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Polyelectrolyte complexes (PECs) have attracted considerable attention owing to their unique physicochemical properties and potential applications as smart materials. Herein, the glass transitions of PECs solvated with varying alcohols are investigated in poly(diallyldimethylammonium)/poly(acrylic acid) (PDADMA/PAA) complexes by using modulated differential scanning calorimetry (MDSC). Solvents with one or two hydroxyl groups are selected to examine the effect of PAA-solvent interactions on the glass transition temperature (Tg). Except for glycerol, all alcohol solvents yield PECs with detectable Tg’s and plasticization behavior. Furthermore, a linear relationship for 1/Tg and the natural logarithm of the number of hydroxyl groups to intrinsic ion pair ratio [ln(nhydroxyl/nintrinsic‑ion‑pair)] is found. This result is significant because prior work demonstrated the relationship only for water and no other solvents. All-atom molecular dynamics (MD) simulations analyze the ability of the solvent to form hydrogen bonds via the solvent’s OH groups to the PAA, revealing that the solvent molecule size and available hydroxyl groups govern the change in the glass transition. Overall, the clear dependence of a PEC’s glass transition on the solvent’s chemical structure provides a simple guideline for predicting their relationship. 

The assembly and dynamics of polyelectrolyte complexes (PECs) and polyelectrolyte multilayers (PEMs) are influenced by water content, pH, and salt concentration. However, the influence of divalent salts on the assembly of polyelectrolyte complexes remains unclear. This work showcases that divalent chloride salts directly impact the glass transition temperature and the ion–ion interactions within PECs. Here, poly(diallyldimethylammonium)–poly(styrene sulfonate) (PDADMA–PSS) PECs are assembled in solutions containing MgCl2 and CaCl2 (following the Hofmeister series). These PECs are studied for the cations’ influence on physicochemical properties (glass transition, polymer composition, ion pairing) at varying salt concentrations (0.03 M, 0.10 M, 0.15 M, and 0.20 M). Modulated differential scanning calorimetry (MDSC) experiments demonstrate that PECs assembled with CaCl2 have a significantly higher glass transition temperature when compared to PECs assembled with MgCl2. Neutron activation analysis (NAA) and nuclear magnetic resonance (NMR) spectroscopy demonstrate that this difference is due to strong ion-specific effects influencing the ratio of intrinsic and extrinsic ion pairings in the system. Furthermore, this study demonstrates a universal linear relationship between the thermal transition and the number of water molecules surrounding oppositely charged polyelectrolyte–polyelectrolyte intrinsic ion pairs, even when the salt contains divalent cations. Ion-specific trends have implications on the glass transition and composition of PDADMA–PSS PECs. Divalent salts not only follow the trend of the Hofmeister series but also introduce bridging into the polyelectrolyte complex; however, the structural relaxation of the PEC remains the same. This study offers a bridge between divalent cation behavior on polymer assembly properties and its transition to industrial applications such as controlled drug delivery, sensors, and water purification. 

Industrial scaleup of MXene synthesis has faced many challenges, both in the process safety and nanosheet yield. As a step toward the scalability of MXenes, we carried out a one-to-one comparison of the industrial scalability and application performance of two methods for producing Ti3C2Tz MXenes: LiF-HCl acid etching and Lewis acid molten salt etching. This study had an emphasis on nanoscale structure, electrical conductivity, electromagnetic interference (EMI) shielding and supercapacitive properties, yield, and process scalability, both at the etched clay stage and delaminated nanosheet stage. This comparison was completed in parallel with the same starting MAX phase, chemicals, and processing equipment, where necessary. The synthesis process influences the structure and terminal groups of MXenes, altering properties and performance. Notably, the electrical conductivity was superior for acid-etched nanosheets at 2200 S/cm, compared to salt-etched nanosheets at 0.66 S/cm. For EMI shielding effectiveness and capacitance, acid-etched nanosheets performed the highest. The yield of the acid-etched nanosheets was ~ 50% and salt-etched nanosheets was 15%. The acid-etched process was scaled up with a small business partner from 1-g to 200-g MAX phase, with similar properties and yield. When the salt-etching process was scaled up to 25 g of MAX, the properties remained similar to the 1 g batch, with a lower yield of ~ 5%. Although the acid-etching process was better for most metrics, the molten salt-etching method is still in its infancy and has advantages regarding process safety. 

Inspired by Nature, we present a polypeptide-based organic redox-active material constructed from renewable feedstocks, L-glutamic acid (an amino acid) and riboflavin (vitamin B₂), to address challenges with start-to-end-of-life management in energy storage systems (ESSs). The amino acid was utilized to establish a degradable polymer backbone, along which many copies of riboflavin were incorporated to serve as the redox-active pendant groups that enabled energy storage. The overall synthesis involved the ring-opening polymerization (ROP) of anl-glutamic acid-derivedN-carboxyanhydride (NCA) monomer, followed by side chain activation with azides and, finally, click coupling to achieve installation of alkyne-functionalized riboflavin moieties. The steric bulkiness and rich chemical functionality of riboflavin resulted in synthetic complexities that required reaction optimization to achieve the desired polymer structure. Electrochemical characterization of the resultant riboflavin polypeptide, in organic electrolyte, showed quasireversible redox activity with a half-wave potential (E_1/2) ofca.−1.10 Vvs.ferrocene/ferrocenium (Fc/Fc⁺). Cell viability assays revealed biocompatibility, as indicated by negligible cytotoxicity for fibroblast cells. The polypeptide design, consisting of labile amide backbone linkages and side-chain ester functionalities that tethered the riboflavin units to the backbone, enabled hydrolytic degradation to recover building blocks for future upcycling or recycling. This bioinspired strategy advances the development of degradable redox-active polymers and promotes sustainable materials design for circular energy storage technologies. 

Salt acts as a plasticizer in polyelectrolyte complexes (PECs), which impacts the physical, thermal, and mechanical properties, thus having implications in applications, such as drug delivery, energy storage, and smart coatings. Added salt disrupts polycation−polyanion intrinsic ion pairs, lowering a hydrated PEC’s glass transition temperature (Tg). However, the relative influence of counterion type on the PEC’s Tg is not well understood. Here, the e#ect of anion type (NaCl, NaBr, NaNO3, and NaI) on the Tg of solid-like, hydrated PECs composed of poly(diallydimethylammonium) (PDADMA)−poly(styrenesulfonate) (PSS) is investigated. With increasing the chaotropic nature of the salt anion, the Tg decreases. The relative di#erences are attributed to the doping level, the amount of bound water, the mobility of water molecules within the PECs, and the strength of interactions between the PEs. For all studied salt concentrations and salt types, the Tg followed the scaling of −1/Tg ≈ ln([IP]/[H2O]), in which [IP]/ [H2O] is the ratio of intrinsic pairs to water. The scaling estimates that about 7 to 17% of the intrinsic ion pairs should be weakened for the PEC to partake in a glass transition. Put together, this study highlights that the Tg in PECs is impacted by the salt anion, but the mechanism of the glass transition remains unchanged. 

Abstract Structural color arises from light scattering rather than organic pigments and can be found in Nature, such as in bird feathers and butterfly wings. Synthetic materials can mimic Nature by leveraging materials with contrasting optical characteristics by controlling each materials’ spatial arrangement in a heterostructure. Two-dimensional MXene nanosheets are particularly interesting due to their unique optical properties, but MXenes have not been used directly as a structural colorant because it is challenging to control the spatial placement of MXenes at the nanometer level. Here, we report the emergence of structural color in layer-by-layer (LbL) assemblies of Ti₃C₂T_zMXene nanosheets and polyelectrolyte heterostructures with controlled block thicknesses. The block thickness and spatial placement of MXene are controlled by the assembly’s salt concentration and number of layer pairs. This work demonstrates that optical characteristics of MXene/polyelectrolyte heterostructures depend on MXene content and placement, while deepening the understanding of MXenes within structural color films. 

The major challenge to fabricate MXene/polymer composites are the processing conditions and poor control over the distribution of the MXene nanosheets within the polymer matrix. Traditional ways involve the direct mix of fillers and polymers to form a random homogeneous composite, which leads to inefficient use of fillers. To address these challenges, researchers have focused on the development of ordered MXene/polymer composite structures using various fabrication strategies. In this review, we summarize recent advances of structured MXene/polymer composites and their processing-structure-property relationships. Two main forms of MXene/polymer composites (films and foams) are separately discussed with a focus on the detailed fabrication means and corresponding structures. These architected composites complement those in which MXenes nanosheets are isotropically dispersed throughout, such as those formed by aqueous solution mixing approaches. This review culminates in a perspective on the future opportunities for architected MXene/polymer composites. 

Abstract Organic batteries are one of the possible routes for transitioning to sustainable energy storage solutions. However, the recycling of organic batteries, which is a key step toward circularity, is not easily achieved. This work shows the direct recycling of poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl) (PTMA) and poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl acrylamide) (PTAm) based composite electrodes. After charge‐discharge cycling, the electrodes are deconstructed using a solubilizing‐solvent and then reconstructed using a casting‐solvent. The electrochemical properties of the original and recycled electrodes are compared using cyclic voltammetry (CV) and galvanostatic charge‐discharge (GCD) cycling, from which it is discovered using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) that recycling can be challenged by the formation of a cathode electrolyte interphase (CEI). In turn, an additive is proposed to modify the CEI layer and improve the properties after recycling. Last, an anionic rocking chair battery consisting of PTAm electrodes as both positive and negative electrodes is demonstrated, in which the electrodes are recycled to form a new battery. This work demonstrates the recycling of composite electrodes for organic batteries and provides insights into the challenges and possible solutions for recycling the next‐generation electrochemical energy storage devices.