions are not described by the "classical" equations of linear and cyclic voltammetry, which is due to both the presence of the migration component of the current and the cathodic passivation of the electrode. It has been established that the introduction of additional water into the electrolyte leads to an increase in the current density of the wave of irreversible discharge of Cr(III) ions on the glassy carbon electrode, which is caused by a significant decrease in the viscosity of the solution. The current efficiency of the chromium deposition reaction decreases when water is introduced into the ionic liquid. The X-ray amorphous coatings electrodeposited from the electrolyte under study, along with chromium, contain carbon and oxygen, the inclusion of which is due to the electrocatalytic properties of the freshly deposited chromium surface.

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Ram, Rakesh, and Sanjib Bhattacharya. "Mixed ionic-electronic transport in Na₂O doped glassy electrolytes: Promising candidate for new generation sodium ion battery electrolytes." Journal of Applied Physics 133, no. 14 (April 14, 2023): 145101. http://dx.doi.org/10.1063/5.0145894.

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In the present communication, newly developed glassy electrolytes, Na2O–ZnO–CdO, have been considered to discuss their electrical transport behavior at ambient temperature. The AC conductivity and relaxation behavior of them have been studied in the light of Almond-West formalism. The electrical conductivity (mixed conduction) is found to be a function of frequency as well as temperature. In the low-frequency range, it shows a flat conductivity owing to the diffusional motion of Na+ ions, whereas at high frequency, the conductivity shows dispersion. The DC conductivity [Formula: see text] and hopping frequency have been computed from the best fitted plots of experimental data. The AC conductivity at different concentrations and a constant temperature has been reported. The variation in the conductivity data with reciprocal temperatures indicates the dynamical behavior of charge carriers via hopping conduction in sodium oxide glassy systems. Mixed conduction in the present system may be dominated by polaron hopping in the samples with a lower Na2O content with a percolation type of motion of the electron/polaron. On the other hand, three-dimensional Na+ motion is the dominating charge carrier for the samples with a higher Na2O content. A negligible small difference in pathways in the I–V characteristics in both the directions should make the present system a promising candidate for the new generation battery electrolyte.

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29

Siekierski, Maciej, Maja Mroczkowska-Szerszeń, Rafał Letmanowski, Dariusz Zabost, Michał Piszcz, Lidia Dudek, Michał M. Struzik, Magdalena Winkowska-Struzik, Renata Cicha-Szot, and Magdalena Dudek. "Ionic Transport Properties of P2O5-SiO2 Glassy Protonic Composites Doped with Polymer and Inorganic Titanium-based Fillers." Materials 13, no. 13 (July 6, 2020): 3004. http://dx.doi.org/10.3390/ma13133004.

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This paper is focused on the determination of the physicochemical properties of a composite inorganic–organic modified membrane. The electrical conductivity of a family of glassy protonic electrolytes defined by the general formula (P2O5)x(SiO2)y, where x/y is 3/7 are studied by Alternating Current electrochemical impedance spectroscopy (AC EIS) method. The reference glass was doped with polymeric additives—poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA), and additionally with a titanium-oxide-based filler. Special attention was paid to determination of the transport properties of the materials thus modified in relation to the charge transfer phenomena occurring within them. The electrical conductivities of the ‘dry’ material ranged from 10−4 to 10−9 S/cm, whereas for ‘wet’ samples the values were ~10−3 S/cm. The additives also modified the pore space of the samples. The pore distribution and specific surface of the modified glassy systems exhibited variation with changes in electrolyte chemical composition. The mechanical properties of the samples were also examined. The Young’s modulus and Poisson’s ratio were determined by the continuous wave technique (CWT). Based on analysis of the dispersion of the dielectric losses, it was found that the composite samples exhibit mixed-type proton mobility with contributions related to both the bulk of the material and the surface of the pore space.

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30

Ingram, Malcolm D., Corrie T. Imrie, Ioannis Konidakis, and Stephan Voss. "Significance of activation volumes for cation transport in glassy electrolytes." Phys. Chem. Chem. Phys. 6, no. 13 (2004): 3659–62. http://dx.doi.org/10.1039/b314879c.

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31

Musinu, A. "Towards a model of silver halide-silver oxysalt glassy electrolytes." Solid State Ionics 34, no. 3 (May 1989): 187–93. http://dx.doi.org/10.1016/0167-2738(89)90038-6.

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32

KNODLER, D., P. PENDZIG, and W. DIETERICH. "Transport and ac response in a model of glassy electrolytes." Solid State Ionics 70-71 (May 1994): 356–61. http://dx.doi.org/10.1016/0167-2738(94)90336-0.

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33

Imrie, Corrie T., Malcolm D. Ingram, and Gillian S. McHattie. "Ion Transport in Glassy Side-Group Liquid Crystalline Polymer Electrolytes." Advanced Materials 11, no. 10 (July 1999): 832–34. http://dx.doi.org/10.1002/(sici)1521-4095(199907)11:10<832::aid-adma832>3.0.co;2-z.

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34

Ndeugueu, Jean Léopold, and Masaru Aniya. "Classification of Glassy and Polymer Electrolytes for Lithium-Ion Batteries by the Bond-Strength-Coordination Number Fluctuation Model." Advanced Materials Research 123-125 (August 2010): 1075–78. http://dx.doi.org/10.4028/www.scientific.net/amr.123-125.1075.

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This article deals with the classification of glassy and polymer electrolytes for lithium-ion batteries into the so-called “strong/fragile” scale, by the means of the bond-strength-coordination number fluctuation model. We have evaluated the strength parameter, which plays a key role in the understanding of the relaxation phenomena, of each lithium-ion conductor under consideration. We have derived a relationship that not only describes accurately the experimental results, but also provides important details on the interrelation between the strength parameter, the bond strength of the structural unit, the binding energy, the coordination number and the glass transition temperature.

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35

Torres III, Victor Manuel, Steve Martin, and Presley Philipp. "Preparation of Li-Si-P-S-O-N Glasses: The Impact of Lipon Incorporation on Ionic Conductivity." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 480. http://dx.doi.org/10.1149/ma2022-024480mtgabs.

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Lithium glassy solid electrolytes (GSEs) are an alternative to liquid electrolytes in the development of solid-state batteries. Mixed oxy-sulfide nitride GSEs incorporate the useful properties of sulfide glasses, which show high ionic conductivity, of oxide glasses which display excellent chemical stability, and of nitride glasses which exhibit good electrochemical stability. In our investigation of these new GSEs, the following compositional series was explored Li2S + SiS2 + [(1-x)Li0.67PO2.83 + xLiPON]. Differential scanning calorimetry (DSC) was employed to determine the crystallization and glass temperatures of these GSEs. In addition, electrochemical impedance spectroscopy (EIS) was used to determine the temperature-dependent ionic conductivity of theses GSEs. X-ray Photoelectron Spectroscopy (XPS) was conducted on the glasses to further understand the chemical bonding environment of nitrogen. It was found that x = 0.2 displayed the highest ionic conductivity suggesting that nitrogen incorporation can be used to optimize mixed oxy-sulfide glasses. Support of this research by NSF Grant NSF-DMR-1936913 is acknowledged.

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36

Gurkan, Burcu, William Dean, and Drace Penley. "(Invited) Concentrated Hydrogen Bonded Electrolytes: Definition and Bulk & Interfacial Properties." ECS Meeting Abstracts MA2022-02, no. 55 (October 9, 2022): 2112. http://dx.doi.org/10.1149/ma2022-02552112mtgabs.

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We broadly refer to deep eutectic solvents (DESs) as concentrated H-bonded electrolytes (CoHBEs) where a composition specific to the “deep eutectic temperature” does not have to be met as long as the electrolyte possesses high salt concentration of the salt or the redox active specie and suppressed volatility are desired in energy storage, electrocatalysis, and electrodeposition processes. Liquid heterogeneity owing to H-bonding, similar to ionic liquids and DESs, CoHBEs present distinct electrode-electrolyte interfacial behavior. As a way to probe the electrode-electrolyte behavior of CoHBEs as a function of composition, we have performed electrochemical impedance spectroscopy and surface enhanced Raman spectroscopy (SERS). The potential dependent differential capacitance of choline chloride and ethylene glycol (1:2, 1:4, 1:6 molar ratio) mixtures do not present camel shaped curves as in the case of more extreme examples of concentrated electrolytes such as ionic liquids. The interfacial behavior is more similar to dilute systems, however, the H-bonding network presents a less mobile diffuse layer. While on glassy carbon, there is no specific ion adsorption, on metal electrodes chloride adsorption is observed. In chloride-free systems that are based choline oxalate mixed with ethylene glycol, capacitance is measured to be almost independent of the applied voltage on glassy carbon and gold. This is attributed to the strong binding energy of the solvation structure, as determined from theory, that hinders voltage-induced reorientations. Consistent to this behavior, the oxalate system also presents a very high viscosity. In addition, the voltage sweep range is limited in the case of oxalate system as it has narrower electrochemical window. On the other hand, choline acetate, which has a very similar chemical structure to the oxalate, undergoes specific ion adsorption particularly on gold electrode at a positive applied potential as confirmed by SERS. This is believed to be due to the reduced binding energy as calculated by density functional theory with -1 charge of the acetate in comparison to -2 charge in oxalate that leads to the desolvation and then the surface adsorption of the acetate. In the case of the choline bis(trifluorosulfonyl)imide and ethylene glycol mixture, a wider electrochemical window accompanied by a dampened u-shaped capacitance was observed with no specific ion adsorption. This study presents tuning of DESs and more broadly CoHBEs in terms of the bulk physical properties, the interfacial behavior near an electrode, and the coupled structuring effects through the variation in anion charge density and the extent of H-bonding.

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Schauser, Nicole S., Katherine J. Harry, Dilworth Y. Parkinson, Hiroshi Watanabe, and Nitash P. Balsara. "Lithium Dendrite Growth in Glassy and Rubbery Nanostructured Block Copolymer Electrolytes." Journal of The Electrochemical Society 162, no. 3 (December 29, 2014): A398—A405. http://dx.doi.org/10.1149/2.0511503jes.

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Adams, S. "Ag migration pathways in crystalline and glassy solid electrolytes AgI–AgMxOy." Solid State Ionics 105, no. 1-4 (January 1, 1998): 67–74. http://dx.doi.org/10.1016/s0167-2738(97)00450-5.

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39

Satyanarayana, N., A. Karthikeyan, and M. Venkateswarlu. "Monte Carlo simulation of ion conduction in silver based glassy electrolytes." Materials Science and Engineering: B 47, no. 3 (June 1997): 210–17. http://dx.doi.org/10.1016/s0921-5107(97)00040-8.

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40

Prasada Rao, R., T. D. Tho, and S. Adams. "Ion transport pathways in molecular dynamics simulated alkali silicate glassy electrolytes." Solid State Ionics 192, no. 1 (June 2011): 25–29. http://dx.doi.org/10.1016/j.ssi.2009.12.010.

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Karthikeya, A., and N. Satyanarayana. "Solid-state batteries using silver-based fast ionic conducting glassy electrolytes." Journal of Power Sources 51, no. 3 (October 1994): 457–62. http://dx.doi.org/10.1016/0378-7753(94)80113-4.

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42

Deshpande, V. K. "Factors affecting ionic conductivity in the lithium conducting glassy solid electrolytes." Ionics 10, no. 1-2 (January 2004): 20–26. http://dx.doi.org/10.1007/bf02410300.

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43

Ingram, Malcolm D., Philipp Maass, and Armin Bunde. "Frequency-Dependent Conductivity. Ionic Conductivity and Memory Effects in Glassy Electrolytes." Berichte der Bunsengesellschaft für physikalische Chemie 95, no. 9 (September 1991): 1002–6. http://dx.doi.org/10.1002/bbpc.19910950910.

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44

NOWAK, ANDRZEJ P., and ANNA LISOWSKA-OLEKSIAK. "ELECTROCHEMICAL ACTIVITY OF COMPOSITE MATERIAL POLY(3, 4-ETHYLENEDIOXYTHIOPHENE) MODIFIED BY SILVER HEXACYANOFERRATE." Functional Materials Letters 04, no. 02 (June 2011): 205–8. http://dx.doi.org/10.1142/s1793604711001889.

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An electrochemical way to prepare poly(3, 4-ethylenedioxythiophene) (pEDOT) modified by silver hexacyanoferrate (Aghcf) is presented. The electrode material is synthesized in two-stage procedure. The first stage is galvanic silver electrodeposition on a glassy carbon substrate electrode. The second step is silver stripping followed by Aghcf formation during monomer oxidation. Deposited composite layer is compact but not homogenous in a micro-scale. The low spin iron centre redox activity depends on a kind of the electrolyte. Potassium and nitrate ions are the most suitable for redox couple reversibility. The redox activity diminishes in contact with electrolytes in series KNO 3 > K 2 SO 4 > KBr . In the presence of chloride ions redox activity of silver hexacyanoferrate is inhibited. Spectroelectrochemical measurements proved electrochromic character of the film.

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45

Modak, Sanat Vibhas, Joseph Valle, David G. Kwabi, and Jeff Sakamoto. "(Digital Presentation) Evaluating Stability and Performance of Nasicon Membranes for Crossover Mitigation in Aqueous Redox-Flow Batteries." ECS Meeting Abstracts MA2022-01, no. 48 (July 7, 2022): 1997. http://dx.doi.org/10.1149/ma2022-01481997mtgabs.

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Most polymer-based membranes that are used in prototypical aqueous redox-flow batteries (RFBs) do not adequately prevent crossover of small-molecule reactants, causing high rates of capacity fade. Ceramic superionic conductor membranes are an attractive alternative due to their superior abilities to mitigate crossover;1 they can thus enable the deployment of electrolytes containing earth-abundant, small-molecule reactants.2 3 We test the performance and stability of a von Alpen sodium superionic conductor Na3.1Zr1.55Si2.3P0.7O11 (NaSICON) as an RFB membrane by examining its resistance, permeability and interfacial morphology as a function of electrolyte composition and temperature. The resistance of NaSICON is stable for several weeks while immersed in neutral to strongly alkaline ([OH-] = 3 M) aqueous electrolytes, and its permeability to polysulfide-based and permanganate-based small-molecule RFB reactants is negligible compared to that of Nafion. The glassy phase of the NaSICON microstructure at the membrane-electrolyte interface undergoes small amounts of etching while in contact with aqueous electrolytes containing sodium ions, which becomes more extensive when potassium ions are present in the electrolyte, leading in certain instances to complete disintegration of the membrane. We report a ferrocyanide-permanganate flow cell at a pH of 14.5 with a ~ 700 μm-thin NaSICON membrane supporting weeks of cycling with apparently negligible reactant crossover and very low capacity fade (< 0.04 %/day). Area-specific resistance of NaSICON falls dramatically with increasing temperature and decreasing membrane thickness, and a membrane that is 100 µm thick or thinner can enable power densities at above-ambient temperatures that are comparable to power densities of polymer membrane-containing flow cells. (1) Yu, X.; Gross, M. M.; Wang, S.; Manthiram, A. Aqueous Electrochemical Energy Storage with a Mediator-Ion Solid Electrolyte. Advanced Energy Materials 2017, 7 (11), 1602454, https://doi.org/10.1002/aenm.201602454. DOI: https://doi.org/10.1002/aenm.201602454 (acccessed 2021/03/12). (2) Wei, X.; Xia, G.-G.; Kirby, B.; Thomsen, E.; Li, B.; Nie, Z.; Graff, G. G.; Liu, J.; Sprenkle, V.; Wang, W. An aqueous redox flow battery based on neutral alkali metal ferri/ferrocyanide and polysulfide electrolytes. J. Electrochem. Soc. 2016, 163 (1), A5150-A5153. DOI: 10.1149/2.0221601jes]. (3) Colli, A. N.; Peljo, P.; Girault, H. H. High energy density MnO4-/MnO42- redox couple for alkaline redox flow batteries. Chem Commun (Camb) 2016. DOI: 10.1039/c6cc08070g.

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Modak, Sanat Vibhas, Flora Tseng, Joseph Valle, Jeff Sakamoto, and David G. Kwabi. "Evaluating the Stability and Performance of Nasicon in Low-Cost High Charge Density Redox Flow Battery Electrolytes." ECS Meeting Abstracts MA2022-02, no. 46 (October 9, 2022): 1707. http://dx.doi.org/10.1149/ma2022-02461707mtgabs.

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Solid superionic conductor membranes are being considered as alternatives to polymer-based membranes for use in redox flow batteries (RFBs) due to their superior abilities to mitigate reactant crossover,1 and enable the deployment of aqueous electrolytes comprising small, inorganic earth-abundant reactants.2,3 Much however remains to be understood about the evolution of the electrochemical performance and microstructural stability of these membranes while they are immersed in aqueous electrolytes. In this work, we evaluate the suitability of von Alpen sodium superionic conductor (NaSICON) as a prospective RFB membrane material by examining its resistance, permeability and interfacial morphology over time as a function of electrolyte pH and composition, as well as temperature. NaSICON is found to have a stable resistance profile for several weeks while immersed in neutral to strongly alkaline ([OH-] = 3 M) aqueous electrolytes. Its permeability to polysulfide-based and permanganate-based small-molecule RFB reactants is negligible compared to that of Nafion. Its area-specific resistance falls dramatically with increasing temperature and decreasing membrane thickness; we project that a membrane with a thickness of 100 μm or lower, if operated slightly above ambient temperature (~ 40 °C), can enable power densities comparable to or better than those of conventional polymer membrane-containing RFBs. Nevertheless, the glassy phase of the NaSICON microstructure at the membrane-electrolyte interface was found to undergo small amounts of etching while in contact with aqueous electrolytes containing sodium ions; this etching became significantly more extensive when potassium ions were present in the electrolyte, leading in certain instances to complete disintegration of the membrane. The extraordinary high stability of NaSICON in strongly alkaline electrolyte permits the construction of flow cells containing a positive electrolyte based on permanganate, a high-potential, inexpensive reactant with high volumetric capacity (> 100 Ah/L). The flow cells had open-circuit voltages 1.2 V and greater, along with negligible reactant crossover and very low capacity fade (< 0.02 %/day). This work highlights the promise of ceramic membranes as effective separators in RFBs operating under neutral pH to strongly alkaline pH conditions. It also points to the need for further research on the long-term stability of the membrane and its interface with the electrolyte in solid-state membranes under investigation as separators in aqueous RFBs. (1) Yu, X.; Gross, M. M.; Wang, S.; Manthiram, A. Aqueous Electrochemical Energy Storage with a Mediator-Ion Solid Electrolyte. Advanced Energy Materials 2017, 7 (11), 1602454, https://doi.org/10.1002/aenm.201602454. DOI: https://doi.org/10.1002/aenm.201602454 (acccessed 2021/03/12). (2) Wei, X.; Xia, G.-G.; Kirby, B.; Thomsen, E.; Li, B.; Nie, Z.; Graff, G. G.; Liu, J.; Sprenkle, V.; Wang, W. An aqueous redox flow battery based on neutral alkali metal ferri/ferrocyanide and polysulfide electrolytes. J. Electrochem. Soc. 2016, 163 (1), A5150-A5153. DOI: 10.1149/2.0221601jes]. (3) Colli, A. N.; Peljo, P.; Girault, H. H. High energy density MnO4-/MnO42- redox couple for alkaline redox flow batteries. Chem Commun (Camb) 2016. DOI: 10.1039/c6cc08070g.

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Kumar Gupta, Pankaj, Akshay Dvivedi, and Pradeep Kumar. "Effect of Electrolytes on Quality Characteristics of Glass during ECDM." Key Engineering Materials 658 (July 2015): 141–45. http://dx.doi.org/10.4028/www.scientific.net/kem.658.141.

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Electrochemical discharge machining (ECDM) is an ideal process for machining of nonconductive materials in micro-domain. The material removal takes place due to combined action of localised sparks and electrolysis in an electrolytic chamber. The electrolyte is most important process parameter for ECDM as it governs spark action as well as electrolysis. This article presents a comparison of three preferred electrolytes used in ECDM viz. NaCl, KOH and NaOH on drilling of glass workpiece material. The quality characteristics measured are material removal rate (MRR) and hole overcut. Results reveal that NaOH provides 9.7 and 3.8 times higher MRR than NaCl and KOH respectively. MRR and hole overcut are found significantly affected by spark characteristics.

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Li, Jing, Hua Qing Xie, and Yang Li. "Template-Free Electrochemical Synthesis of Well-Aligned Polypyrrole Nanofibers for Electrochemical Supercapacitors." Advanced Materials Research 512-515 (May 2012): 1776–79. http://dx.doi.org/10.4028/www.scientific.net/amr.512-515.1776.

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A new well-aligned nanofibers structure of polypyrrole (WAPPy) has been successfully grown on glassy carbon electrode by using a simple, reliable, and template-free electrochemical technique. The unique structure and design not only reduces the diffusion resistance of electrolytes in the electrode material but also enhances its electrochemical performance. Electrochemical supercapacitors based on WAPPy achieved a specific capacitance of 365 F g-1 with an applied charge/discharge current density of 1 A g-1 over a potential window of -0.5 to 0.5 V. For comparison, the granules PPy particles have been also electrochemical synthesized by using KCl as electrolyte (PPy-Cl). The specific capacitance of PPy-Cl electrode is 120 F g-1. The high specific capacitance and good stability of the WAPPy electrode has great potential in various applications such as energy storage.

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Staacke, Carsten G., Tabea Huss, Johannes T. Margraf, Karsten Reuter, and Christoph Scheurer. "Tackling Structural Complexity in Li2S-P2S5 Solid-State Electrolytes Using Machine Learning Potentials." Nanomaterials 12, no. 17 (August 26, 2022): 2950. http://dx.doi.org/10.3390/nano12172950.

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The lithium thiophosphate (LPS) material class provides promising candidates for solid-state electrolytes (SSEs) in lithium ion batteries due to high lithium ion conductivities, non-critical elements, and low material cost. LPS materials are characterized by complex thiophosphate microchemistry and structural disorder influencing the material performance. To overcome the length and time scale restrictions of ab initio calculations to industrially applicable LPS materials, we develop a near-universal machine-learning interatomic potential for the LPS material class. The trained Gaussian Approximation Potential (GAP) can likewise describe crystal and glassy materials and different P-S connectivities PmSn. We apply the GAP surrogate model to probe lithium ion conductivity and the influence of thiophosphate subunits on the latter. The materials studied are crystals (modifications of Li3PS4 and Li7P3S11), and glasses of the xLi2S–(100 – x)P2S5 type (x = 67, 70 and 75). The obtained material properties are well aligned with experimental findings and we underscore the role of anion dynamics on lithium ion conductivity in glassy LPS. The GAP surrogate approach allows for a variety of extensions and transferability to other SSEs.

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Bartolotta, A., G. Di Marco, E. Bonetti, and G. Carini. "Mechanical behavior of polymeric electrolytes in the glassy and rubber-like regions." Solid State Communications 67, no. 5 (August 1988): 561–64. http://dx.doi.org/10.1016/0038-1098(84)90183-2.

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