Journal articles: 'Ion Conducting Polymer Electrolytes'

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Kohl, Paul, Mrinmay Mandal, Mengjie Chen, Habin Park, and Parin Shah. "(Invited) Anion Conducting Solid Polymer Ionomers Electrolytes for Fuel Cells and Electrolyzers." ECS Meeting Abstracts MA2022-02, no. 46 (October 9, 2022): 1718. http://dx.doi.org/10.1149/ma2022-02461718mtgabs.

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Ion conducting polymer electrolytes provide an enabling technology for the creation of low temperature fuel cells, hydrogen producing water electrolyzers, and flow batteries. The critical parameters of solid polymer electrolytes include ionic conductivity, ion selectivity, chemical resistance and dimensional stability in the presence of excess water. High pH operation using anion conductive polymer electrolytes has several potential advantages over acid-based polymer devices including low-cost catalysts, hydrocarbon (non-perfluorinated) polymer, and low cost cell components. However, the identification and synthesis of stable, hydroxide conducting solid polymer electrolytes has been elusive. In this study, a family of hydroxide conducting, poly(norbornene) solid polymer electrolytes were synthesized and used in high-performance, durable membrane electrode assemblies for fuel cells and electrolyzers. In addition to membranes, covalently bonded, self-adherent, hydroxide conducting ionomers were used to form high-performance, durable membrane electrode assembly for water electrolysis. Electrodes made by grind-spray method were compared to electrodes prepared by the solvent-cast method. The self-adhesive ionomers and membranes are based on hydroxide conducting poly(norbornene) polymers. The effect of porous transport layer material and porosity was examined. High performance electrolysis with very low degradation rates was achieved using stainless steel and nickel porous transport layers.

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Watanabe, Masayoshi. "Ion Conducting Polymers Polymer Electrolytes." Kobunshi 42, no. 8 (1993): 702–5. http://dx.doi.org/10.1295/kobunshi.42.702.

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Scrosati, Bruno. "Ion-conducting polymer electrolytes." Philosophical Magazine B 59, no. 1 (January 1989): 151–60. http://dx.doi.org/10.1080/13642818908208454.

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Ghorbanzade, Pedram, Laura C. Loaiza, and Patrik Johansson. "Plasticized and salt-doped single-ion conducting polymer electrolytes for lithium batteries." RSC Advances 12, no. 28 (2022): 18164–67. http://dx.doi.org/10.1039/d2ra03249j.

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Lee, Kyoung-Jin, Eun-Jeong Yi, Gangsanin Kim, and Haejin Hwang. "Synthesis of Ceramic/Polymer Nanocomposite Electrolytes for All-Solid-State Batteries." Journal of Nanoscience and Nanotechnology 20, no. 7 (July 1, 2020): 4494–97. http://dx.doi.org/10.1166/jnn.2020.17562.

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Lithium-ion conducting nanocomposite solid electrolytes were synthesized from polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), LiClO4, and Li1.3Al0.3Ti1.7(PO4)3 (LATP) ceramic particles. The synthesized nanocomposite electrolyte consisted of LATP particles and an amorphous polymer. LATP particles were homogeneously distributed in the polymer matrix. The nanocomposite electrolytes were flexible and self-standing. The lithium-ion conductivity of the nanocomposite electrolyte was almost an order of magnitude higher than that of the PEO/PMMA solid polymer electrolyte.

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Hoffman, Zach J., Alec S. Ho, Saheli Chakraborty, and Nitash P. Balsara. "Limiting Current Density in Single-Ion-Conducting and Conventional Block Copolymer Electrolytes." Journal of The Electrochemical Society 169, no. 4 (April 1, 2022): 043502. http://dx.doi.org/10.1149/1945-7111/ac613b.

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The limiting current density of a conventional polymer electrolyte (PS-PEO/LiTFSI) and a single-ion-conducting polymer electrolyte (PSLiTFSI-PEO) was measured using a new approach based on the fitted slopes of the potential obtained from lithium-polymer-lithium symmetric cells at a constant current density. The results of this method were consistent with those of an alternative framework for identifying the limiting current density taken from the literature. We found the limiting current density of the conventional electrolyte is inversely proportional to electrolyte thickness as expected from theory. The limiting current density of the single-ion-conducting electrolyte was found to be independent of thickness. There are no theories that address the dependence of the limiting current density on thickness for single-ion-conducting electrolytes.

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Ogata, N., K. Sanui, M. Rikukawa, S. Yamada, and M. Watanabe. "Super ion conducting polymers for solid polymer electrolytes." Synthetic Metals 69, no. 1-3 (March 1995): 521–24. http://dx.doi.org/10.1016/0379-6779(94)02553-b.

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K Manjula, K. Manjula, and V. John Reddy. "Na+ Ion Conducting Nano-Composite Solid Polymer Electrolyte – Application to Electrochemical Cell." Oriental Journal Of Chemistry 38, no. 5 (October 31, 2022): 1204–8. http://dx.doi.org/10.13005/ojc/380515.

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Various concentrations of Multi Walled Carbon Nanotubes (MCNT) fillers dispersed PVDF- HFP: NaClO4 nanocomposite polymer electrolytes (NPE) were prepared by solution casting technique. The dispersion of MCNT nano fillers raised the accessibility of more ions for attaining the highest conductivity. Electrical conductivity, Ohmic resistance (RΩ), Polarisation resistanace (Rp), and Warburg impedance (W) were studied using electrochemical impedance spectroscopy (EIS), which revealed ion transport mechanics in the polymer electrolytes. The best ionic conductivity is found to be 8.46 × 10-3 Scm-1 for the 7 wt.% dispersed MCNT Nanocomposite Solid Polymer electrolyte among all polymer electrolyte samples. Electrochemical cell was made by PVDF-HFP:NaClO4 : MCNT polymer electrolyte and exhibited 1.95 V open circuit voltage and 2.5 mA short circuit current, respectively.

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Zhang, Heng, Chunmei Li, Michal Piszcz, Estibaliz Coya, Teofilo Rojo, Lide M. Rodriguez-Martinez, Michel Armand, and Zhibin Zhou. "Single lithium-ion conducting solid polymer electrolytes: advances and perspectives." Chemical Society Reviews 46, no. 3 (2017): 797–815. http://dx.doi.org/10.1039/c6cs00491a.

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Single lithium-ion conducting solid polymer electrolytes (SLIC-SPEs), with a high lithium-ion transference number, the absence of the detrimental effect of anion polarization, and low dendrite growth rate, could be an excellent choice of safe electrolyte materials for lithium batteries in the future.

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Leena Chandra, Manuel Victor, Shunmugavel Karthikeyan, Subramanian Selvasekarapandian, Manavalan Premalatha, and Sampath Monisha. "Study of PVAc-PMMA-LiCl polymer blend electrolyte and the effect of plasticizer ethylene carbonate and nanofiller titania on PVAc-PMMA-LiCl polymer blend electrolyte." Journal of Polymer Engineering 37, no. 6 (July 26, 2017): 617–31. http://dx.doi.org/10.1515/polyeng-2016-0145.

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Abstract lithium ion conducting polymer electrolyte is one of the essential components of modern rechargeable lithium batteries because of its good interfacial contact with electrodes and effective mechanical properties. A solid lithium ion conducting polymer blend electrolyte is prepared using poly (vinyl acetate) (PVAc) and poly (methyl methacrylate) (PMMA) polymers with different molecular weight percentages (wt%) of lithium chloride (LiCl) by the solution casting technique with tetrahydrofuran as a solvent. The polymer electrolytes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), Thermogravimetry (TG), AC impedance spectroscopy and ionic transport measurements. XRD and FTIR studies confirm the amorphous nature of the polymer electrolyte and the complexation of salt with polymer. The thermal behavior of polymer electrolytes has been studied from DSC and TG. The highest conductivity obtained using AC impedance spectroscopy is 1.03×10−5 Scm−1 at 303 K for 70 wt%PVAc:30 wt%PMMA:0.8 wt% of LiCl polymer-salt complex. The plasticizer ethylene carbonate (EC) and nanofiller titania (TiO2) were added to the optimized high conducting blend polymer electrolyte. An enhancement in conductivity by one order of magnitude was observed for the plasticized 70 wt%PVAc-30 wt%PMMA-0.8 wt% LiCl polymer electrolyte at ambient temperature. The ionic conductivity value obtained using AC impedance spectroscopy for the plasticized 70 wt%PVAc-30 wt%PMMA-0.8 wt% LiCl polymer electrolyte was 1.03×10−4 Scm−1. The highest conductivity obtained for 70 wt%PVAc-30 wt%PMMA-0.8% LiCl-6 mg TiO2 was 4.45×10−4 Scm−1. Dielectric properties of polymer films are studied and discussed. The electrochemical stability of 1.69 V and 2.69 V was obtained for 70 wt%PVAc-30 wt%PMMA-0.8% LiCl and 70 wt%PVAc-30 wt%PMMA-0.8% LiCl-6 mg TiO2 polymer electrolytes, respectively, using linear sweep voltammetry. The value of Li+ ion transference number was estimated by the DC polarization method and was found to be 0.99 for the highest conducting 70 wt%PVAc-30 wt%PMMA-0.8 wt% LiCl-6 mg TiO2 nanocomposite polymer electrolyte.

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Park, Bumjun, Rassmus Andersson, Sarah G. Pate, Jiacheng Liu, Casey P. O’Brien, Guiomar Hernández, Jonas Mindemark, and Jennifer L. Schaefer. "Ion Coordination and Transport in Magnesium Polymer Electrolytes Based on Polyester-co-Polycarbonate." Energy Material Advances 2021 (September 15, 2021): 1–14. http://dx.doi.org/10.34133/2021/9895403.

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Magnesium-ion-conducting solid polymer electrolytes have been studied for rechargeable Mg metal batteries, one of the beyond-Li-ion systems. In this paper, magnesium polymer electrolytes with magnesium bis(trifluoromethane)sulfonimide (Mg(TFSI)2) salt in poly(ε-caprolactone-co-trimethylene carbonate) (PCL-PTMC) were investigated and compared with the poly(ethylene oxide) (PEO) analogs. Both thermal properties and vibrational spectroscopy indicated that the total ion conduction in the PEO electrolytes was dominated by the anion conduction due to strong polymer coordination with fully dissociated Mg2+. On the other hand, in PCL-PTMC electrolytes, there is relatively weaker polymer–cation coordination and increased anion–cation coordination. Sporadic Mg- and F-rich particles were observed on the Cu electrodes after polarization tests in Cu|Mg cells with PCL-PTMC electrolyte, suggesting that Mg was conducted in the ion complex form (MgxTFSIy) to the copper working electrode to be reduced which resulted in anion decomposition. However, the Mg metal deposition/stripping was not favorable with either Mg(TFSI)2 in PCL-PTMC or Mg(TFSI)2 in PEO, which inhibited quantitative analysis of magnesium conduction. A remaining challenge is thus to accurately assess transport numbers in these systems.

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Engler, Anthony, Habin Park, Nian Liu, and Paul Kohl. "Cyclic Carbonate-Based, Single-Ion Conducting Polymer Electrolytes for Li-Ion Batteries: Electrolyte Design." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 2437. http://dx.doi.org/10.1149/ma2022-0122437mtgabs.

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Solid polymer electrolytes (SPEs) have been the focus of study to address Li-ion battery issues including thermal runaway by mitigating the danger from volatile solvents. A single ion conductor has a high transference number which eliminates uncontrolled mass transport by immobilizing the anion to the polymer matrix. Problems with undesired side reactions and lithium dendrite growth can also be improved by providing a mechanical barrier. Unfortunately, single-ion conducting SPEs suffer from poor lithium-ion mobility and conductivity due to the immobilized nature of the anions, poor ion-pair dissociation, and the slower time scale diffusion in a polymer matrix compared to liquid electrolytes. In this study, cyclic carbonate-based polymer electrolytes were synthesized to mimic the beneficial properties of conventional carbonate-based liquid electrolytes, such as high level of ion dissociation and solid electrolyte interphase (SEI) formation. A series of copolymers were synthesized varying the structure and composition of the anionic monomer and polar cyclic carbonate containing monomer. The tertiary hydrogen on these carbonate monomers can act as a crosslinking point in free radical polymerizations or UV curing processes to provide robust mechanical properties to the SPEs at elevated temperatures. Although the inherent conductivities of the single-ion SPEs are on the order of 10-7 mS/cm, the addition of plasticizers can improve these conductivities to 0.1 mS/cm.

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Li, Jak, Jinli Qiao, and Keryn Lian. "Investigation of polyacrylamide based hydroxide ion-conducting electrolyte and its application in all-solid electrochemical capacitors." Sustainable Energy & Fuels 1, no. 7 (2017): 1580–87. http://dx.doi.org/10.1039/c7se00266a.

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Hallinan, Daniel T., Michael P. Blatt, Kyoungmin Kim, Nam Nguyen, Stephanie F. Marxsen, Sage Smith, Rufina G. Alamo, and Justin G. Kennemur. "Advancements in Polymer Blend Electrolytes for Lithium-Ion Conduction." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2566. http://dx.doi.org/10.1149/ma2022-0272566mtgabs.

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Increasing the energy density of lithium-ion batteries requires, among other advances, electrolytes that are compatible with lithium metal and next-generation cathodes. Polymer electrolytes play an important role in this regard, but overcoming slow ion transport is a major challenge. Hybrid electrolytes that combine fast ion transport of ceramic electrolytes and processability of polymer electrolytes are promising. To take advantage of transport in both phases, transference numbers should be comparable. Thus, single-ion conducting polymer electrolytes have received major focus in recent years. In addition to the benefit in hybrid electrolytes, single-ion conduction yields numerous transport and efficiency advantages in neat polymer electrolytes. Due to formulation simplicity and motivated by block copolymer advancements, our team has focused on polymer blend electrolytes. State of the art in these electrolytes will be reviewed including recent advancements from our team using precision polyanions with polyether solvating polymer. This presentation will cover miscibility, conductivity, and transference numbers as a function of composition and temperature. Distinct differences between blends containing the different anionic forms will be explained in the context of ion correlation. Important future directions for the subfield of polymer blend electrolytes will also be discussed.

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Park, Habin, Anthony Engler, Nian Liu, and Paul Kohl. "Dynamic Anion Delocalization of Single-Ion Conducting Polymer Electrolyte for High-Performance of Solid-State Lithium Metal Batteries." ECS Meeting Abstracts MA2022-02, no. 3 (October 9, 2022): 227. http://dx.doi.org/10.1149/ma2022-023227mtgabs.

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Lithium metal batteries (LMBs) have been considered as next-generation energy storages due to their extremely high theoretical specific capacity (3860 mAh g-1). However, current LMBs, using conventional liquid electrolytes, still could not fulfill the demand of soaring expansion of energy era, such as electrical vehicles, because of their safety issues, originated by uncontrollable electrolytic side reaction on the lithium, resulting unstable solid-electrolyte interphase (SEI) and vicious lithium dendritic growth [1]. Also, carbonate-based liquid electrolytes have an intrinsic flammability, and the lithium dendrite, which short-circuits a cell, can lead to severe safety hazard with the unfavorable flammability of current liquid system when they are ignited. Therefore, solid-state electrolytes have been spotlighted recently for a pathway for safe, and high energy and power LMBs, due to their superior thermal stability and low vapor pressure, while maintaining suitable electrolytic performances. In this study, solid-state single-ion conducting polymer electrolytes (SICPEs), utilizing dynamic anion delocalization (DAD), realizing high ionic conductivity and dimensional stability for high-performance LMB, are studied. The SICPEs enable superior lithium transference number, resulting in highly reduced concentration gradient of lithium cation along the electrolyte to suppress the undesirable lithium dendritic growth. However, SICPEs have prominently lower ionic conductivity than dual-ion conducting polymer electrolyte (DICPEs), which is a critical issue to make a slower charge/discharge for SICPEs [2]. Although an approach utilizing gel polymer electrolyte (GPE), using a liquid solvent as a plasticizer, has been exploited to increase the ionic conductivity of SICPEs, GPEs have struggled with lower mechanical stability, compared to solid state, and still existing flammability issue with the plasticizer. The novel plasticizer, which is described here, can interact with bulky anionic polymer matrix, so that the negative charge can be dispersed onto the whole complex by DAD. Once the bulky complex is formed by DAD, the dissociation of lithium cation from anionic matrix can be easier with the decreased activation energy and higher ionic conduction. While increasing the ionic conductivity with DAD, the nature of polymeric plasticizer will highly suppress flammability. DAD allows the membrane endure more tensile strength due to the dynamic structural change in crosslinking state, so that the polymer electrolyte can tolerate dendritic growth of lithium by morphological change on an electrode surface. The obvious advantages of DAD-induced solid polymer electrolytes in this study for a high energy and power, and ultra-safe LMB can present a novel approach of polymer electrolyte design to the astronomical demand of energy storages. [1] F. Ahmed, I. Choi, M.M. Rahman, H. Jang, T. Ryu, S. Yoon, L. Jin, Y. Jin, W. Kim, ACS Appl. Mater. Interfaces 2019, 11, 34930-34938. [2] D.-M. Shin, J.E. Bachman, M.K. Taylor, J. Kamcev, J.G. Park, M.E. Ziebel, E. Velasquez, N.N. Jarenwattananon, G.K. Sethi, Y. Cui, J.R. Long, Adv. Mater. 2020, 32, 1905771.

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Villaluenga, Irune, Kevin H. Wujcik, Wei Tong, Didier Devaux, Dominica H. C. Wong, Joseph M. DeSimone, and Nitash P. Balsara. "Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries." Proceedings of the National Academy of Sciences 113, no. 1 (December 22, 2015): 52–57. http://dx.doi.org/10.1073/pnas.1520394112.

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Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10−4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li+/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.

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Walkowiak, Mariusz, Monika Osińska, Teofil Jesionowski, and Katarzyna Siwińska-Stefańska. "Synthesis and characterization of a new hybrid TiO2/SiO2 filler for lithium conducting gel electrolytes." Open Chemistry 8, no. 6 (December 1, 2010): 1311–17. http://dx.doi.org/10.2478/s11532-010-0110-3.

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AbstractThis paper describes the synthesis and properties of a new type of ceramic fillers for composite polymer gel electrolytes. Hybrid TiO2-SiO2 ceramic powders have been obtained by co-precipitation from titanium(IV) sulfate solution using sodium silicate as the precipitating agent. The resulting submicron-size powders have been applied as fillers for composite polymer gel electrolytes for Li-ion batteries based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF/HFP) copolymeric membranes. The powders, dry membranes and gel electrolytes have been examined structurally and electrochemically, showing favorable properties in terms of electrolyte uptake and electrochemical characteristics in Li-ion cells.

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Menisha, Mithunaraj, M. A. K. L. Dissanayake, and K. Vignarooban. "Quasi-Solid State Polymer Electrolytes Based on PVdF-HFP Host Polymer for Sodium-Ion Secondary Batteries." Key Engineering Materials 950 (July 31, 2023): 99–104. http://dx.doi.org/10.4028/p-obe3dm.

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Prices of lithium raw materials keep on increasing exponentially due to their heavy consumption for lithium batteries used in portable electronic devices as well as automobiles. Also, the global lithium deposits are very limited. Hence, sodium-ion batteries (SIBs) have been heavily investigated as cheaper alternatives to expensive lithium-ion batteries, mainly due to the abundance of sodium raw materials. However, one of the major bottlenecks faced by the material research community to commercialize SIBs is the poor ionic conductivity of sodium-ion conducting electrolytes at ambient temperature, especially in the solid-state. Very recently, quasi-solid state polymer electrolytes (QSSPEs) have been proposed to overcome this challenge. In this work, a set of QSSPEs have been synthesized by using poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) host polymer and NaBF4 ionic salt dissolved in EC/PC plasticizer/solvent mixture. The highest conducting composition; 6 PVdF-HFP: 14 NaBF4: 40 EC: 40 PC (wt.%); showed an ambient temperature ionic conductivity of 4.1x10-3 S cm-1. The activation energy is almost same for all the sample compositions studied in this work suggesting that the activation process is mainly controlled by EC/PC. DC polarization test on highest conducting electrolyte composition with a configuration of SS/QSSPE/SS revealed that the electrolyte is predominantly ionic conductor with negligible electronic conductivity; a much desired property for a good electrolyte. Linear sweep voltammetric studies confirmed that the electrochemical stability window of the highest conducting electrolyte is about 3.6 V. This highest conducting electrolyte composition is found to be highly suitable for practical applications in sodium batteries.

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Jia, Bin, Yan Yin, Jiang Ping Wu, Jing Zhang, Kui Jiao, and Qing Du. "Water Sorption and Percolation for Proton-Conducting Electrolyte Membranes for PEM Fuel Cells." Advanced Materials Research 578 (October 2012): 54–57. http://dx.doi.org/10.4028/www.scientific.net/amr.578.54.

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The relationship between water sorption behavior and proton conduction in polymer electrolyte membranes based on sulfonated polyimide electrolyte membranes is studied from view points of polymer structure, ion exchange capacity, and percolation theory. The results indicate that the polymer chemical structure and ion exchange capacity show significant effects on water sorption and thus proton conductivity for various membranes. The density values of wet membranes decreased gradually with an increase in water uptake. Polymer electrolytes with flexible side-chain terminated with sulfonic acid group displayed smaller percolation threshold compared with main-chain-type polymer, indicating a better microphase-separation structure.

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Liang, Hai-Peng, Maider Zarrabeitia, Zhen Chen, Sven Jovanovic, Steffen Merz, Josef Granwehr, Stefano Passerini, and Dominic Bresser. "Polysiloxane-Based Single-Ion Conducting Polymer Electrolyte for High-Performance Li‖NMC₈₁₁ Batteries." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 326. http://dx.doi.org/10.1149/ma2022-012326mtgabs.

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The ongoing electrification of the transportation sector is triggering a continuous search for batteries with higher energy density. One approach to achieve this goal is the transition to lithium-metal anodes. However, the practical implementation brings about severe safety issues such as the dendritic deposition and growth of metallic lithium and the consequent risk of accidental short circuiting of the cell, resulting in a thermal runaway.1 Solid-state electrolytes such as polymers are considered a viable strategy to overcome this issue, especially single-ion conducting polymers, owing to the absence of the detrimental reversed cell polarization, the uniform Li+ flux, and frequently higher limiting current densities.2,3 In fact, the latter is of utmost importance for the fast charging of battery cells as well as the eventual power density. So far, however, the cycling performance at high dis-/charge rates and high current densities for battery cells comprising a polymer electrolyte remained little investigated and commonly non-satisfactory. Here, we report the development of a polysiloxane-based single-ion conducting polymer electrolyte (PSiOM) with a Li+ conductivity exceeding 10−4 S cm−1 at ambient temperature and excellent stability towards both lithium metal and high-energy LiNi0.8Co0.1Mn0.1O2 (NMC811) as the active material for the positive electrode. This new polymer electrolyte enables dendrite-free lithium deposition, thanks to the formation of a suitable electrode|electrolyte interface and interphase and the uniform Li+ flux. Moreover, PSiOM allows for an outstanding capacity retention of, e.g., 90% at 1C and 86% at 2C after 300 cycles and rapid charging and discharging at C rates as high as 5C. It is important to note that we used reasonable active material mass loadings for these tests (>7 mg cm-2), which means that the current densities applied were up to 7.20 mA cm−2 at 40 °C and 2.88 mA cm−2 at 20 °C. To the best of our knowledge, these current densities are among the highest reported so far for polymer-based electrolytes. References (1) Kalhoff, J.; Eshetu, G. G.; Bresser, D.; Passerini, S. Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives. ChemSusChem 2015, 8 (13), 2154–2175. (2) Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chemical Society Reviews 2017, 46 (3), 797–815. (3) Nguyen, H.-D.; Kim, G.-T.; Shi, J.; Paillard, E.; Judeinstein, P.; Lyonnard, S.; Bresser, D.; Iojoiu, C. Nanostructured Multi-Block Copolymer Single-Ion Conductors for Safer High-Performance Lithium Batteries. Energy & Environmental Science 2018, 11 (11), 3298–3309.

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Kumar, R., Shuchi Sharma, N. Dhiman, and D. Pathak. "Study of Proton Conducting PVdF based Plasticized Polymer Electrolytes Containing Ammonium Fluoride." Material Science Research India 13, no. 1 (April 5, 2016): 21–27. http://dx.doi.org/10.13005/msri/130104.

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Polymer electrolytes based on polyvinyledene fluoride (PVdF) and ammonium fluoride (NH4F) have been prepared and characterized. Films of polyvinyledene fluoride and ammonium fluoride have been prepared by solution casting technique using tetrahydrofuran (THF) as a solvent. Maximum conductivity of 1.17 x 10-7 S/cm at room temperature has been obtained for polymer electrolytes containing 10wt% NH4F. The conductivity of polymer electrolyte has been increased by three orders of magnitude from 10-7 to 10-4 S/cm with the addition of dimethylformamide (DMF) as plasticizer. The increase in conductivity has been explained to be due to the dissociation of undissociated salt/ion aggregates present in the polymer electrolytes with the addition of high dielectric constant plasticizer (DMF). Maximum conductivity of 1.26 x 10-4 S/cm has been observed for plasticized polymer electrolytes. The variation of conductivity with temperature suggests that these polymer electrolytes are thermally stable and small change in conductivity with temperature is suitable for their use in practical applications like solid state batteries, fuel cells, electrochromic devices, supercapacitors etc.

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Park, Habin, Anthony Engler, Nian Liu, and Paul Kohl. "Cyclic Carbonate-Based, Single-Ion Conducting Polymer Electrolytes for Li-Ion Batteries: Battery Performance." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 329. http://dx.doi.org/10.1149/ma2022-012329mtgabs.

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Solid polymer electrolytes (SPEs) are a pathway for safe, and high energy and power lithium batteries due to their thermal stability and low vapor pressure. Although polymers can be flexible and dimensional stability, it is lithium dendritic suppression can be a challenge for any electrolyte. Conventional SPEs have both mobile cations and anions, which migrate and cause concentration polarization. The low transference number for lithium ions in an electrolyte contributes lithium concentration gradients causing concentration polarization and lithium dendrites [1,2]. Single-ion conducting SPEs have been reported to demonstrate lithium ion only conduction in the electrolyte as well as retain their high mechanical stability during cycling. However, their low ionic conductivity is due to stationary phase of the tethered anion in the polymer matrix and cation-anion complexation [3]. In this study, a cyclic carbonate neutral moiety was included in the SPE to help dissociate the lithium cation from the tethered anion matrix to increase the ionic conductivity and help form the solid electrolyte interphase (SEI) layer. The cyclic carbonate unit in the SPE is similar to the cyclic carbonate solvent in a conventional lithium ion battery and could participate in the solvation of the lithium cation in the SPE. The cyclic carbonate monomer in the SPE can participate in SEI-forming electrochemical reactions on the electrode surface and suppress undesirable side reactions and lithium dendritic growth. Satisfactory level of rate and cycling performance was achieved with the novel neutral monomers in the single-ion conducting SPEs. [1] H. Zhang, C. Li, M. Piszcz, E. Coya, T. Rojo, L.M. Rodriguez-Martinez, M. Armand, Z. Zhou, Chem. Soc. Rev. 2017, 46, 797-815. [2] F. Ahmed, I. Choi, M.M. Rahman, H. Jang, T. Ryu, S. Yoon, L. Jin, Y. Jin, W. Kim, ACS Appl. Mater. Interfaces 2019, 11, 34930-34938. [3] D.-M. Shin, J.E. Bachman, M.K. Taylor, J. Kamcev, J.G. Park, M.E. Ziebel, E. Velasquez, N.N. Jarenwattananon, G.K. Sethi, Y. Cui, J.R. Long, Adv. Mater. 2020, 32, 1905771.

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Waidha, Aamir Iqbal, Vanita Vanita, and Oliver Clemens. "PEO Infiltration of Porous Garnet-Type Lithium-Conducting Solid Electrolyte Thin Films." Ceramics 4, no. 3 (July 23, 2021): 421–36. http://dx.doi.org/10.3390/ceramics4030031.

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Composite electrolytes containing lithium ion conducting polymer matrix and ceramic filler are promising solid-state electrolytes for all solid-state lithium ion batteries due to their wide electrochemical stability window, high lithium ion conductivity and low electrode/electrolyte interfacial resistance. In this study, we report on the polymer infiltration of porous thin films of aluminum-doped cubic garnet fabricated via a combination of nebulized spray pyrolysis and spin coating with subsequent post annealing at 1173 K. This method offers a simple and easy route for the fabrication of a three-dimensional porous garnet network with a thickness in the range of 50 to 100 µm, which could be used as the ceramic backbone providing a continuous pathway for lithium ion transport in composite electrolytes. The porous microstructure of the fabricated thin films is confirmed via scanning electron microscopy. Ionic conductivity of the pristine films is determined via electrochemical impedance spectroscopy. We show that annealing times have a significant impact on the ionic conductivity of the films. The subsequent polymer infiltration of the porous garnet films shows a maximum ionic conductivity of 5.3 × 10−7 S cm−1 at 298 K, which is six orders of magnitude higher than the pristine porous garnet film.

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Yang, Y. "Blended lithium ion conducting polymer electrolytes based on boroxine polymers." Solid State Ionics 140, no. 3-4 (April 1, 2001): 353–59. http://dx.doi.org/10.1016/s0167-2738(01)00820-7.

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Yu, Jiwon, Hyung-kyu Lim, Gyeong S. Hwang, and Sangheon Lee. "Role of Agent Molecules for Low-Temperature Activation of Lithium-Ion Transport for Solid-State Polymer Electrolytes." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 234. http://dx.doi.org/10.1149/ma2022-012234mtgabs.

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The realization of all-solid-state lithium-ion batteries (LIBs) is often considered as the final challenge in the development of LIBs. Replacing Li-ion conductive liquid electrolytes with high-performance solid-state electrolytes is indispensable for the development of all-solid-state LIBs. Solid-state electrolytes under development fall into three classes: polymers, oxides, and sulfides. Polymer-based electrolytes have advantages over oxides and sulfides, such as formation of low-resistance electrolyte/electrode interfaces, good processability, and high energy-density owing to low density. Therefore, polymer-based solid-state electrolytes are being developed in both industry and academia as a practical route for realizing high-capacity LIBs.[1] For application in commercial LIBs, the electrolyte should have an ionic conductivity higher than 10-4 S/cm at room temperature. Conventional solid polymer electrolytes, such as polyethylene oxide (PEO)-based electrolytes, do not meet the performance requirements due to insufficient ionic conductivity in the range of 10-6 to 10-5 S/cm. Recently, polyphenylene sulfide (PPS)-based polymer electrolytes have been reported to yield ion conductivities as high as those of liquid electrolytes over a wide temperature range (> 1.0 × 10-4 S/cm at 25 °C, > 1.0 × 10-3 S/cm at 80 °C, and > 1.0 × 10-3 S/cm at −40 °C).[2] These electrolytes consist of base polymer chains containing PPS, Li salts that can dissociate into cations and anions, and neutral agent molecules. However, the detailed Li-ion transport mechanism in terms of the respective roles of the molecular components of PPS electrolytes is yet to be determined. This limited understanding hinders the further improvement of PPS-based electrolytes. In this study, we perform a series of first-principle calculations and demonstrate that certain types of neutral molecules (so-called agent molecules) accelerate solid-state lithium-ion migration when mixed with lithium salts.[3] We find that the intermolecular interaction in a selected agent-molecule/lithium-salt binary system is governed by the strong coupling between lithium and oxygen atoms. Upon the addition of agent molecules, the anionic species surrounding the lithium of lithium salts is replaced by the agent molecules. The resulting weakened Coulomb energy coupling between lithium and oxygen atoms is determined to be a key factor in enabling fast lithium-ion migration via facile dissociation of lithium salts and subsequent formation of ion-hopping sites in the form of lithium-free oxygen-cages. The structure-based interpretation of agent molecules suggests that neutral molecules with functional groups which enhance chemical resonance can be selected as potential agent molecules. We believe that the results obtained in this study serve as a theoretical basis for the future development of solid-state polymer electrolytes, particularly toward mitigating the dependence of lithium-ion transport on the movement of polymer chains. References [1] P.V. Wright, Polymer electrolytes-the early days, Electrochim. Acta, 43 (1998) 1137-1143, https://doi.org/10.1016/S0013-4686(97)10011-1. [2] M.A. Zimmerman, Solid ionically conducting polymer material, U.S. Patent US 2017/0005356 A1, January 5, 2017. [3] J. Yu, M. Lee, Y. Kim, H.-K. Lim, J. Chae, G.S. Hwang, S. Lee, Agent molecule modulated low-temperature activation of solid-state lithium-ion transport for polumer electrolytes, J. Power Sources 505 (2021), 229917. Figure 1

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Cui, Wei Wei, Dong Yan Tang, and Li Li Guan. "A Single Ion Conducting Gel Polymer Electrolyte Based on Poly(lithium 2-Acrylamido-2-Methylpropanesulfonic Acid-Co-Vinyl Triethoxysilane) and its Electrochemical Properties." Advanced Materials Research 535-537 (June 2012): 2053–56. http://dx.doi.org/10.4028/www.scientific.net/amr.535-537.2053.

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Single ion conducting polymer electrolytes synthesized through a copolymer poly(lithium 2-acrylamido-2-methylpropanesulfonic acid-co-vinyl triethoxysilane) and a crosslinker poly(etheylene glycol) dimethacrylate (PEGDMA) were prepared. Scanning electron microscope (SEM) was used to observe the morphology of the surface and cross-section of the polymer electrolyte membrane. AC impedance and linear sweep voltammetry were used to investigate the electrochemical properties of the polymer electrolytes. It was found that the obtained membrane had a typical amorphous structure and possessed a smooth surface. The bulk resistance of the polymer electrolyte increased with the increase in the plasticizer uptake. The electrochemical stability increased with the increase in the content of VTES.

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Isa, Khairul Bahiyah Md, Lisani Othman, Nurul Husna Zainol, Siti Mariam Samin, Woon Gie Chong, Zurina Osman, and Abdul Kariem Mohd Arof. "Studies on Sodium Ion Conducting Gel Polymer Electrolytes." Key Engineering Materials 594-595 (December 2013): 786–92. http://dx.doi.org/10.4028/www.scientific.net/kem.594-595.786.

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Sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) as a polymer host were prepared using the solution casting technique. Sodium trifluoromethane-sulfonate (NaCF3SO3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as the solvent plasticizer. The GPE films were found to be stable up to temperature of 145 °C as shown by TGA analysis. The AC impedance study show that the optimum conductivity of 2.50 x 10-3 S cm-1 at room temperature is achieved for the film containing 20 wt.% of NaCF3SO3 salt. The temperature dependence of conductivity obeys VTF relation in the temperature range of 303 K to 373 K.

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Borzutzki, K., J. Thienenkamp, M. Diehl, M. Winter, and G. Brunklaus. "Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries." Journal of Materials Chemistry A 7, no. 1 (2019): 188–201. http://dx.doi.org/10.1039/c8ta08391f.

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Borzutzki, Kristina, Kang Dong, Jijeesh Ravi Nair, Beatrice Wolff, Florian Hausen, Martin Winter, Ingo Manke, and Gunther Brunklaus. "Lithium Deposition in Single-Ion Conducting Polymer Electrolytes." ECS Meeting Abstracts MA2020-02, no. 4 (November 23, 2020): 790. http://dx.doi.org/10.1149/ma2020-024790mtgabs.

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Gupta, P. N., K. P. Singh, and R. K. Yadav. "Ion transport in proton conducting solid polymer electrolytes." Ionics 4, no. 1-2 (January 1998): 48–52. http://dx.doi.org/10.1007/bf02375779.

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Okamoto, Y., T. F. Yeh, H. S. Lee, and T. A. Skotheim. "Design of alkaline metal ion conducting polymer electrolytes." Journal of Polymer Science Part A: Polymer Chemistry 31, no. 10 (September 1993): 2573–81. http://dx.doi.org/10.1002/pola.1993.080311018.

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Bhattacharya, B., and A. Chandra. "Mixed Anion Effect in Ion Conducting Polymer Electrolytes." physica status solidi (b) 225, no. 1 (May 2001): 179–83. http://dx.doi.org/10.1002/(sici)1521-3951(200105)225:1<179::aid-pssb179>3.0.co;2-5.

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Pandurangan, Perumal. "Recent Progression and Opportunities of Polysaccharide Assisted Bio-Electrolyte Membranes for Rechargeable Charge Storage and Conversion Devices." Electrochem 4, no. 2 (April 10, 2023): 212–38. http://dx.doi.org/10.3390/electrochem4020015.

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Polysaccharide-based natural polymer electrolyte membranes have had tremendous consideration for the various energy storage operations including wearable electronic and hybrid vehicle industries, due to their unique and predominant qualities. Furthermore, they have fascinating oxygen functionality results of a higher flexible nature and help to form easier coordination of metal ions thus improving the conducting profiles of polymer electrolytes. Mixed operations of the various alkali and alkaline metal–salt-incorporated biopolymer electrolytes based on different polysaccharide materials and their charge transportation mechanisms are detailly explained in the review. Furthermore, recent developments in polysaccharide electrolyte separators and their important electrochemical findings are discussed and highlighted. Notably, the characteristics and ion-conducting mechanisms of different biopolymer electrolytes are reviewed in depth here. Finally, the overall conclusion and mandatory conditions that are required to implement biopolymer electrolytes as a potential candidate for the next generation of clean/green flexible bio-energy devices with enhanced safety; several future perspectives are also discussed and suggested.

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Deng, Kuirong, Qingguang Zeng, Da Wang, Zheng Liu, Zhenping Qiu, Yangfan Zhang, Min Xiao, and Yuezhong Meng. "Single-ion conducting gel polymer electrolytes: design, preparation and application." Journal of Materials Chemistry A 8, no. 4 (2020): 1557–77. http://dx.doi.org/10.1039/c9ta11178f.

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35

Singh, Divya, D. Kanjilal, GVS Laxmi, Pramod K. Singh, SK Tomar, and Bhaskar Bhattacharya. "Conductivity and dielectric studies of Li3+-irradiated PVP-based polymer electrolytes." High Performance Polymers 30, no. 8 (June 12, 2018): 978–85. http://dx.doi.org/10.1177/0954008318780494.

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Poly(vinylpyrrolidone) (PVP) complexed with sodium iodide (NaI) is synthesized to investigate the ionic conductivity of alkaline-based polymer electrolytes. In this article, we report the modification of electrical properties of a new ion-conducting polymer electrolyte, namely, PVP complexed with NaI. Modification of polymer electrolyte was carried out before and after the exposure of films by bombarding them at different fluences with respect to Li3+ ion beam at 60 MeV. The preparation and detailed characterization of PVP:NaI is being reported. Further, a correlation with conductivity and dielectric constant has also been established. The modulation in the conductivity is explained in terms of number of charge carriers ( n) and its mobility ( μ), which confirms the behavior of the polymer electrolyte as an alternative strategy to improve the conductivity.

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36

Engler, Anthony, Habin Park, Manas Madhira, Dominic Picca, James Hanus, Nian Liu, and Paul Kohl. "Investigation on Tethered Anion Effects in Solid Polymer Electrolytes for Li-Ion Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 521. http://dx.doi.org/10.1149/ma2022-024521mtgabs.

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Solid polymer electrolytes (SPEs) have been proposed to reduce concentration polarizations within batteries by immobilizing anions to the polymer matrix, which can help stabilize the electrodeposition process and extend Li-ion battery lifetime. Unfortunately, single-ion conducting SPEs continue to suffer from poor conductivity due to coupling with the slow segmental mobility of polymer chains and poor ion pair dissociation. Our group systematically investigated how different tethered anions affect the Li-ion conduction and polymer segmental mobility. Copolymers were synthesized using a common neutral monomer, poly(ethylene glycol) methyl ether methacrylate (PEGMA), with a series of different anionic monomers: 4-styrene sulfonate, 4-styrene phosphonate, 4-styrene TFSI, and methacrylate TFSI. These monomers presented a series of anions of varying strength with the same styrene structure, sulfonate vs. phosphonate vs. TFSI, as well as exploring structural monomer changes for the same TFSI anion, styrene vs. methacrylate, that allows for systematic changing of polymer electrolyte properties. Each copolymer series was further expanded by changing the composition of neutral-to-anionic monomers, ranging from 10-67 mol% anionic. The increased ion exchange capacity of the phosphonate groups led to a high degree of ion aggregation that exhibited hard mechanical properties and very low Li-ion conductivities. Increasing the electron delocalization of the ions from sulfonate to TFSI greatly improved the conductivities and lowered activation energies of ion transport, with methacrylate being slightly better than styrene. Implications of these results will be discussed for next-generation polymer electrolyte design.

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Caradant, Lea, Nina Verdier, Gabrielle Foran, David Lepage, Arnaud Prébé, David Aymé-Perrot, and Mickaël Dollé. "The Influence of Polar Functional Groups in Hot-Melt Extruded Polymer Blend Electrolytes for Solid-State Lithium Batteries." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 210. http://dx.doi.org/10.1149/ma2022-012210mtgabs.

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Following the COP26 Summit in November 2021, more than hundred countries pledged to reach zero-emission by 2070 at the latest and the major car manufacturers committed to selling only electric vehicles by 2040. Currently, lithium-ion batteries (LIBs) are among the most widely used storage systems because of their high energy and power densities and long lifespan.1 The early LIBs are composed of intercalation electrodes, electronically isolated by an ion-conducting organic liquid electrolyte. However, the use of liquid electrolytes presents some disadvantages – especially in regard to consumer safety – related to short-circuits and potential leakages of the flammable liquid solvent. Moreover, in the case of lithium metal batteries, the combination of a liquid electrolyte and a high-capacity lithium metal anode leads to the uncontrolled deposition of lithium during the reduction, forming dendrites between the electrodes. A promising way to avoid this instability and improve battery safety is to replace the liquid electrolyte with an ion-conducting solid electrolyte.2 Among them, solid polymer electrolytes (SPEs) represent one of the most attractive alternatives due to their capacity to effectively conduct ions and higher mechanical resistance than their liquid counterparts.3 An important criterion for selecting polymers for use in SPEs is their ability to dissolve lithium salts through polar functional groups. Salt dissolution results in the replacement of ion-ion interactions in the lithium salt, with ion-dipole interactions in the polymer. The transport mechanisms of these ion-conducting materials differ from those of liquid electrolytes. Cation transport in polymer involves two steps which are considered to be dissociated or not, depending on the model chosen (Arrhenius or Vogel-Fulcher-Tammann, respectively). The application of one of these models provides interesting information on the ionic mobility dynamics in SPEs and, in particular, on the interplay between ionic jumps and polymer chain mobility. In the Arrhenius model, ionic jumps occur between coordinating sites, without taking into account the influence of segmental relaxation. Conversely, the VTF equation implies a strong relationship between these parameters. According to previous studies, higher segmental motions in the amorphous phase of polymers mainly provide ionic transport, which explains the limited ionic conductivity of SPEs at ambient temperature (less than 10-5 S/cm). Another major limitation of SPEs is primarily related to their dual role as electrolyte and binder in composite electrodes, which requires contradictory requirements to be met. Indeed, SPEs must have both sufficient flexibility to allow good interfacial contact between the electrode components and sufficient rigidity to limit short circuits. Polymer blending has emerged as an economic and effective technique to develop new SPEs which may simultaneously combine properties of each polymer and control the intrinsic properties of the resulting blend by adjusting the formulation.4 Moreover, polymer blends can be obtained by a solvent-free processing method, which reduce SPE toxicity and production time (no solvent evaporation). However, polymer blending makes both the salt dissociation processes and the ionic transport more difficult to understand as both polymers can dissolve lithium salts with their polar functional groups. Each polymer has different ionic transport properties depending on its architecture and thermal properties. Currently, no systematic survey comparing the ability of polymers with various functional groups to dissolve lithium salts in blends has thus far been conducted. In this presentation, we will discuss the salt dissociation ability of polar functional groups in various polymer blend SPEs. These groups are limited to those that are most commonly present in SPEs : ether, nitrile, carbonate, ester, alcohol and amide.5 The blends presented have been obtained by extrusion, which allows the effect of solvents on salt/polymer interactions to be neglected. In this work, coupled FTIR, EDX and 7Li NMR analyses allow the interactions between LiTFSI and the polymer blends to be determined with a good degree of certainty. Our original study combines experimental and theoretical approaches to determine effects of polymers’ lithium salt solvating ability on polymer blend electrolyte properties and represents an advancement in understanding and optimizing polymer selection for SPEs, used in lithium-ion batteries. References Xie, W., Liu, X., He, R., Li, Y., Gao, X., Li, X., Peng, Z., Feng, S., Feng, X. and Yang, S. Journal of Energy Storage 2020, 32, 101837. Chen, R., Qu, W., Guo, X., Li, L. and Wu, F. Materials Horizons 2016, 3, 487-516. Gray, F. M. Solid polymer electrolytes, VCH New Tork 1991. Caradant, L., Lepage, D., Nicolle, P., Prébé, A., Aymé-Perrot, D. and Dollé, M. ACS Applied Polymer Materials 2020, 4943-4951. Caradant, L., Verdier, N., Foran, G., Lepage, D., Prébé, A., Aymé-Perrot, D. and Dollé, M. ACS Applied Polymer Materials 2021. Figure 1

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Van Humbeck, Jeffrey F., Michael L. Aubrey, Alaaeddin Alsbaiee, Rob Ameloot, Geoffrey W. Coates, William R. Dichtel, and Jeffrey R. Long. "Tetraarylborate polymer networks as single-ion conducting solid electrolytes." Chemical Science 6, no. 10 (2015): 5499–505. http://dx.doi.org/10.1039/c5sc02052b.

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39

Caradant, Lea, Nina Verdier, Gabrielle Foran, David Lepage, Arnaud Prébé, David Aymé-Perrot, and Mickaël Dollé. "The Influence of Polar Functional Groups in Melt-Blended Polymers Used As New Solid Electrolytes for Lithium Batteries." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2423. http://dx.doi.org/10.1149/ma2022-0272423mtgabs.

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Abstract:

Following the COP26 Summit in November 2021, more than hundred countries pledged to reach zero-emission by 2070 at the latest and the major car manufacturers committed to selling only electric vehicles by 2040. Currently, lithium-ion batteries (LIBs) are among the most widely used storage systems because of their high energy and power densities and long lifespan.1 The early LIBs are composed of intercalation electrodes, electronically isolated by an ion-conducting organic liquid electrolyte. However, the use of liquid electrolytes presents some disadvantages – especially in regard to consumer safety – related to short-circuits and potential leakages of the flammable liquid solvent. Moreover, in the case of lithium metal batteries, the combination of a liquid electrolyte and a high-capacity lithium metal anode leads to the uncontrolled deposition of lithium during the reduction, forming dendrites between the electrodes. A promising way to avoid this instability and improve battery safety is to replace the liquid electrolyte with an ion-conducting solid electrolyte.2 Among them, solid polymer electrolytes (SPEs) represent one of the most attractive alternatives due to their capacity to effectively conduct ions and higher mechanical resistance than their liquid counterparts.3 An important criterion for selecting polymers for use in SPEs is their ability to dissolve lithium salts through polar functional groups. Salt dissolution results in the replacement of ion-ion interactions in the lithium salt, with ion-dipole interactions in the polymer. The transport mechanisms of these ion-conducting materials differ from those of liquid electrolytes. Cation transport in polymer involves two steps which are considered to be dissociated or not, depending on the model chosen (Arrhenius or Vogel-Tamman-Fulcher, respectively). The application of one of these models provides interesting information on the ionic mobility dynamics in SPEs and, in particular, on the interplay between ionic jumps and polymer chain mobility. According to previous studies, higher segmental motions in the amorphous phase of polymers mainly provide ionic transport, which explains the limited ionic conductivity of SPEs at ambient temperature (less than 10-5 S/cm). Another major limitation of SPEs is primarily related to their dual role as electrolyte and binder in composite electrodes, which requires contradictory requirements to be met. Indeed, SPEs must have both sufficient flexibility to allow good interfacial contact between the electrode components and sufficient rigidity to limit short circuits. Polymer blending has emerged as an economic and effective technique to develop new SPEs which may simultaneously combine properties of each polymer and control the intrinsic properties of the resulting blend by adjusting the formulation.4 Moreover, polymer blends can be obtained by a solvent-free processing method, which reduce SPE toxicity and production time and cost. However, polymer blending makes both the salt dissociation processes and the ionic transport more difficult to understand as both polymers can dissolve lithium salts with their polar groups. Each polymer has different ionic transport properties depending on its architecture and thermal properties. Currently, no systematic survey comparing the ability of polymers with various functional groups to dissolve lithium salts in blends has thus far been conducted. In this presentation, we will discuss the salt dissociation ability of polar functional groups in various polymer blend SPEs. These groups are limited to those that are most commonly present in SPEs : ether, nitrile, carbonate, ester, alcohol and amide.5 The blends presented have been obtained by extrusion, which allows the effect of solvents on salt/polymer interactions to be neglected. Coupled FTIR, EDX and 7Li NMR analyses allow the interactions between LiTFSI and the polymer blends to be determined with a good degree of certainty. Our original study combines experimental and theoretical approaches to determine effects of polymers’ lithium salt solvating ability on blend electrolyte properties. Finally, this survey highlights an ideal polymer couple with the most promising and complementary properties, usable as SPE for LIBs. Indeed, this blend presents encouraging properties, compared to single-polymer SPEs, such as higher ionic conductivities over a wide temperature range, as well as improved mechanical and thermal stability properties and cycling performances. References Xie, W., Liu, X., He, R., Li, Y., Gao, X., Li, X., Peng, Z., Feng, S., Feng, X. and Yang, S. Journal of Energy Storage 2020, 32, 101837. Chen, R., Qu, W., Guo, X., Li, L. and Wu, F. Materials Horizons 2016, 3, 487-516. Gray, F. M. Solid polymer electrolytes, VCH New Tork 1991. Caradant, L., Lepage, D., Nicolle, P., Prébé, A., Aymé-Perrot, D. and Dollé, M. ACS Applied Polymer Materials 2020, 4943-4951. Caradant, L., Verdier, N., Foran, G., Lepage, D., Prébé, A., Aymé-Perrot, D. and Dollé, M. ACS Applied Polymer Materials 2021. Figure 1

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Kaneto, Keiichi, Fumito Hata, and Sadahito Uto. "Estimation of ion dimension doped in conducting polymers electrochemically." MRS Advances 3, no. 27 (2018): 1543–49. http://dx.doi.org/10.1557/adv.2017.639.

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ABSTRACTElectroactive conducting polymers are suitable for soft actuators (artificial muscles). The actuation is induced by electrochemical oxidation of conducting polymer (film) in an electrolyte solution, due to insertion of bulky counter ions (dopant ions). The magnitude of deformation (strain) depends on the size of dopant ions and the degree of oxidation. It is worthwhile to know the relationship between the magnitudes of deformation and ion size. An electrodeposited Polypyrrole film was electrochemically cycled in aqueous electrolytes of NaCl, NaBr, NaNO3, NaBF4 and NaClO4. The strain of film during electrochemical oxidation and reduction was precisely measured using a laser displacement meter and a handmade apparatus. From the strain and electrical charges inserted in the film during oxidation, the volumes and radii of dopant ions were estimated, assuming the isotropic expansion of the film. The estimated anion radii of Cl-, Br-, NO3-, BF4- and ClO4- were 235, 246, 250, 270 and 290, respectively. The results were discussed taking the crystallographic and hydrated ion radii in literatures into consideration.

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Chen, Yazhou, Guodong Xu, Xupo Liu, Qiyun Pan, Yunfeng Zhang, Danli Zeng, Yubao Sun, Hanzhong Ke, and Hansong Cheng. "A gel single ion conducting polymer electrolyte enables durable and safe lithium ion batteries via graft polymerization." RSC Advances 8, no. 70 (2018): 39967–75. http://dx.doi.org/10.1039/c8ra07557c.

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Lu, Xiaochuan. "Highly Conductive PEO-Based Polymer Composite Electrolyte for Na Battery Applications." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 510. http://dx.doi.org/10.1149/ma2022-024510mtgabs.

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State-of-the-art Li- or Na-ion batteries typically use organic solvents in the electrolytes, which might cause serious safety issues. Replacing the liquid electrolytes with nonflammable, dense solid-state electrolytes can potentially solve this problem. Among all types of solid electrolytes, PEO-based polymer electrolytes (PBPEs) have attracted great attentions due to their excellent flexibility, chemical stability, and easiness for processing. In this talk, we will present our recent progress in development of flexible, Na-ion conducting PBPEs. In particular, we tried to incorporate various amounts of ionic liquid (i.e., PY14FSI) into PEO + NaFSI electrolytes that can increase the amount of amorphous phase in the polymer and thus achieve higher ionic conduction. It was found that the highest conductivity was achieved with the composition of P(EO)20NaFSI + 2.4PY14FSI (2 x 10-3 and 3 x 10-4 S cm-1 at 60oC and RT with a Na+ transference number of ~0.1). We further verified the performance of the electrolyte with a composition of P(EO)20NaFSI + 1.6PY14FSI in symmetric and full cells. The critical current density of the electrolyte in Na symmetric cells was as high as 0.5 mA/cm2 at 60oC and the cells also showed an excellent stability during ~700 cycles at a current density of 0.1 mA/cm2. A full cell with Na3V2(PO4)3 as the cathode showed an initial capacity of 100 mAh/g-1 and a Coulombic Efficiency of ~94%. All of these demonstrated a PBPE with excellent chemical, mechanical, and electrochemical performance and properties for Na battery application. Figure 1

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Hashmi, S. A., R. J. Latham, R. G. Linford, and W. S. Schlindwein. "Conducting polymer-based electrochemical redox supercapacitors using proton and lithium ion conducting polymer electrolytes." Polymer International 47, no. 1 (September 1998): 28–33. http://dx.doi.org/10.1002/(sici)1097-0126(199809)47:1<28::aid-pi3>3.0.co;2-c.

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44

Nag, Aniruddha, Mohammad Asif Ali, Ankit Singh, Raman Vedarajan, Noriyoshi Matsumi, and Tatsuo Kaneko. "N-Boronated polybenzimidazole for composite electrolyte design of highly ion conducting pseudo solid-state ion gel electrolytes with a high Li-transference number." Journal of Materials Chemistry A 7, no. 9 (2019): 4459–68. http://dx.doi.org/10.1039/c8ta10476j.

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45

Minimala, NS, R. Sankaranarayanan, and S. Aafrin Hazaana. "Conductivity Studies in Poly Methyl Methacrylate Based Solid Polymer Electrolytes Complexed with Different Chloride Salts." Shanlax International Journal of Arts, Science and Humanities 9, S1-May (May 14, 2022): 116–20. http://dx.doi.org/10.34293/sijash.v9is1-may.5947.

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Ionic conducting polymers are of considerable interest recently, as they have wide range of applications including electrical storage devices. The present study is aimed at designing and characterizing one such ion conducting polymer complexed with various ionic salts. Here, solid polymer electrolyte films consisting of Poly methyl methacrylate (PMMA) complexed with various chloride salts (X) (X= KCl, NaCl, MgCl2) have been prepared by the solvent casting technique. Fourier transform infrared spectroscopy (FTIR) confirmed the formation of polymer-ion complex. The ionic conductivity studies have also been carried out using AC impedance spectroscopy technique. Interestingly, the maximum value of conductivity (8.268 X 10-8 S/cm) has been observed for PMMA/NaCl complex at ambient temperature.

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Chandra, Archana, Angesh Chandra, R. S. Dhundhel, and Alok Bhatt. "Synthesis and ion conduction mechanism of a new sodium ion conducting solid polymer electrolytes." Materials Today: Proceedings 33 (2020): 5081–84. http://dx.doi.org/10.1016/j.matpr.2020.02.848.

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47

Passerini, S., F. Alessandrini, T. Momma, H. Ohta, H. Ito, and T. Osaka. "Co-continuous Polymer Blend Based Lithium-Ion Conducting Gel-Polymer Electrolytes." Electrochemical and Solid-State Letters 4, no. 8 (2001): A124. http://dx.doi.org/10.1149/1.1382691.

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48

Cheng, Chih-Chia, and Duu-Jong Lee. "Supramolecular assembly-mediated lithium ion transport in nanostructured solid electrolytes." RSC Advances 6, no. 44 (2016): 38223–27. http://dx.doi.org/10.1039/c6ra07011f.

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49

Sutton, Preston, Martino Airoldi, Luca Porcarelli, Jorge L. Olmedo-Martínez, Clément Mugemana, Nico Bruns, David Mecerreyes, Ullrich Steiner, and Ilja Gunkel. "Tuning the Properties of a UV-Polymerized, Cross-Linked Solid Polymer Electrolyte for Lithium Batteries." Polymers 12, no. 3 (March 5, 2020): 595. http://dx.doi.org/10.3390/polym12030595.

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Lithium metal anodes have been pursued for decades as a way to significantly increase the energy density of lithium-ion batteries. However, safety risks caused by flammable liquid electrolytes and short circuits due to lithium dendrite formation during cell cycling have so far prevented the use of lithium metal in commercial batteries. Solid polymer electrolytes (SPEs) offer a potential solution if their mechanical properties and ionic conductivity can be simultaneously engineered. Here, we introduce a family of SPEs that are scalable and easy to prepare with a photopolymerization process, synthesized from amphiphilic acrylic polymer conetworks based on poly(ethylene glycol), 2-hydroxy-ethylacrylate, norbornyl acrylate, and either lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) or a single-ion polymethacrylate as lithium-ion source. Several conetworks were synthesized and cycled, and their ionic conductivity, mechanical properties, and lithium transference number were characterized. A single-ion-conducting polymer electrolyte shows the best compromise between the different properties and extends the calendar life of the cell.

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Nellithala, Dheeraj, Parin Shah, and Paul Kohl. "(Invited) Durability and Accelerated Aging of Anion-Conducting Membranes and Ionomers." ECS Meeting Abstracts MA2022-02, no. 43 (October 9, 2022): 1606. http://dx.doi.org/10.1149/ma2022-02431606mtgabs.

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Abstract:

Low-temperature, polymer-based fuel cells and water electrolyzers using anion conductive polymers have several potential advantages over acid-based polymer electrolyzers. However, the long-term durability of the ion conducting polymer has not been investigated to the same extent as proton conducting polymers. Further, accelerated aging test conditions with known acceleration factors have not been developed. In this study, a family of poly(norbornene) polymers used in fuel cells and electrolyzers was aged under a variety of conditions to determine the aging rate and acceleration factors. In particular, the relationship between temperature, alkalinity, and time were investigated.

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Journal articles on the topic 'Ion Conducting Polymer Electrolytes'

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