Ion‐conducting polymer gels of polyacrylamide embedded with K2CO3

A highly ionic conductive solid‐gel membrane based on polyacrylamide hydrogels with a K₂CO₃ additive was investigated. The polymer‐based gel was prepared by adding ionic species K₂CO₃ to a monomer solution followed by polymerization. After polymerization, the ionic species was embedded in the polymer‐based gel, where it remained. The ionic species behaved like a liquid electrolyte, whereas the polymer‐based solid‐gel membrane provided a smooth impenetrable surface that allowed for the exchange of ions. The gel membranes were obtained in the form of thin films of reasonable mechanical strength. Their ambient temperature conductivities were in the range 10^?2 to 10^?1 S/cm. The effect of K₂CO₃ concentration on the conductivity of the gels prepared was examined in the temperature range from 0 to 100°C. The microstructure and chemical composition of the gels studied were characterized by environmental scanning electron microscopy and FTIR, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2076–2081, 2004     

LiClO4 salt concentration effect on the properties of PVC‐modified low molecular weight LENR50‐based solid polymer electrolyte

A work was carried out on a solid polymeric electrolyte system comprising blends of poly (vinyl chloride) and liquid 50% epoxidized natural rubber (LENR50) as a polymer host with LiClO₄ as a salt and prepared by solution casting technique. In this paper, the main study was the effect of LiClO₄ salt concentration on the electrolyte properties. The effect of the salt on the electrolyte properties was characterized and analyzed with impedance spectroscopy (EIS), X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and scanning electron microscopy (SEM). The EIS result showed that highest ionic conductivity was obtained at 30 wt % salt with a value of 2.3 × 10^?8 S cm^?1. The XRD results revealed that the LiClO₄ salt was fully complexed within the polymer host as no sharp peaks were observed. However, above 30 wt % of salt, some sharp peaks were observed. This phenomenon was caused by the association of ions. Meanwhile, DSC analysis showed that T_g increased as the salt content increased. This implied that LiClO₄ salt had interaction with polymer host by forming coordination bond. The morphologies' studies showed that good homogeneity and compatibility of the electrolyte were achieved. Upon the addition of the salt, formation of micropores occurred. It was noted that micropores which aid in mobility of ions in the electrolyte system has increased the ionic conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Investigations on pyridinium salts as a solid‐state ionics

The object of this work is to prepare polymer poly(2vinylpyridine), P‐2VP, and its salts like P‐2VP‐HI, P‐2VP‐HIO₃, and P‐2VP‐HIO₄. The formation of P‐2VP salts was confirmed by IR and ¹H NMR techniques. Conductivities of these were determined in solid state at various temperatures from 30 to 90°C. Observations indicated that the addition of I^? or IO₃^? or IO₄^? ions affect the ionic conductivity of P‐2VP. Molecular mass determination and analytical results indicated that 94, 92.5, and 95% of the pyridine molecules in the P‐2VP chain were hydroiodated, iodated, and periodated, respectively, with the corresponding acids of iodine. The total ionic transport number and activation energy of the polymers were also determined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effect of crosslinking on the adsorption behavior of copper (II) onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone)

The adsorption behavior of Cu(II) ions onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone), polymer I, and onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone) crosslinked with different amounts of divinylbenzene (DVB), polymers II, III, and IV, in aqueous solutions was investigated using batch adsorption experiments as a function of contact time, pH, and temperature. The amount of metal ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest uptake was achieved at pH 7.0 and by using perchlorate as an ionic strength adjuster for polymers I, II, III, and IV. Results revealed that the adsorption capacity (q_e and Q_m) of Cu(II) ions decreases with increasing crosslinking due to the decrease of chelation sites. In addition, the rate of adsorption (k₂) of Cu(II) ions decreases with the increase of crosslinking because it becomes more difficult for Cu(II) ions to diffuse into the chelation sites. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated. The experimental data of the adsorption process was found to correlate well with the Langmuir isotherm model. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of various electrophoretically deposited nano‐silica contents on the properties of poly(vinylidene fluoride‐co‐hexafluoropropylene)‐based electrospun polymer electrolytes

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (P(VDF‐HFP)) based composite polymer electrolyte (CPE) membranes were successfully prepared by electrospinning followed by electrophoretic deposition processes, and desirable polymer electrolytes were obtained after being activated in liquid electrolytes. The physicochemical properties of the CPEs with different electrophoretically deposited nano‐SiO₂ contents were investigated by SEM, XRD, TGA, linear sweep voltammetry and electrochemical impedance spectroscopy measurements. When the ratio of electrophoretically deposited nano‐SiO₂ to P(VDF‐HFP) is up to 4 wt%, the results show that the CPE membrane presents a very uniform surface with abundant interconnected micropores and possesses excellent mechanical tensile strength with high thermal and electrochemical stability; the ionic conductivity at room temperature can reach 3.361 mS cm^?1 and the reciprocal temperature dependence of the ionic conductivity follows a Vogel ? Tamman ? Fulcher relationship. The interfacial resistance of the assembled Li/CPE/Li simulated cell can rapidly increase to a steady value of about 950 Ω from the initial value of about 700 Ω at 30 °C during 15 days' storage. The battery performance test suggests that the CPE also shows excellent compatible properties with commercial LiCoO₂ and graphite materials. © 2015 Society of Chemical Industry     

Metal‐chloride‐anion‐containing polymers with expanded π‐conjugation systems derived from through‐space interactions in the piperazinium ring

Reactions of N‐(2,4‐dinitrophenyl)pyridinium chloride (salt(Cl)) with H⁺MCl₄^?1 (M ≡ Fe and Bi) resulted in an anion exchange between Cl^? and MCl₄^? to yield Zincke salts with metal chloride anions, namely salt(Fe) and salt(Bi), respectively. Reactions of the Zincke salts with piperazine resulted in ring‐opening of the pyridinium ring, yielding ionic polymers with 5‐piperazinium‐2,4‐dienylideneammonium metal chloride units, namely polymer(Fe) and polymer(Bi). The corresponding model compounds were synthesized via reactions using salt(Bi) or salt(Cl) as starting materials. The UV–visible spectra of the polymers had absorption maxima at longer wavelengths than those of the model compounds. This indicated that the π‐conjugation system is expanded along the polymer main chain. Superconducting quantum interference device measurements indicated that polymer(Fe) was paramagnetic. Cyclic voltammetry analysis suggested that the polymers underwent electrochemical oxidation. © 2019 Society of Chemical Industry     

Dissolution and formation of polyacrylonitrile in low‐temperature molten salts

The solubility and the polymerization of polyacrylonitrile in low‐temperature molten salts was investigated. It was found, that the polymer dissolves in eutectic mixtures of molten sodium thiocyanate and potassium thiocyanate (NaSCN/KSCN) as well as in the molten hydrate lithium perchlorate (LiClO₄*3H₂O). The polymer can be regenerated by cooling the melt or diluting with water. The chemical interaction between the molten salt and the polymer was investigated by ¹³C‐NMR spectroscopy. These measurements show that the dissolution of the polymer in molten KSCN/NaSCN is accompanied by the splitting of the the hydrogen bonds. Starting from acrylonitrile, the formation of polyacrylonitrile by a radical polymerization in a molten salt becomes successful. The polymerization of acrylonitrile in an eutectic mixture of KSCN/NaSCN results in the formation of atactic polyacrylonitrile with high molecular weight. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2113–2117, 2000     

Effect of methylsisesquioxane filler on the properties of ionic liquid based polymer electrolyte

Composite electrolyte comprising methylsisesquioxane (MSQ) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF₄) ionic liquid (IL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix had been prepared. The polymer matrix was formed by free radical polymerization of HEMA macromer, and MSQ was produced in situ from methyl-trimethoxysilane by the sol-gel method. Infrared spectroscopy and dynamic mechanical analysis were employed to give insight into the interactions among the methylsisesquioxane filler, BMImBF₄ and the PHEMA polymer matrix. The PHEMA-IL-MSQ hybrids and the PHEMA-IL electrolyte without MSQ were investigated regarding their ionic conductivity and thermal and electrochemical properties. BMImBF₄ increased the thermal stability of the polymer and provided the ion conductivity; MSQ filler as the additive increased the mechanical strength of the polymer and provided the ion conductive pathway. The electrolyte with MSQ at the 10 wt% showed the highest ionic conductivity of 5×10⁻⁴ S cm⁻¹ which was five times higher than that of the electrolyte without MSQ, and the electrochemical window was up to 3.6 V.     

A fluorescent chemosensor based on optically active 2,2′‐binaphtho‐20‐crown‐6 for metal ions

A chiral conjugated polymer can be obtained by the polymerization of (S)‐6,6′‐dibromo‐2,2′‐binaphtho‐20‐crown‐6 and 1,4‐divinyl‐2,5‐dibutoxybenzene via a palladium‐catalyzed Heck cross‐coupling reaction. The chiral conjugated polymer shows strong green‐blue fluorescence. The responsive properties of the chiral polymer to metal ions were investigated using fluorescence and UV‐visible absorption spectra. K⁺, Pb²⁺, Cd²⁺ and Ba²⁺ enhance the fluorescence of the polymer; in contrast, Hg²⁺ causes effective quenching of the fluorescence of the polymer. The obvious influences on the fluorescence indicate that the 2,2′‐binaphtho‐20‐crown‐6 moiety plays an important role in fluorescence recognition for Hg²⁺ due to the effective photo‐induced electron transfer or charge transfer between the conjugated polymer backbone and the receptor ions. The responsive properties of the polymer to metal ions show that the chiral conjugated polymer incorporating 2,2′‐binaphtho‐20‐crown‐6 moieties in the main‐chain backbone as recognition sites can act as an excellent fluorescent probe for the sensitive detection of Hg²⁺. Copyright © 2010 Society of Chemical Industry     

Adsorption of Cu2+ ions with poly(N‐isopropylacrylamide‐co‐methacrylic acid) micro/nanoparticles

Chelation efficiency of stimuli‐responsive poly(N‐iospropylacrylamide‐co‐methyacrylic acid) (PNIPAAm‐MAA) nanoparticles with Cu²⁺ ions from CuSO₄·5H₂O solution and from wood treated with copper‐based preservatives was studied. It was shown that particle size played a very important role in the adsorption process. The nano‐scale particles showed much improved Cu ion adsorption efficiency, compared with the micro hydrogels. The amount of Cu ion adsorption increased with increase of MAA ratio in copolymers and adsorption efficiency decreased with increased particle size. Furthermore, the adsorption amount varied with adsorption temperature at temperatures both below and above the corresponding low critical solution temperature (LCST). The high adsorption efficiency of Cu ions by PNIPAAm‐MAA polymer particles provides an effective technique for recovering metal ions (e.g., Cu²⁺) from wood treated with metal‐based preservatives. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A new carbon nanotubes (CNTs)–poly acrylonitrile (PAN) composite electrolyte for solid state dye sensitized solar cells

A new carbon nanotube (CNTs)–poly acrylonitrile (PAN) composite electrolyte was prepared by the thermal polymerization of acrylonitrile (AN) with CNTs for solid-state dye sensitized solar cells (DSSCs). It was found that the uniform CNT–PAN composite was formed due to the thermal polymerization of AN on CNTs. The strong bonding between CNTs and PAN could be confirmed by the characterization of XPS and Raman spectroscopy, resulting in the lowering of crystallinity and the increasing the ionic conductivity of composite electrolytes. On comparison with bare CNTs and the other composite electrolytes, the formation of triiodide (I₃⁻) ions in CNT–PAN composite electrolytes was drastically increased which was expected from the high ionic conductivity of electrolyte via I₃⁻/I⁻ redox couple. DSSCs fabricated with CNT–PAN composite electrolytes achieved relatively high conversion efficiency of 3.9% with an open circuit voltage (V_OC) of 0.57 V, short circuit current density (J_SC) of 10.9 mA/cm² and fill factor of 63.6%, which attributed to supply the higher extent of I₃⁻ ions from CNT–PAN composite electrolyte during the charge transport process.     

Fabrication and properties of crosslinked poly(propylene carbonate maleate) gel polymer electrolyte for lithium‐ion battery

The poly(propylene carbonate maleate) (PPCMA) was synthesized by the terpolymerization of carbon dioxide, propylene oxide, and maleic anhydride. The PPCMA polymer can be readily crosslinked using dicumyl peroxide (DCP) as crosslinking agent and then actived by absorbing liquid electrolyte to fabricate a novel PPCMA gel polymer electrolyte for lithium‐ion battery. The thermal performance, electrolyte uptake, swelling ratio, ionic conductivity, and lithium ion transference number of the crosslinked PPCMA were then investigated. The results show that the T_g and the thermal stability increase, but the absorbing and swelling rates decrease with increasing DCP amount. The ionic conductivity of the PPCMA gel polymer electrolyte firstly increases and then decreases with increasing DCP ratio. The ionic conductivity of the PPCMA gel polymer electrolyte with 1.2 wt % of DCP reaches the maximum value of 8.43 × 10⁻³ S cm⁻¹ at room temperature and 1.42 × 10⁻² S cm⁻¹ at 50°C. The lithium ion transference number of PPCMA gel polymer electrolyte is 0.42. The charge/discharge tests of the Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3O₂ cell were evaluated at a current rate of 0.1C and in voltage range of 2.8–4.2 V at room temperature. The results show that the initial discharge capacity of Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3 O₂ cell is 115.3 mAh g⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Application of polymer gel electrolyte with graphite powder in quasi‐solid‐state dye‐sensitized solar cells

A polymer gel electrolyte with ionic conductivity of 5.11 mS cm⁻¹ was prepared by using poly (acrylonitrile‐co‐styrene) as polymer matrix, acetonitrile and tetrahydrofuran as binary organic mixture solvent, NaI + I₂ as electrolyte, graphite powder and 1‐methylimidazole as additives. The components ratio of the polymer gel electrolyte was optimized, and the influence of the components and temperature on the ionic conductivity of the polymer gel electrolyte and photoelectronic properties of dye sensitized solar cell were investigated. On the basis of the polymer gel electrolyte with the optimized conditions, a quasi‐solid‐state dye‐sensitized solar cell was fabricated and its light‐ to‐electricity energy conversion efficiency of 3.25% was achieved under irradiation of 100 mW cm⁻². POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Grafting of sulfonated monomer onto an amino‐silane functionalized 2‐aminoterephthalate metal − organic framework via surface‐initiated redox polymerization: proton‐conducting solid electrolytes

A post‐polymerization method for metal–organic frameworks (MOFs) has been developed to produce super‐acidic solid nanoparticles. Thus, the NH₂MIL‐53(Al) MOF was functionalized with (3‐aminopropyl)triethoxysilane (APTES) from amine groups to yield active site anchored MOF nanoparticles. Then, sulfonated polymer/MOF hybrid nanoparticles were prepared by redox polymerization of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (MOF‐g‐PAMPS), initiated onto the surfaces of aminopropyl‐functionalized NH₂MIL‐53(Al) nanoparticles. The synthesis and modification of NH₂MIL‐53(Al) nanoparticles were characterized by Fourier transform infrared (FTIR) spectroscopy and TGA. FTIR and TGA results indicated that APTES modifier agent and AMPS monomer were successfully grafted onto the MOF nanoparticles. The grafting efficiency of PAMPS polymer onto the MOF nanoparticles was estimated from TGA thermograms to be 33%. Also, sulfonated polymer/MOF hybrid nanoparticles showed a proton conductivity as high as 4.9 × 10^?5 S cm^?1. Nitrogen adsorption of modified NH₂MIL‐53(Al) showed also a decrease in pore volume. The morphology and crystalline structure of MOF nanoparticles before and after the modification processes were studied by SEM and XRD, respectively. © 2015 Society of Chemical Industry     

Effects of polymer matrix and salt concentration on the ionic conductivity of plasticized polymer electrolytes

Two polar polymers with different dielectric constants, poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO), were each blended with a chlorine-terminated poly(ethylene ether) (PEC) and one of the two salts, LiBF₄ and LiCF₃CO₂, to form PEC plasticized polymer electrolytes. The room-temperature ionic conductivity of the PEC plasticized polymer electrolytes reached a value as high as 10^?4 S/cm. The room-temperature ionic conductivity of the PVDF-based polymer electrolytes displayed a stronger dependence on the PEC content than did the PEO-based polymer electrolytes. In PVDF/PEC/LiBF₄ polymer electrolytes, the dynamic ionic conductivity was less dependent on temperature and more dependent on the PEC content than it was in PEO/PEC/LiBF₄ polymer electrolytes. The highly plasticized PVDF-based polymer electrolyte film with a PEC content greater than CF4 (CF4 defined as the molar ratio of the repeat units of PEC to those of PVDF equal to 4) was self-supported and nonsticky, while the corresponding PEO-based polymer electrolyte film was sticky. In these highly plasticized PVDF-based polymer electrolytes, the curves of the room-temperature ionic conductivity vs. the salt concentration were convex because the number of carrier ions and the chain rigidity both increased with increase of the salt content. The maximum ionic conductivity at 30°C was independent of the PEC content, but it depended on the anion species of the lithium salts in these highly plasticized polymer electrolytes. © 1995 John Wiley & Sons, Inc.     

Aminated poly‐N‐vinylformamide as a modern retention aid of alkaline paper sizing with acid rosin sizes

Partially aminated poly‐N‐vinylformamides (APNVF) were prepared by the hydrolysis of PNVF and used as the retention aid of rosin size. The dual retention aids system, consisting of this modern polymer and aluminum sulfate (alum) for neutral‐alkaline paper sizing using acid rosin sizes, was evaluated by experiment. The results indicated that APNVF was very effective and a small amount of the polymer used together with alum considerably increased the size retention and sizing degree of paper under neutral‐alkaline conditions. The cationic charge density of APNVF significantly influenced the sizing efficiency of the rosin sizes. Furthermore, the retention of alkaline filler CaCO₃ and paper strength were improved by the polymer addition. It is clear that the polymer can be used as a multifunctional additive for papermaking. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1805–1810, 2000     

Physical and electrochemical properties of low molecular weight poly(ethylene glycol)‐bridged polysilsesquioxane organic–inorganic composite electrolytes via sol–gel process

A new class of ionic conducting organic/inorganic hybrid composite electrolyte with high conductivity, better electrochemical stability and mechanical behavior was prepared through the sol–gel processing between ethylene‐bridged polysilsesquioxane and poly(ethylene glycol) (PEG). The composite electrolyte with 0.05 LiClO₄ per PEG repeat unit has the best conductivity up to 10^?4 S/cm at room temperature with the transference number up to 0.48 and an electrochemical stability window as high as 5.5 V versus Li/Li⁺. Moreover, the effect of the PEG chain length on the properties of the composite electrolyte has also been studied. The interactions between ions and polymer have also been investigated for the composite electrolyte in the presence of LiClO₄ by means of FTIR, DSC, and TGA. The results indicated the interaction of Li⁺ ions with the ether oxygen of the PEG, and the formation of transient crosslinking with LiClO₄, resulting in an increase of the T_g of the composite electrolyte. The VTF‐type behavior of the ionic conductivity implied that the diffusion of the charge carriers was assisted by the segmental motions of the polymer chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2752–2758, 2007     

Synthesis and characterization of pH‐ and salt‐responsive hydrogels based on etherificated sodium alginate

Hydrogels composed of etherificated sodium alginate (ESA), sodium acrylic acid (NaAA), and poly (vinyl alcohol) (PVA) were synthesized by aqueous solution polymerization. The effects of reaction variables such as terminal pH, ions, and ionic strength on hydrogel swelling ratio (SR) were determined and compared. SR was influenced strongly by pH and ionic strength. SR increased with increasing pH but tended to decrease with PVA content. At a given ionic strength, SR of ESA/NaAA/PVA hydrogel was dependent on the valence of anion; SR was higher in multivalent anion salt solution than in monovalent anion salt solution, i.e., SR_K2SO4 > SR_KCl and SR_Na2SO4 > SR_NaCl. The swelling kinetic of the hydrogels showed Fickian kinetic diffusion in acidic media and non‐Fickian behavior in alkaline media. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Composite polymer electrolyte incorporating WO3 nanofillers with enhanced performance for dendrite-free solid-state lithium battery

All solid-state lithium batteries (ASS-LBs) with polymer-based solid electrolytes are a prospective contender for the next-generation batteries because of their high energy density, flexibility, and safety. Among all-polymer electrolytes, PEO-based solid polymer electrolytes received huge consideration as they can dissolve various Li salts. However, the development of an ideal PEO-based solid polymer electrolyte is hindered by its insufficient tensile strength and lower ionic conductivity due to its semi-crystalline and soft chain structure. In order to lower the crystallization and improve the performance of PEO-based solid polymer electrolyte, tungsten trioxide (WO₃) nanofillers were introduced into PEO matrix. Herein, a PEO₂₀/LiTFSI/x-WO₃ (PELI-xW) (x = 0%, 2.5%, 5%, 10%) solid composite polymer electrolyte was prepared by the tape casting method. The solid composite polymer electrolyte containing 5 wt% WO₃ nanofillers achieved the highest ionic conductivity of 7.4 × 10^-4 S cm^-1 at 60 °C. It also confirms a higher Li-ion transference number of 0.42, good electrochemical stability of 4.3V, and higher tensile strength than a PEO/LiTFSI (PELI-0W) fillers-free electrolyte. Meanwhile, the LiFePO₄│PELI-xW│Li ASS-LBs demonstrated high performance and cyclability. Based on these findings, it can be considered a feasible strategy for the construction of efficient and flexible PEO-based solid polymer electrolytes for next-generation solid-state batteries.