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In this work, blends of polyethylene oxide (PEO) and poly(sodium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl) imide) (PNaMTFSI) in different compositions were investigated for their application as solid electrolytes for sodium batteries. PNaMTFSI and PEO are miscible, exhibiting only one Tg in the whole range of compositions. PNaMTFSI was shown to reduce the crystal growth rate of PEO crystals but increase PEO nucleation, making the overall crystallization rate higher in blends with 15 and 30 wt % PNaMTFSI. The ionic conductivity is also affected by the blend composition. The highest values of ionic conductivity were observed with 15 and 30 wt % PNaMTFSI at high temperatures equal to 5.84 × 10–5 and 7.74 × 10–5 S cm–1 at 85 °C, respectively, with values of sodium-ion transference numbers of higher than 0.83 and electrochemical stability between 3.5 and 4.5 V versus Na+/Na0 depending on the composition, which opens the possibility of its use in sodium batteries. Finally, a comparison was made between the effect of sodium and lithium on these types of electrolytes, showing that sodium electrolytes have a lower ionic conductivity due to the larger size of the Na cation. The differences in the spherulitic growth rate and overall crystallization rate between Li and Na-containing electrolytes were compared and rationalized in terms of the blends’ intermolecular interactions and the relative contribution of primary nucleation and growth. We acknowledge the funding by Agencia Estatal de Investigación (no. PLEC2021-007929). This work has received funding from the Basque Government through grant no. IT1503-22.

Graft copolymers between conducting PEDOT and biodegradable PCL were synthesized and investigated for 3D printing scaffolds for patterning of muscle cells.

Herein we report a novel family of deep eutectic monomers and the corresponding polymers, made of (meth)acrylic ammonium salts and a series of biobased polyphenols bearing catechol or pyrogallol motifs. Phenolic chemistry allows modulating molecular interactions by tuning the ionic polymer properties from soft adhesive to tough materials. For instance, pyrogallol and hydrocaffeic acid-derived ionic polymers showed outstanding adhesiveness (>1 MPa), while tannic acid/gallic acid polymers with dense hydrogen bond distribution afforded ultratough elastomers (stretchability ≈1000% and strength ≈3 MPa). Additionally, phenolic polymeric deep eutectic solvents (polyDES) featured metal complexation ability, antibacterial properties, and fast processability by digital light 3D printing. This work was supported by Marie Sklodowska-Curie Research and Innovation Staff Exchanges (RISE) under grant agreement no. 823989 “IONBIKE”. The financial support from CONICET and ANPCyT (PICT 2018-01032) (Argentina) is also gratefully acknowledged.

Solid-state lithium batteries are considered one of the most promising battery systems due to their high volumetric energy density and safety. Poly(ethylene oxide) (PEO) is the most commonly used solid polymer electrolyte in solid-state batteries. In this article, we introduce new polyphosphoester polymer electrolytes, which show improved flame retardant properties in comparison with PEO. For this purpose, new polyphosphoester copolymers were synthesized, including phosphoester, poly(ethylene glycol) (PEG) and UV cross-linkable vinyl units. Solid polymer electrolyte films based on polyphosphoester copolymers and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared by curing under UV-light. The crystallinity present in the copolymers due to the PEG segment decreases with the amount of salt in the electrolyte, as seen by DSC. Solid polymer electrolytes based on polyphosphoester copolymers show ionic conductivity values as high as 2 × 10−4 S cm−1 at 70 °C. FTIR analysis showed that lithium cations complexed with phosphoester groups provoked an increase in the lithium transference number to 0.26 as compared to that of PEO 0.17. Pyrolysis flow combustion calorimetry (PCFC) or micro-calorimetry results demonstrated the improved flame retardancy of the polyphosphoesters in comparison to a reference PEO based polymer electrolyte. The selected polyphosphoester solid electrolyte was investigated in a solid-state lithium cell Li0/polymer electrolyte/LFP battery showing a specific capacity retention close to 80% and coulombic efficiency greater than 98% over 100 cycles at 70 °C.

The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime. This work received funding from the Basque Government through grant IT1503 - 22. S.K.K . acknowledges funding by the U.S. Department of Energy, Office of Science, grants DE- SC0018182, DE-SC0018135, and DE-SC0018111. The authors acknowledged the financial support of Fundacion Losano, PIP2011 848, and PUE No. 22920160100007 (CONICET) . The authors acknowledge the support of Ana Martínez Amesti, Microscopy: Polymer Characterization Research Service, SGIker (UPV/EHU) .

The constant increase of plastic waste released into the environment is a global problem which is raising concern to the general population. Although there are many different approaches for recycling plastics, chemical recycling is currently seen as one of the most promising technologies in that it allows plastic waste to fit into a sustainable, circular economy. Herein we investigate the chemical recycling of bisphenol A polycarbonate (BPA-PC) using diols of different chain lengths to yield bisphenol A and innovative carbonate-containing diols. Subsequently, the latter are polymerised into a series of unique value-added aliphatic polycarbonates (APC). The new polymers obtained by this method have shown promising values of ionic conductivity that make them attractive candidates to be implemented as sustainable polymer electrolytes for solid-state batteries. This procedure opens the way for recycling methods to produce unique, innovative materials using plastic waste as an alternative sustainable feedstock.

Current electrolytes for lithium batteries are usually composed of at least two chemical compounds, an organic solvent such as a cyclic carbonate and a lithium salt such as LiPF6. Here, the concept of using a single-component electrolyte is demonstrated in lithium batteries based on new lithium borate ionic liquids at room temperature. The design concept of this class of lithium ionic liquids (LiILs) is based on an asymmetrically substituted central tetracoordinate boron atom with oligoethylene glycol groups, fluorinated electron-attracting groups, and one alkane group. The optimized borateLi+ LiILs show a high ionic conductivity value of >10−4 S cm−1 at 25 °C, high lithium transference numbers ( = 0.4 – 0.5) and electrochemical stability (>4 V). Some of the LiILs present high compatibility with lithium-metal electrodes showing stable polarization profiles in platting/stripping tests. The selected LiIL is investigated as single-component electrolytes in lithium-metal battery cells showing discharge capacity values in Li0/LiIL/lithium–iron phosphate and Li0/LiIL/lithium titanate cells of 124 and 75 mAh g−1, respectively, at a C-rate of 0.2 C and 65 °C with low-capacity loss. This work was funded and supported by a Grant for Basque Government through grant IT1309-19, and European Commission's funded Marie Skłodowska–Curie project POLYTE-EID (Project No. 765828) and Spanish MCIN/AEI/PID2020-119026GB-I00. G.G.-G. is grateful to “Secretaría de Educación, Ciencia, Tecnología e Innovación” from Ciudad de México for the postdoctoral fellowship through grant SECTEI/133/2019. G.G.-G. also thanks the PhD. IOSM for being the driving force and constant support.

In this work, blends of Poly(ethylene oxide), PEO, and poly(1,6-hexanediol), PHD, were prepared in a wide composition range. They were examined by Differential Scanning Calorimetry (DSC), Polarized Light Optical Microscopy (PLOM) and Wide Angle X-ray Scattering (WAXS). Based on the results obtained, the blends were partially miscible in the melt and their crystallization was a function of miscibility and composition. Crystallization triggered phase separation. In blends with higher PEO contents both phases were able to crystallize due to the limited miscibility in this composition range. On the other hand, the blends with higher PHD contents display higher miscibility and therefore, only the PHD phase could crystallize in them. A nucleation effect of the PHD phase on the PEO phase was detected, probably caused by a transference of impurities mechanism. Since PEO is widely used as electrolyte in lithium batteries, the PEO/PHD blends were studied with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI), and the effect of Li-salt concentration was studied. We found that the lithium salt preferentially dissolves in the PEO phase without significantly affecting the PHD component. While the Li-salt reduced the spherulite growth rate of the PEO phase within the blends, the overall crystallization rate was enhanced because of the strong nucleating effect of the PHD component. The ionic conductivity was also determined for the blends with Li-salt. At high temperatures (&gt, 70 °C), the conductivity is in the order of ~10−3 S cm−1, and as the temperature decreases, the crystallization of PHD was detected. This improved the self-standing character of the blend films at high temperatures as compared to the one of neat PEO.

Implantable electrophoretic drug delivery devices have shown promise for applications ranging from treating pathologies such as epilepsy and cancer to regulating plant physiology. Upon applying a voltage, the devices electrophoretically transport charged drug molecules across an ion‐conducting membrane out to the local implanted area. This solvent‐flow‐free “dry” delivery enables controlled drug release with minimal pressure increase at the outlet. However, a major challenge these devices face is limiting drug leakage in their idle state. Here, a method of reducing passive drug leakage through the choice of the drug co‐ion is presented. By switching acetylcholine's associated co‐ion from chloride to carboxylate co‐ions as well as sulfopropyl acrylate‐based polyanions, steady‐state drug leakage rate is reduced up to sevenfold with minimal effect on the active drug delivery rate. Numerical simulations further illustrate the potential of this method and offer guidance for new material systems to suppress passive drug leakage in electrophoretic drug delivery devices., Drug leakage is a safety concern for long‐term implantable electrophoretic drug delivery devices. In this work, co‐ion engineering is proposed as a clinically viable method to drastically reduce drug leakage rate, without any sacrifices on the device active performance. The co‐ion engineering method is drug‐independent and can be readily applied to existing electrophoretic drug delivery devices.

In this work, we develop novel single-ion polymer electrolytes by mixing poly(lithium 1-[3-(methacryloyloxy) propylsulfonyl]-1-(trifluoromethanesulfonyl) imide) (PLiMTFSI) and poly(ethylene oxide) (PEO) with different molecular weights. The impact of PLiMTFSI on the crystallization and conductivity of the blends was explored in detail. When PLiMTFSI (an amorphous polymer) is added to PEO, the crystallization ability of PEO decreases. However, blends with high-molecular weight PEO (1000 kg/mol) experience a lower reduction in crystallinity and melting points. As a result, lower conductivity values were obtained in these blends, which is why most of the study was then focused on blends incorporating a lower-molecular weight PEO (100 kg/mol). We show that the melting point, degree of crystallinity, spherulitic growth, and overall crystallization kinetics decrease in the presence of PLiMTFSI, which are all signs of miscibility. Furthermore, the blends show a single glass transition temperature over the whole composition range. Therefore, our results indicate that PEO and PLiMTFSI are miscible, as corroborated by applying the Nishi-Wang equation and obtaining negative χ12 values (i.e., the Flory-Huggins interaction parameter) for all blends. Our results show that intermediate molecular weight blends (100 kg/mol PEO and 50 kg/mol PLiMTFSI) showed the highest ionic conductivity value. Interestingly, a value of 2.1 × 10-4 S/cm was obtained at 70 °C, which is one of the highest reported so far for a free-standing film of single-ion conducting polymer electrolytes. Finally, employing dielectric spectroscopy, the contribution of ion density and ion mobility to ionic conductivity could be separated. It was found that ion mobility is the parameter that has a greater weight in the conduction process., We wish to thank the Consejo Nacional de Ciencia y Tecnología (the National Council of Science and Technology) (CONACYT), Mexico, for the grant awarded to J.L.O.-M. no. 471837. L.P. has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement no. 797295. We acknowledge funding from the Basque Government through grant IT1309-19 and IT1175-19. Authors would like to thank IONBIKE-RISE project, and this project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 823989.

Iongel-based CO2 separation membranes were prepared by fast (&lt, 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C2mim]+ cation and anions such as [TFSI]&minus, [FSI]&minus, [C(CN)3]&minus, and [B(CN)4]&minus, The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and free-standing iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO2 solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO2 solubility, were found to be strictly dependent on the IL content and the anion&rsquo, s nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA&ndash, C(CN)3 iongels presented the highest CO2 solubility values ranging from 72 to 80 mmol/g. Single CO2 permeabilities of 583 &plusmn, 29 Barrer and ideal CO2/N2 selectivities of 66 &plusmn, 3 were obtained with the PEGDA&ndash, 70 C(CN)3 iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO2 separation.

Lignin is a cheap, abundant and non-toxic group of complex phenolic polymers obtained in large amounts from the papermaking and cellulosic biofuel industries. Although the application of lignin has been explored in these and several more industries, there are limited applications of lignin in the energy industry. However, numerous research revealed a great interest in the exploration of this renewable biopolymer in storage energy devices. Some of these applications include the use of lignin as an expander for lead–acid batteries, electrodes for primary and rechargeable batteries, electrodes for electronic double layer capacitors and electrochemical pseudocapacitors, and to feed different types of fuel cells. The use of lignin in energy storage devices improves not only the performance of these devices but also decreases the price and toxicity, contributing to obtaining greener energy devices. Based on the above, this review provides an overview of the main research work related to the use of lignin as a renewable component, suitable to replace some synthetic and toxic compounds used in the fabrication of energy storage devices with particular emphasis on batteries, advanced supercapacitors, and solar and fuel cells.

A poly( ortho -phenylenediamine- co -aniline) copolymer is synthesized via the oxidative route, using a 1:1 M ratio of aniline to ortho -phenylenediamine ( o PDA) and ammonium persulfate as the oxidizing agent. Infrared spectroscopy indicates that the copolymer contains the functional groups typically present in polyaniline and poly( ortho -phenylenediamine); whereas UV-vis-NIR spectroscopy shows that the copolymer adopts a phenazine-type structure. Cyclic voltammetry evidences the copolymer synthesis, as a redox peak at −65 mV, different from those exhibited by polyaniline (160 mV and 600 mV) or poly( o -phenylenediamine) (−240 mV) is observed. Finally, electrochemical impedance spectroscopy and the charge/discharge test provide support to propose the copolymer application in electrodes for supercapacitors.

Poly(ethylene oxide) (PEO) is the most widely used polymer in the field of solid polymer electrolytes for batteries. It is well known that the crystallinity of polymer electrolytes strongly affects the ionic conductivity and its electrochemical performance. Nowadays, alternatives to PEO are actively researched in the battery community, showing higher ionic conductivity, electrochemical window, or working temperature range. In this work, we investigated polymer electrolytes based on aliphatic polyethers with a number of methylene units ranging from 2 to 12. Thus, the effect of the lithium bis(trifluoromethanesulfone) imide (LiTFSI) concentration on the crystallization behavior of the new aliphatic polyethers and their ionic conductivity was investigated. In all the cases, the degree of crystallinity and the overall crystallization rate of the polymers decreased drastically with 30 wt % LiTFSI addition. The salt acted as a low molecular diluent to the polyethers according to the expectation of the Flory&ndash, Huggins theory for polymer&ndash, diluent mixtures. By fitting our results to this theory, the value of the interaction energy density (B) between the polyether and the LiTFSI was calculated, and we show that the value of B must be small to obtain high ionic conductivity electrolytes.

The use of Polyaniline (PAni) as conductive filler in several kinds of non-conductive polymers, such as elastomers, has been extensively studied in the production of easily processable semiconductors. This work focuses on the use of a PAni/clay nanocomposite (PCN) – instead of pristine PAni – as conductive filler of styrene-butadiene rubber (SEBS) to produce a PCN/SEBS semiconducting elastomer. In order to accomplish this, a novel solvent-free and low-temperature press-processing technique was proposed and applied. It was also compared to the traditional rubber mechanical processing method. The preparation of PCN/SEBS was conducted by following a two-stage procedure: Pain in situ synthesis and mechanical mixing. PCN/SEBS was characterized by Raman spectroscopy, dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM), the electrical properties were measured by means of the two-probe technique and electrochemical impedance spectroscopy (EIS). It was found that the traditional processing method led to a highly insulating material, while the proposed procedure results in semiconducting composites, showing electrical conductivity values up to 10−7 S cm−1. From the mechanical standpoint, this novel treatment results in composites with lower stiffness at low temperatures and similar elastic behavior at the transition region when compared to the material produced by the typical mixing chamber procedure. Although this method still needs to be improved since these materials show less homogeneity than their counterparts and they crumble at ∼100 °C, this work sets the foundation for an alternative processing method to obtain PAni-based semiconducting elastomers.

Unformatted preprint version of the submitted article The overall crystallization kinetics of polymer nanocomposites is determined by nucleation and crystal growth, which are both greatly affected by confinement. Heterogeneous nucleation is influenced by the interphase area between filler and polymer matrix. Starting with a homogeneous nematic aqueous dispersion of a mixture containing polyethylene glycol (PEG) and varying amounts of a high aspect ratio layered silicate (hectorite, Hec), nanocomposite films were casted displaying a systematic variation of the degree of PEG confinement. This is achieved by a partial phase segregation upon drying, where independently of filler content a thermodynamically stable, 1 dimensional crystalline hybrid with constant volume of intercalated PEG (0.81 nm corresponding to a fraction 75 wt% and 55 vol%, respectively) is formed. This intercalated hybrid phase is incorporated into segregated PEG domains. The segregation is a kinetically controlled process and the length scale of segregation increases with PEG available in surplus of the hybrid. Due to the very large lateral extension of the Hec, the segregated domains are increasingly two dimensional. As evidenced by transmission electron micrographs and powder X-ray diffraction, the segregation produces composite structures where, in dependency of filler content, PEG slabs of different thickness are separated by domains of the intercalated hybrid material. The crystallization behavior of these bi-phasic materials was investigated by Differential Scanning Calorimetry (DSC) and Polarized Light Optical Microscopy (PLOM). DSC results reveal a competition between the nucleating effect of Hec, which was particularly important at low amounts, and the PEG confinement effect at higher filler loadings. Applying a self-nucleation protocol, the nucleation efficiency of the hectorite was shown to be up to 67%. The isothermal crystallization kinetics accelerated at low Hec contents (nucleation), went through a maximum and then decreased (confinement) as Hec content increased. Additionaly, a clear correlation between filler content and the Avrami index was obtained supporting the increase in confinement as filler loading increased. The authors thank Florian Puchtler for producing the synthetic sodium hectorite, Marco Schwarzmann for the SEM and TEM measurements and sample preparation via cryo ion slicing, and Dr. Sabine Rosenfeldt for the SAXS measurements. We appreciate the support of the Keylab for Optical and Electron Microscopy and the Keylab for Small Scale Polymer Processing of the Bavarian Polymer Institute (BPI). This work was supported by the German Science Foundation (DFG) within the collaborative research project SFB 1357. J.M. acknowledges support from the Provincial Council of Gipuzkoa under the program Fellow Gipuzkoa and partial financial support to the IBERDROLA Foundation. J.L.O.M. wish to thank the National Council of Science and Technology (CONACYT) in México for his grant 471837. We acknowledge funding by Mineco MAT2017-83014-C2-1-P project and by the Basque Government through grant IT1309-19. This work has also received funding from the European Union´s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 778092.

Polyaniline/iota-carrageenan (ι-CGN) biocomposites were synthesized via in situ methodology using ammonium persulfate as the oxidizing agent. Both ionic (band at 1131 cm −1 ) and hydrogen bond (bands at 2500 and 3500 cm −1 ) interactions between polyaniline and ι-CGN were determined by infrared spectroscopy. Such intermolecular interactions provided the biocomposites with a cross-linked structure that provided the materials with hydrogel behavior. Biocomposite electro-conductivity, determined by the 4-probe technique, was in the range of semiconductors (10 −3 to 10 −2 S cm −1 ); whereas electro-activity, assessed by cyclic voltammetry, showed the oxidation–reduction transitions typical of polyaniline. Based on the properties of polyaniline and ι-CGN, some applications for the new materials in the field of biosensor design, electrochemical capacitors, or tissue engineering scaffolds are possible. It is worth saying that both electro-conductive and electro-active properties of polyaniline/ι-CGN biocomposites are reported here for the first time.

A series of poly(ortho-phenylenediamine-co-aniline)/iota-carrageenan biocomposites were synthesized via oxidative polymerization. Infrared spectroscopy revealed the ionic interaction between the sulfate groups in iota-carrageenan (i-CRG) and the quaternary amine groups in the copolymer, demonstrating that i-CRG exerts the function as the dopant. Cyclic voltammetry showed redox potentials around 35 mV, indicating that the i-CRG presence does not constrain electroactivity. Additionally, the biocomposites presented ionic and electrical conductivity (in the range of 10−5-10-3 S cm-1) determined respectively by electrochemical impedance spectroscopy and the four-point technique. Interestingly, it was observed by scanning electron microscopy that i-CRG played the role as a template since its presence, depending on the weight ratio respecting the copolymer, caused copolymer morphology modification. This set of properties is highly advantageous due to the combination of conduction mechanisms and electroactive behavior, which can be used in applications related to energy storage devices such as supercapacitors and chemical sensors.

Mixed ionic-electronic conductors, such as poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) are postulated to be the next generation materials in energy storage and electronic devices. Although many studies have aimed to enhance the electronic conductivity and mechanical properties of these materials, there has been little focus on ionic conductivity. In this work, blends based on PEDOT stabilized by the polyelectrolyte poly(diallyldimethylammonium) (PolyDADMA X) are reported, where the X anion is either chloride (Cl), bis(fluorosulfonyl)imide (FSI), bis(trifluoromethylsulfonyl)imide (TFSI), triflate (CF3SO3) or tosylate (Tos). Electronic conductivity values of 0.6 S cm&minus, 1 were achieved in films of PEDOT:PolyDADMA FSI (without any post-treatment), with an ionic conductivity of 5 &times, 10&minus, 6 S cm&minus, 1 at 70 &deg, C. Organic ionic plastic crystals (OIPCs) based on the cation N-ethyl-N-methylpyrrolidinium (C2mpyr+) with similar anions were added to synergistically enhance both electronic and ionic conductivities. PEDOT:PolyDADMA X / [C2mpyr][X] composites (80/20 wt%) resulted in higher ionic conductivity values (e.g., 2 &times, 5 S cm&minus, C for PEDOT:PolyDADMA FSI/[C2mpyr][FSI]) and improved electrochemical performance versus the neat PEDOT:PolyDADMA X with no OIPC. Herein, new materials are presented and discussed including new PEDOT:PolyDADMA and organic ionic plastic crystal blends highlighting their promising properties for energy storage applications.