Polymer Gel Research Articles

3D-Printed Flexible Polyacrylamide/Alginate Gel Polymer Electrolyte for Zinc-Ion Batteries

Flexible and wearable electronics are increasingly popular and utilized in various forms. Batteries have become essential as an energy source for wearable electronics. To meet demands of such electronics, these batteries must remain flexible, lightweight, possess good electrochemical performance, customizable shape, and ensure safety. Zinc-ion batteries (ZIBs) have emerged as a promising energy source for these applications. However, ZIBs encounter challenges due to the lack of flexible electrolytes. Polyacrylamide (PAM) is a polymer widely used as gel polymer electrolytes (GPEs) owing to its versatile electrical conductivity and excellent flexibility. However, PAM alone lacks the mechanical strength required to support flexible and wearable electronics adequately. To address this limitation, alginate (Alg), a polysaccharide with good compatibility with PAM, is incorporated in varying concentrations (0-3 %wt.) to form interpenetrating networks (IPN) hydrogels, with a chemical network of PAM and a physical network of alginate to enhance the overall mechanical properties. Following this, the 3D-printed PAM/Alg hydrogels are immerged in a 2M ZnSO4 electrolyte to create PAM/Alg gel polymer electrolytes (PAM/Alg-GPEs). This process significantly improves the mechanical properties of PAM/Alg-GPEs. Subsequently, the ionic conductivity of these 3D-printed PAM/Alg-GPEs is evaluated using electrochemical impedance spectroscopy (EIS). The results demonstrate that PAM/Alg-GPEs exhibit the desired flexibility along with sufficient electrochemical performance, making them promising candidates for use as wearable electrolytes in zinc-ion batteries.

Three-dimensional source position verification in image-guided high-dose-rate brachytherapy using an XCT-based gel dosimeter.

Comprehensive quality assurance (QA) for a seamless workflow of high-dose-rate brachytherapy, from imaging to planning and irradiation, is uncommon, and QA of the source dwell position is performed in one- or two-dimensions. Gel dosimetry using magnetic resonance imaging (MRI) is effective in verifying the three-dimensional distribution of doses for image-guided brachytherapy (IGBT). However, MRI scanners are not readily accessible, and MRI scanning is time-consuming. Nevertheless, X-ray computed tomography (XCT) is available for IGBT planning. In this study, we designed and developed an efficient method for QA for a seamless workflow of IGBT with a new commercially available XCT-based polymer gel dosimeter. To enable direct insertion of brachytherapy applicators, the gelatinizing agent of the dosimeter was modified. A cylindrical polyvinyl chloride jar was filled with the modified gel dosimeter, which was subsequently used to determine the reproducibility of source dwell positions, detectability of source positional errors from intentionally introduced catheter length offsets, effect of looped source transfer tubes on the average displacement, extent of inter-observer variation, and gel robustness following multiple needle-insertions. Three ProGuide sharp needles were inserted into the jar. The dwell time at each point was determined to identify the irradiated volume with a diameter of approximately 10mm on XCT images. All the times were the same. The plan was delivered using an afterloader with an Ir-192 radioactive source, and the irradiated gel dosimeter was scanned using an XCT scanner. The subtracted images were generated from pre- and post-irradiated images. Volumes with incremented Hounsfield units were manually identified and contoured. The centroid of the volume was defined as the measured source dwell position. Subsequently, planned source dwell positions were extracted from the DICOM file of the plan. Finally, the source dwell positions in plan and irradiated gel were compared in three axes. The hardness of the dosimeter was 1250% greater than that of the previously reported gel dosimeter. Source dwell positions were visually identified in the XCT image. Testing of CT acquisition, planning, irradiation, and analysis was completed in approximately 1h. In the reproducibility test of source dwell positions, created by inserting three needles (each with three source dwell positions), the average displacements of the source positions from the first source dwell position were within 0.5mm in all three directions. In the detectability test, displacements were less than 1mm in the x-y plane but greater than 1mm in the z-axis, which was the source path direction. When errors of 1-3mm were intentionally introduced, the measured displacement was within 0.7mm of the median (range: 0.21-1.65mm) of intentional errors. When the transfer tube was looped, the source dwell position displaced by approximately 1mm. After 20 needle-insertions, the source dwell position displacement was within 1mm. The maximum inter-observer variation of contouring was 0.57mm. The XCT-based gel dosimeter enabled verification of three-dimensional source dwell positions for a seamless workflow of IGBT with high precision and efficiency.

The Effects of Polymerization on the Performance of Viologen-Based Electrochromic Devices

In this work, electrochromic devices were prepared using the redox couple ethyl viologen diperchlorate and 1,1′-diethyl ferrocene in propylene carbonate as an aprotic solvent to facilitate ions separation and diffusion inside the devices. Electrochromic devices were made using electrochromic gel mixtures at the concentrations of 55%, 60% and 65% with respect to the bisphenol A polymer. In particular, two sets of gels were made: one set contained the bisphenol A not-polymerized while and the second one contained the polymerized polymer. Different techniques, such as cyclic voltammetry, UV-vis-NIR, and Raman spectroscopy, were used to study such systems to understand the differences in terms of performances between the different sets of electrochromic devices. Cyclic voltammetry confirmed that the oxidation process of the 1,1′-diethyl ferrocene and the reduction of the ethyl viologen diperchlorate occurred at about 0.4 V. Interesting variations in the transmittances were found between the two groups of samples. The best values of CE were provided by the electrochromic devices based on the polymerized electrochromic gel mixture at a concentration of 60% (EM60). The EM60 device result was CE = 92.82 C/cm2 in the visible region and CE = 80.38 C/cm2 in the near–infrared region, confirming that these devices can be used for energy-saving applications. A structural characterization of the materials used in the two sets of electrochromic devices was made using Raman spectroscopy, and the analysis supports the electrochemical models used to explain the processes involved during operation of the electrochromic systems.

Review on polymer electrolytes for lithium‐sulfurized polyacrylonitrile batteries

AbstractLithium‐sulfur (Li‐S) batteries are deemed as the next generation of energy storage devices due to high theoretical specific capacity (1675 mAh g−1) and energy density (2600 Wh kg−1). However, the commercial application has always been constrained by lithium polysulfide (LiPSs) shuttling effects and still has a long way to go. Sulfurized polyacrylonitrile (SPAN) is a promising alternative candidate to replace traditional sulfur cathode and is conducive to eliminating LiPSs by realizing “solid‐solid” direct conversion in conventional carbonate electrolytes. However, an over 25% irreversible capacity loss is exhibited inevitably in the first discharge process, the inherent structure of SPAN and the related reaction mechanism remain unclear. In this review, the structure characteristics and electrochemical behaviors of SPAN are summarized for better interpreting current knowledge and favoring the design of high performance materials. In the past few decades, many problems in traditional Li‐S batteries have been solved by improving electrolytes. Polymer electrolytes (PEs) have been widely used due to structural designability, multi‐functionality, exceptional chemical stability, and excellent processability. Surprisingly, the relevant researches on PEs compatible with SPAN remains limited currently. Therefore, the recent modification strategies of gel polymer electrolytes and solid polymer electrolytes in Li‐SPAN batteries are introduced in terms of Li+ transfer and interface engineering, the design principles are concluded, the specific challenges encountered by polymer‐based electrolytes are summarized and the instructive directions for future research on PEs are demonstrated, facilitating the commercialization of Li‐SPAN batteries.

Effect of Nanosized Al2O3 Dispersion on the Structural and Electrochemical Properties of PMMA/TEGDME-Based Mg-Ion Conducting Polymer Gel Electrolyte

Effect of Nanosized Al2O3 Dispersion on the Structural and Electrochemical Properties of PMMA/TEGDME-Based Mg-Ion Conducting Polymer Gel Electrolyte

Sodium polyacrylate hydrogel electrolyte: Flexible rechargeable supercapacitor using thermally reduced graphene oxide nanosheets

The alternative source of the gel polymer electrolyte (GPE) is introduced by developing the sodium polyacrylate (S-PANa) solid hydrogel electrolyte, which is the front runner in the recent flexible and wearable electronic devices due to their excellent mechanical property, high ionic conductivity, and electrochemical stability. In this work, we synthesized the S-PANa solid hydrogel electrolyte and utilized it for the flexible symmetric supercapacitor using thermally reduced graphene oxide nanosheets (TRGO) coated on carbon cloth as an electrode. The prepared S-PANa hydrogel is of a highly porous nature and has better surface roughness, as examined by the Field Emission Scanning Electron Microscopy (FE-SEM) and 3D nano profiler analysis. The electrochemical characterization of the assembled flexible solid-state hydrogel supercapacitor (FSHSC) reveals the electric double-layer capacitive behavior with an excellent device capacitance of 45.77 mF/cm2. The significant role of diffusion charge re-distribution, overcharging issues, ohmic drop, and leakage current of the FSHSC is studied, followed by self-discharge and leakage current analysis. Moreover, the FSHSC device delivers the maximum energy density of 5.15 μWh/cm2 with a remarkable retention capacitance of 99 % over 10,000 continuous cycles. Further, in practical utilization, the solar-charged FSHSC device can effectively power the electronic LED for a long duration and enhance its efficiency for the development of a sustainable backup power system. Overall, these experimental results demonstrated the significant use of the S-PANa hydrogel-based flexible device, which can be an alternative source in future energy storage systems instead of using gel electrolyte-based flexible devices.

Quantitative Macromolecular Modeling Assay of Biopolymer-Based Hydrogels

The rubber elasticity theory has been lengthily applied to several polymeric hydrogel substances and upgraded from idealistic models to consider imperfections in the polymer network. The theory relies solely on hyperelastic material models in order to provide a description of the elastic polymer network. While this is also applicable to polymer gels, such hydrogels are rather characterized by their water content and visco-elastic mechanical properties. In this work, we applied rubber elasticity constitutive models through hyperelastic parameter identification of hydrogels based on their stress–strain response to compression. We further performed swelling experiments and determined the intrinsic properties, i.e., density, of the specimens and their components. Additionally, we estimated their equilibrium swelling and employed it in the swelling-equilibrium theory in order to determine the polymer–solvent interaction parameter of each hydrogel with regard to cross-linking. Our results show that the average mesh size obtained from the rubber elasticity theory can be regarded as a concentration-dependent characteristic length of the hydrogel’s network and couples the non-linear elastic response to the specimens’ inherent visco-elasticity through hysteresis as a quantifier of energy dissipation under large deformation.

Designing Bilayer Heterostructure Functional Polymer Electrolytes with Interfacial Engineering Strategy for High‐Performance Lithium Metal Batteries

AbstractThe uncontrollable lithium (Li) dendrites growth and complex electrode/electrolyte interface (EEI) problems are hindering the further application of high energy density lithium metal batteries (LMBs) in practice. Herein, a bilayer heterostructure gel polymer electrolyte (BGPE) is designed by directly curing functional boron‐containing monomers on the electrode surface to ensure excellent conductivity while solving the interface problems, achieving durable high voltage resistance and Li dendrites suppression. The unoccupied p‐orbital boron moiety of the 3D crosslinked network in BGPE not only improves the Li+ transference number (0.78), but also enhances the interfacial stability of the Li metal and inhibits the dendrites growth by anchoring PF6− anions and regulating the uniform Li deposition, thus ensuring a long cycle for Li/BGPE/Li cells. In addition, the functional additives tris(trimethylsilyl) phosphite and tris(pentafluorophenyl)borane can preferentially oxidize and decompose to form stable B, F, and Si‐rich EEIs, and effectively regulate the uniform growth of EEI. Thus, the LiNi0.5Co0.2Mn0.3O2/BGPE/Li and LiFePO4/BGPE/Li full cells exhibit stable cycling and excellent rate performance. This work provides a guiding design direction to address the EEI problems for high energy density LMBs.

Effect of SiO2 on the Performance of Cellulose/Poly(Vinylidene Fluoride) Films as Polymer Electrolytes for Lithium Ion Battery

AbstractPolymer electrolytes serve as highly efficient alternatives to liquid electrolytes, especially in terms of safety in lithium ion batteries. Among various polymers, Cellulose contains electron‐donating atoms which can coordinate with lithium salts and be used as polymer electrolyte. Also, cellulose can be blended with other polymers to improve their properties. Polymer electrolytes suffer from poor mechanical properties. Adding nanoparticles not only surmounts the drawback of poor mechanical properties but also improves physical and electrochemical properties. In this study, different weight ratios of PVDF/cellulose blend films containing silicon dioxide (SiO2) are prepared via solution casting method. The results explored ionic conductivity in order of 10−4 S cm−1. In addition, high transfer numbers (0.74<t+<0.98), wide electrochemical window (up to 6 V), acceptable charge capacity, and long cycle stability are attained. In details, for 90/10 (wt./wt.) cellulose/PVDF, the ionic conductivity reached 4.4×10−⁴ S cm−1, and the ion transfer number was obtained 0.98. Additionally, the electrochemical stability window for these gel polymer electrolytes exceeded 5 V. The sample containing 90 % cellulose achieved an optimal charge capacity of 225.3, with 93.4 % capacity retention after 200 cycles at 0.2 C.

Smartly tuning supramolecular chirality in polymer gels via photoexcitation-induced cooperative self-assembly

Smartly tuning supramolecular chirality in polymer gels via photoexcitation-induced cooperative self-assembly

Ethanolamine-modified gel electrolyte of zinc ion battery

The rapid growth of wearable electronic devices has spurred the development of flexible energy storage systems. However, the limitations of conventional rigid commercial batteries have hindered the advancement of wearable technology. Consequently, the development of stable, safe, highly flexible, and cost-effective flexible batteries has become a key focus in current battery research. Herein, we introduce a novel multifunctional flexible Prussian Blue–zinc battery utilizing a PVA-ZnCl₂ polymer gel electrolyte (EGPE) enhanced with ethanolamine (ETA), aimed at addressing the deficiencies of traditional electrolytes in terms of safety and mechanical performance. The Zn||Zn symmetric cell using EGPE electrolyte demonstrated an impressive long-term cycling stability of over 3000 hours at a current density of 0.15 mA cm−2. In contrast, the symmetrical cell using 0.8 M ZnCl2 aqueous electrolyte maintained its stability for only 400 hours. In addition, the prepared flexible zinc Prussian blue device maintained more than 65 % of its initial capacity of the device and its coulombic efficiency was close to 100 % after 400 cycles at an extreme current density of 10 A g−1. Furthermore, flexible device using the EGPE was able to maintain a stable power supply under various bending, torsion, folding and shearing conditions. Such innovative gel electrolyte demonstrated considerable prospects for utilisation in portably equipped devices and energy storage systems.

Selective Sorption of Noble Metals on Polymer Gel Modified with Ionic Liquid.

The solid phase extraction of Au, Ir, Pd, Pt, and Rh on a polymer gel modified with ionic liquid containing methylimidazolium groups (MIA-PG) has been investigated. The positively charged surface of the sorbent is highly suitable for the sorption of stable chlorido complexes of the studied analytes, while the retention of base metals Cu, Fe, Ni, Zn, and Mn is negligible. Optimization experiments performed showed that, at 0.05 M HCl, the degree of sorption of Au, Ir, Pd, and Pt is above 95%, and only for Rh, the maximum degree is 65%; complete elution is achieved in the mixture of thiourea in HCl. The results obtained from the equilibrium adsorption studies are fitted in various adsorption models, such as Langmuir and Freundlich, and the model parameters have been evaluated. The kinetics analysis indicated that the adsorption of Au, Ir, Pd, Pt, and Rh onto the sorbent follows the pseudo-second-order model. Intraparticle diffusion and ion exchange reactions were the rate-limiting steps. Analytical procedures were developed for Pd, Pt, and Rh determination in road dust and soil and for Au determination in copper ore and copper concentrate. The procedures are validated by the analysis of certified reference materials. Analytical figures of merit confirmed their applicability in routine laboratory practice.

Stretchable Coaxial Gel Polymer Electrolyte Based on a Styrene–Ethylene–Butylene–Styrene Block Copolymer Nanofiber for Stretchable Lithium-Ion Batteries

Stretchable Coaxial Gel Polymer Electrolyte Based on a Styrene–Ethylene–Butylene–Styrene Block Copolymer Nanofiber for Stretchable Lithium-Ion Batteries

Polymerization-Induced Self-Assembly Providing PEG-Gels with Dynamic Micelle-Crosslinked Hierarchical Structures and Overall Improvement of Their Comprehensive Performances.

Polymer gels are fascinating soft materials and have become excellent candidates for wearable electronics, biomedicine, sensors, etc. Synthetic gels usually suffer from poor mechanical properties, and integrating good mechanical properties, adhesiveness, stability, and self-healing performances in one gel is more difficult. Herein, polymerization-induced self-assembly (PISA) providing PEG-gels with an overall improvement in their comprehensive performances is reported. PISA synthesis is carried out in PEG (solvent) to efficiently produce various nanoparticles, which are used as the nanofillers in the subsequent synthesis of PEG-gels with dynamic micelle-crosslinked hierarchical structures. Compared to hydrogels, PEG-gels show excellent long-term stability due to the nonvolatile feature of PEG solvent. The hierarchical PEG-gels (with nanofillers) exhibit better mechanical and adhesive properties than the homogeneous-gels (without nanofillers). The energy dissipation mechanism of the PEG-gels is analyzed via stress relaxation and cyclic mechanical tests. High-density hydrogen bonds between the micelles and PAA matrix can be broken and reformed, endowing better self-healing properties of the dynamic micelle-crosslinked PEG gels. This work provides a simple strategy for producing hierarchical structural gels with enhanced properties, which offers fundamentals and inspirations for the designing of various advanced functional materials.

Gel polymer electrolytes containing SiO2 spheres with tuned sizes to increase rechargeability of quasi-solid-state Zn-air batteries

Rechargeable zinc–air batteries (RZABs) with high energy densities and low costs have attracted tremendous interest for meeting the ever-growing demand for flexible and portable applications. In these batteries, the quasi-solid/solid-state electrolyte plays a critical role in the battery performance, such as the cycling performance rate and power output. In this study, porous poly (vinyl alcohol) (PVA) and poly (acrylic acid) (PAA) composite gel polymer electrolytes (GPEs) were modified by incorporating SiO2 as a water retainer. For this reason, SiO2 spheres of different sizes were synthesized by varying the temperature (5, 20, 60, and 80 °C) and reaction time (2, 6, 18, and 24 h). According to the SEM micrographs, the average size ranged from 107 to 710 nm depending on the conditions. The porous PVA/PAA–SiO2 GPEs obtained by selecting three SiO2 sizes (107, 425, and 630 nm) exhibited higher water retention capability than the unmodified GPE. Among them, the GPE with SiO2–630 nm displayed the highest battery performance (1.46 V, 85 mWcm−2 @ 0.8 V). This was achieved using CoMn2O4 spinel as a bifunctional electrocatalyst, with a catalyst loading of 2 mg cm−2. The quasi-solid-state RZAB displayed twice the rechargeability of the RZAB assembled with Pt/C+IrO2/C (120 vs. 62 cycles). According to post-mortem tests, this can be related to the improved water retention, the decrease in the size of the formed Zn dendrites, and the stability of the bifunctional material. Thus, fine-tuning of the electrocatalyst/electrolyte interface strongly affects the rechargeability.

Brush-Like Polymeric Gels Enabled Photonic Crystals toward Ultrasensitive Cosolvent Chromism.

Responsive photonic crystals (RPCs) exhibit dynamic chromism upon trigger by various solvents, showing potential applications in qualitative identification and quantitative analysis of multicomponent solvents. However, distinguishing similar solvents, especially traces of cosolvents, remains challenging due to the limited sensitivity of RPCs. To address this, we herein introduce brush-like polymeric gels inside photonic crystals, forming a brush-like polymeric photonic gel (BPPG) that can trace tiny component changes. In this BPPG system, the acrylate backbones and polyethylene glycol (PEG) side-chains stretch incrementally due to the cosolvency of ethanol-water mixtures, resulting in highly sensitive chromatic responses within ethanol-rich concentrations. With water content varying slightly from 0 to 1 vol %, the reflection wavelength of BPPG can sharply redshift over 30 nm, leading to very noticeable changes in structural color. This enhanced sensitivity makes BPPG suitable for real-time, in situ purity monitoring of absolute ethanol during storage, transportation, and other applications.

Recyclable cellulose-based vitrimer electrolytes for lithium ion batteries

Cellulose as polymer electrolytes in lithium-ion batteries (LIBs) has a number of advantages such as low cost, readily available, abundant, environmentally friendly, and contains electron-donating groups within its structure. Beside, vitrimers are a novel class of polymer materials made of dynamic covalent networks that can undergo bond-exchange processes. Beyond cellulose's special qualities, cellulose-based vitrimer production is highly desired for enhancing electrolytes mechanical qualities, thermal stability, cyclability, and ionic conductivity. In this study, cellulose-based vitrimeric polymer electrolytes are prepared. At first, poly(glycidyl methacrylate-co-methyl acrylate) by different ratios of comonomers is prepared and then cellulose is cross-linked by prepared copolymers. Prepared vitrimers are recycled four steps through transesterification reaction and as-prepared and recycled crosslinked celluloses are used as gel polymer electrolytes (GPEs). The results showed the best ionic conductivity of as-prepared samples in order of 10−4 S/cm whereas ionic conductivity increased to order of 10−3 S/cm for recycled samples. Also, high lithium-ion transfer number of >0.8 was achieved for recycled samples. All as-prepared and recycled electrolytes had excellent electrochemical stability window (> 5 V). Also, improved specific capacity (>178 mA h g−1 with capacity retention upper than 90 % after 200 cycles at 0.2C of LiCoO2/GPEs/Gr) was attained.

Scaling the ionic conductivity and electrochemical properties of bio-based gel polymer electrolytes reinforced with Al2O3 nanofibers for energy storage applications

Scaling the ionic conductivity and electrochemical properties of bio-based gel polymer electrolytes reinforced with Al2O3 nanofibers for energy storage applications

Water as Dual-Function Plasticizer and Cosolvent in Gel Electrolytes for Dye-Sensitized Solar Cells.

This study presents a novel approach to developing eco-friendly dye-sensitized solar cells (DSSCs) using natural and renewable materials for gel polymer electrolytes (GPEs), reducing reliance on unsustainable solvents. Water is added to polar aprotic solvents, specifically ethylene carbonate/propylene carbonate (EC/PC), across various mass fractions (0:100 to 100:0). An amphiphilic hydroxypropyl cellulose (HPC) natural polymer is employed to formulate GPEs within this water-EC/PC cosolvent system, achieving successful gelation up to 50:50 mass fractions. Incorporating water reduced the gel strength and viscosity of the GPEs. Water acted as a plasticizer, enhancing the polymer chains mobility, and creating a more flexible and permeable structure. This increased ion diffusion coefficients and ion mobility, resulting in a maximum ionic conductivity of 18.17 mS cm-1. The highest efficiency achieved in DSSCs using these GPEs is 5.81%, with elevated short-circuit current density and reduced recombination losses. However, some compositions experienced syneresis, affecting their stability. The GPE with a 40:60 mass fraction exhibited superior long-term stability because it is free from syneresis, though it achieved a lower efficiency (4.83%), making it the best-performing sample. This work demonstrates the feasibility and benefits of using gel polymer electrolytes in an aqueous system, improving DSSC efficiency and sustainability.

Charge Separation Induced by Asymmetric Surface Charge Effects in Quasi‐Solid State Electrolyte for Sustainable Anion Storage

AbstractCompared with conventional lithium‐ion battery systems, anion‐intercalation in graphite cathodes opens avenues for the development of batteries with groundbreaking power density. This study explores the enhancement of dual‐ion batteries (DIBs) by gel polymer electrolyte (GPE) enhanced with surface‐charged nanoclays, focusing on overcoming traditional challenges such as electrolyte decomposition, anion‐solvent co‐intercalation, and interfacial instability at the graphite cathode. Three nanoclays including montmorillonite, kaolinite, and halloysite are compared by incorporating them into GPE and evaluating their effect on the electrochemical properties, ion conduction, and mechanical integrity of DIBs. Particular attention is paid to the halloysite because of its differential internal and external surface charges, which generate charge separation, facilitate optimal lithium‐ion transport, and mitigate undesirable anion‐solvent interactions. These results indicate that halloysite‐incorporated GPE (HS‐G) significantly improves DIB performance, as demonstrated by extended cycle life, robust capacity retention at fast charge/discharge rates of 20 C, and operational stability over a wide temperature range (0–60 °C). These improvements are attributed to the unique structural advantages of HS‐G, including effective charge separation, enhanced anion diffusion, and reduced solvent co‐intercalation, which provide an environmentally friendly and cost‐effective approach to advanced DIB applications.