Ionic Domains Research Articles

Supramolecular Modifying Nafion with Fluoroalkyl-Functionalized Polyoxometalate Nanoclusters for High-Selective Proton Conduction.

Fluoroalkyl-grafted polyoxometalate nanoclusters are used as supramolecular additives to precisely modify the ionic domains of Nafion, which can increase the proton conductivity and selectivity simultaneously. The resulting hybrid membranes show significantly enhanced power density in fuel cells and improved energy efficiency in vanadium flow batteries.

Poly(p-terphenyl-piperidine-bromoacetophenone) anion exchange membranes with pendant N-spirocyclic cations: Cations synergistic build efficient ion transport networks

The establishment of well-developed ionic conduction channels and the preparation of excellent chemical stability are urgent needs for anion exchange membranes. In this study, we successfully prepared poly (p-terphenyl-piperidine-bromoacetophenone) polymers using superacid catalysis. Then a series of QPTPP-N-ASU-x AEMs were prepared by introducing N-spirocyclic side chain cations (N-ASU) with different grafting rates. The introduction of N-spirocyclic cations with better alkali resistance increases multiple OH− transport sites, contributes to the microphase separation structure, and is synergistic with piperidine cations to rapidly construct ion transport networks, giving the membranes good conductivity and alkali resistance stability. The AFM showed that QPTPP-N-ASU-5% AEM had a remarkable microstructure and formed large ionic domains, the conductivity of the membrane was 121.2 mS cm−1, corresponding to a peak power density of 477.25 mW cm−2. The conductivity residual of QPTPP-N-ASU-5% AEM was 94.15 % and 87.71 % after immersion in 2 M and 4 M NaOH at 80 °C for 1440 h. It shows that membrane has good potential for application.

Biopolymeric electrolyte-based membrane on nanocrystalline cellulose/polyvinyl alcohol for a conceivable usage in proton exchange membrane fuel cell

In this study, we developed eco-friendly biopolymer electrolytes by blending nanocrystalline cellulose (NCC) with polyvinyl alcohol (PVA) and crosslinking them using glutaraldehyde. These membranes, denoted as NCC-x/PVA-y, were fabricated via the solution casting method. We thoroughly investigated the effects of different NCC to PVA ratios on various properties, including water uptake, swelling ratio, thermal and mechanical characteristics, proton conductivity, hydrogen permeation, and single Proton Exchange Membrane Fuel Cell (PEMFC) performances. Increasing the NCC concentration (ranging from 20 % to 60 %) led to enhanced surface roughness and compactness of ionic domains, resulting in improved dimensional stability and reduced hydrogen permeability across the membranes. Among the tested ratios, NCC-50/PVA-50 exhibited the highest proton conductivity, measuring 0.3 × 10−2 S cm−1. Notably, this ratio demonstrated a 60 % lower swelling ratio and lower hydrogen permeability (0.76 × 10−13 cm2/scmHg) compared to Nafion 117 (514 × 10−13 cm2/scmHg), indicating its superior performance. Furthermore, the NCC-50/PVA-50 membrane consistently maintained open-circuit voltages exceeding 0.9 V under all conditions, highlighting its effective proton transport capabilities and minimal fuel penetration. Density Functional Theory (DFT) analysis confirmed the successful cross-linking of NCC/PVA with glutaraldehyde, emphasizing its compatibility and potential for proton conductivity in PEMFC applications.

Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions

The interface between aqueous solutions and the facets of kaolinite plays an important role in a wide range of technological applications including tribology, paper production, oil recovery, waste water treatment and medical devices. This is made possible by kaolinite's layered structure, with its two basal surfaces -aluminol and siloxane-exhibiting different properties and reactivity. Using a combination of high-resolution atomic force microscopy (AFM) and atomistic molecular dynamics (MD) simulations, we probe in situ the hydration structure over both facets, in water and in the presence of added NaCl. The AFM images reflect the facets' first hydration layer, as confirmed from simulations. Complementary AFM spectroscopy measurements show an excellent agreement between the conservative component and MD's water density profiles, with discrete hydration layers on both facets and little sensitivity to added ions. The dissipative component of the measured tip-sample interactions is more sensitive to the presence of ions, with MD suggesting a link with the local water dynamics and transient instabilities between stable hydration layers. These effects are facet-dependant and more pronounced on the aluminol facet where the first water layer is better defined. Increasing the salt concentration allows hydrated ions to form more stable layers, with hints of organised ionic domains. The results provide unique insights into both the equilibrium molecular structure and dynamics of the kaolinite facets, potentially informing applications involving interfacial processes.

Supramolecular Modifying Nafion with Fluoroalkyl‐Functionalized Polyoxometalate Nanoclusters for High‐Selective Proton Conduction

Proton exchange membranes with high selectivity are urgently required in energy and electronic technologies. Nafion, a state‐of‐the‐art commercial proton exchange membrane material, faces significant challenges. It suffers from the permeation of undesirable substances, like hydrogen in fuel cells and vanadium ions in redox flow batteries, due to the unmatched sizes between its ionic domains (3~5 nm) and these substances. In this work, we present a supramolecular modification strategy that simultaneously enhances the proton conductivity and selectivity of Nafion. We employ fluoroalkyl‐grafted polyoxometalate (POMs) nanoclusters as supramolecular additives to modify Nafion via co‐assembly. These POMs can precisely and robustly decorate at Nafion ionic domains, with their fluoroalkyl chains anchoring into the perfluorinated matrix while their inorganic clusters stay in the ionic regions. The hybrid membranes, with continuous proton hopping sites and nanoscale steric hindrance offered by POMs, exhibit a 56% increase in proton conductivity and a 100% improvement in proton/vanadium selectivity. This leads to significantly enhanced power density and energy efficiency in fuel cells and vanadium flow batteries, respectively. These results underscore the intriguing potential of molecular cluster additives in improving the functions of ion‐conducting membranes.

Robust and tunable hydrogels strengthened by dynamic amphiphilic ionic domains

Hydrogels have gained increasing attentions in wearable electronics, but endure notch-sensitive and poor mechanical behavior in real-world applications. Herein, a robust and tunable hydrogel network was constructed by involving a polymerizable amphiphilic ionic liquid in polymer chains through a facile and novel strategy without additional chemical crosslinkers. The ingeniously designed dynamic amphiphilic ionic domains that are tuned by the structural domain and functional domain are crucial for reinforcing the structural integrity and allowing the polymer chains to accomplish reversible unfolding and ordered migration. The robust and functional microstructures effectively prevent crack propagation, enhancing the fracture strain (1200–2390%), tensile stress (380–1560 kPa), toughness (5–15 MJ m−3), and conductivity (0.13–0.2 mS cm−1). The obtained hydrogel acts as an excellent mechanoresponsive sensor to perceive various external stimuli to sensitively detect diverse human activities including large body motions and subtle muscle movements via electrical signals. Additionally, this strategy shows good applicable potential for preparing high-performance hydrogels based on monomers containing active double bonds, overcoming the disadvantages of poor mechanical properties of traditional free radical polymerization gels. It is anticipated that the design of dynamic amphiphilic ionic domains will provide guidance for regulating the polymer network of hydrogels and show great application potentials in real-life scenarios.

Spider-silk-inspired strong and tough hydrogel fibers with anti-freezing and water retention properties

Ideal hydrogel fibers with high toughness and environmental tolerance are indispensable for their long-term application in flexible electronics as actuating and sensing elements. However, current hydrogel fibers exhibit poor mechanical properties and environmental instability due to their intrinsically weak molecular (chain) interactions. Inspired by the multilevel adjustment of spider silk network structure by ions, bionic hydrogel fibers with elaborated ionic crosslinking and crystalline domains are constructed. Bionic hydrogel fibers show a toughness of 162.25 ± 21.99 megajoules per cubic meter, comparable to that of spider silks. The demonstrated bionic structural engineering strategy can be generalized to other polymers and inorganic salts for fabricating hydrogel fibers with broadly tunable mechanical properties. In addition, the introduction of inorganic salt/glycerol/water ternary solvent during constructing bionic structures endows hydrogel fibers with anti-freezing, water retention, and self-regeneration properties. This work provides ideas to fabricate hydrogel fibers with high mechanical properties and stability for flexible electronics.

A Molecular-Sieving Interphase Towards Low-Concentrated Aqueous Sodium-Ion Batteries

HighlightsA molecular-sieving electrode coating towards low-concentrated aqueous sodium-ion batteries is constructed by applying a composite of NaX zeolite and NaOH-neutralized Nafion.Resulting from a molecular sieving effect of zeolite channels and size-shrunken ionic domains in Nafion, the as-prepared coating layer reject hydrated Na+ ions and allow fast dehydrated Na+ permeance.200 cycles of Na2MnFe(CN)6//NaTi2(PO4)3 full cells can be achieved in a practically feasible 2 m aqueous electrolyte.

Lyotropic ionic liquid crystal gels derived from polyimidazolium hydrogen sulfate for enhanced proton conductivity

AbstractAnisotropic gels developed from polymer networks accommodating lyotropic liquid crystals are promising electrolytes but electrochemically inert polymers prevent ions from being conducted efficiently. In this work, we synthesized protic ionic liquid polymer in lyotropic ionic liquid crystal to improve proton conduction across the polymer skeleton in anisotropic gels. In situ polymerization of 1‐vinylimidazolium hydrogen sulfate ionic liquid dissolved in aqueous 1‐tetradecyl‐3‐methylimidazolium hydrogen sulfate lyotropic liquid crystal gave chemical liquid crystal gels exhibiting both dynamic order and mechanical strength. The protic ionic liquid polymer bridged the hydrogen bond chains between neighboring ionic lyotropic liquid crystal domains to give a proton conductivity of 117 mS cm−1 at 25°C. Macroscopic alignment of the liquid crystal gel achieved by mechanical shearing promoted proton conductivity to 137 mS cm−1. The macroscopically aligned liquid crystal gel acted stably in a fuel cell device, delivering a peak power density 2.95 times higher than the unaligned one. Gelation of lyotropic ionic liquid crystals with protic ionic liquid polymer provides an effective strategy to develop anisotropic gel electrolytes for electrochemical devices.

Synergistic incorporation of Ti3C2Tx with sulfonated poly(phenylene oxide) membranes: Unravelling multifaceted advancements in physicochemical, electrochemical, and antibacterial domains for enhanced electrodialytic desalination

This study delves into the solution-phase incorporation of Ti3C2Tx nanosheets into sulfonated poly(phenylene oxide) (SPPO) to prevail the conventional challenge of distant ionic channels in membranes. A series of membranes incorporating MXene (Ti3C2Tx nanosheets) at varying weight percentages (1 wt%, 2 wt%, and 5 wt%) underwent meticulous scrutiny of their physicochemical and electrochemical attributes. Among this series, MXe-02 emerged as particularly noteworthy, showing remarkable water sorption (WS= 43.8%), ion exchange capacity (IEC: 1.65 ± 0.05 meqg−1), and ionic conductivity (IC: 2.83×10−2 S cm−1), coupled with minimal dimensional change of 8.57% compared to its pristine counterpart, SPPO-B (WS=35.70%, IEC: 1.03±0.05 meqg−1, IC: 1.98×10–2 S cm−1). Advanced analytical techniques such as atomic force microscopy (AFM) and field emission-scanning electron microscopy (FE-SEM) provided insights into hydrophilic-hydrophobic phase separation, ionic domain clustering, and membrane surface attributes pivotal for enhancing electrochemical properties. Beyond optimal concentrations (>2 wt%), a significant composite-agglomeration effect hindered further advancements in physicochemical and electrochemical aspects, as verified by zeta potential measurements. The optimized MXe-02 membrane boasted a notable transport number of 0.89 with a substantial limiting current density (Ilim = 45 mA cm−2), offering a wide window for swift electrodialytic desalination. Moreover, MXe-02 membranes demonstrated an energy consumption of 0.98 kWh kg−1 and 93.52% energy efficiency, affirming their efficacy for brackish water desalination. Antibacterial properties were evaluated against Escherichia coli and Staphylococcus aureus, revealing MXe-02 and MXe-05's distinct zones of inhibition against S. aureus, highlighting their excellent antibacterial efficacy against Gram-positive bacteria. This comprehensive study shows the intricate interplay of MXene-incorporated membranes, offering valuable insights for advancing electrochemical and antibacterial performance in water desalination.

Permeation of urea and water through sulfonated poly(styrene‐isobutylene‐styrene) membranes with counterion substitution

AbstractThis study describes the influence of counterion substitution on the transport of urea and water through sulfonated poly(styrene‐isobutylene‐styrene) (SIBS) membranes. SIBS was sulfonated to 66.4% to allow for enough ionic domains to transport urea and water through the membrane. Counterions, including alkyl‐substituted ammonium ions, influenced the ionic domains creating a selective barrier that hindered the transport of urea and water through SIBS. Permeability measurements demonstrated that counterion substitution significantly affected the transport of urea. Membranes with higher charge counterions exhibited a more pronounced reduction in permeability due to the formation of crosslinks and increased restriction on molecular diffusion. Membranes substituted with ammonium salts showed reduced permeability due to the alkyl chains' hydrophobic nature, which created a physical barrier against the passage of urea molecules. Pure water flux tests indicated that counterion substitution also reduced the water flux of the membranes. Membranes with +1 counterions showed a small reduction in the water flux, while membranes with higher charge counterions and alkyl chain substitutions exhibited larger reductions, highlighting the influence of crosslinking and hydrophobicity on water transport.

Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes.

The predictive design of flexible and solvent-free polymer electrolytes for solid-state batteries requires an understanding of the fundamental principles governing the ion transport. In this work, we establish a correlation among the composite structures, polymer segmental dynamics, and lithium ion (Li+) transport in a ceramic-polymer composite. Elucidating this structure-property relationship will allow tailoring of the Li+ conductivity by optimizing the macroscopic electrochemical stability of the electrolyte. The ion dissociation from the slow polymer segmental dynamics was found to be enhanced by controlling the morphology and functionality of the polymer/ceramic interface. The chemical structure of the Li+ salt in the composite electrolyte was correlated with the size of the ionic cluster domains, the conductivity mechanism, and the electrochemical stability of the electrolyte. Polyethylene oxide (PEO) filled with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl) imide (LiFSI) salts was used as a matrix. A garnet electrolyte, aluminum substituted lithium lanthanum zirconium oxide (Al-LLZO) with a planar geometry, was used for the ceramic nanoparticle moieties. The dynamics of the strongly bound and highly mobile Li+ were investigated using dielectric relaxation spectroscopy. The incorporation of the Al-LLZO platelets increased the number density of more mobile Li+. The structure of the nanoscale ion-agglomeration was investigated by small-angle X-ray scattering, while molecular dynamics (MD) simulation studies were conducted to obtain the fundamental mechanism of the decorrelation of the Li+ in the LiTFSI and LiFSI salts from the long PEO chain.

Random sulfonated poly(arylene ether sulfone) and sulfonated poly(arylene ether ketone) membranes for fuel cell applications

AbstractIn this study, sulfonated poly(arylene ether sulfone) (SPAES) and sulfonated poly(arylene ether ketone) (SPAEK) were randomly synthesized, employing a presulfonation process. This presulfonation process resulted in a more controlled and reproducible sulfonation level. The respective polymers were prepared using 2,2‐Bis(4‐hydroxyphenyl) propane at 50% molar ratio, which also provided some membrane elasticity. The resulting polymers, each had 25% of the block containing the sulfonic domains (SPAES A 25 and SPAEK A 25). Better conductive membranes were achieved for the random sulfone polymers than for the random ketone polymers, with values, respectively, of 0.24 and 0.07 S cm−1 at 80°C. The lower proton conductivity from the ketone‐based polymer was compensated with very low methanol permeability (0.25 × 10−6 cm2 s−1) and outstanding oxidative stability. The selectivity of both polymer membranes exceeded the reported values for the state‐of‐the‐art Nafion® 117 and other commercially available options. Both polymer membranes, with their unique combination of ionic domains, elastomeric blocks, and resulting morphology, could be viable candidates for fuel cell applications.

Understanding of Ionic Structure Change Under Hydration Levels by Using CSAFM

Proton exchange membranes (PEMs) are a key component of proton exchange membrane fuel cells. They work as gas separator, insulator, and proton conductor. Thus, characterization of the membrane is a crucial process for developing PEM. However, this work is not easy because its complicated phase separated morphological structure and widely varying ionic structure under hydration. Current sensing atomic force microscopy (CSAFM) measures nano current flow between a tip and the sample surface and can map the nano current flow distribution of scanned area. In this study, the ionic structure of Nafion under different hydration condition is studied by using CSAFM. Specifically, the area variation of ionic domain on the membrane surface under different relative humidity is characterized by quantitative method based on CSAFM measurement. The study is done by several steps. First, the Nafion 212 is scanned in the environmental chamber by varying 15% to 65% relative humidity. In this process, the current distribution and the morphology are simultaneously mapped at each RH. Second, the local net charge value of protons, which is connected with area of ionic domain on the membrane surface, are calculated based on current distribution. In this process, the area of ionic domain on the membrane surface under different RH is estimated. The study shows several remarkable results. First of all, the non-uniform ionic domain increasing is observed from sequentially mapped current distribution on the surface under different RH. Second, the reliable estimation method of ionic domain variation is introduced by this study.

Effect of swelling on dyeing of cotton fabric in supercritical CO2 with ionic liquid domain reverse micelles

Effect of swelling on dyeing of cotton fabric in supercritical CO2 with ionic liquid domain reverse micelles

Enhanced ionic conductivity in block copolymer electrolytes through interfacial passivation using mixed ionic liquids.

We present a strategic approach for enhancing the ionic conductivity of block copolymer electrolytes. This was achieved by introducing mixed ionic liquids (ILs) with varying molar ratios, wherein the imidazolium cation was paired with either tetrafluoroborate (BF4) anion or bis(trifluoromethylsulfonyl)imide (TFSI) anion. Two polymer matrices, poly(4-styrenesulfonate)-b-polymethylbutylene (SSMB) and poly(4-styrenesulfonyl (trifluoromethanesulfonyl)imide)-b-polymethylbutylene (STMB), were synthesized for this purpose. All the SSMB and STMB containing mixed ILs showed hexagonal cylindrical structures, but the type of tethered acid group significantly influenced the interfacial properties. STMB electrolytes demonstrated enhanced segregation strength, which was attributed to strengthened Coulomb and hydrogen bonding interactions in the ionic domains, where the ILs were uniformly distributed. In contrast, the SSMB electrolytes exhibited increased concentration fluctuations because the BF4 anions were selectively sequestered at the block interfaces. This resulted in the effective confinement of imidazolium TFSI along the ionic domains, thereby preventing ion trapping in dead zones and facilitating rapid ion diffusion. Consequently, the SSMB electrolytes with mixed ILs demonstrated significantly improved ionic conductivities, surpassing the expected values based on the arithmetic average of the conductivities of each IL, whereas the ionic conductivity of the STMB was aligned with the expected average. The methodology explored in this study holds great promise for the development of solid-state polymer electrolytes.

Sulfonated Poly(2,6-dimethyl-1,4-phenylene ether)-Modified Mixed-Matrix Bifunctional Polyelectrolyte Membranes for Long-Run Anthrarufin-Based Redox Flow Batteries.

The resurgence in designing polyelectrolyte membrane (PEM) materials has propound grid-scale electrochemical energy storage devices. Herein, we report on studies corroborating the synergistic influence of ionic domain microstructure modification and intercalation of telechelic bis-piperidinium-functionalized graphene oxide (GO) to fabricate stable bifunctional membranes from sulfonated poly(2,6-dimethyl-1,4-phenylene ether) (sPPE) for efficient anthrarufin-based alkaline redox flow batteries. A critically long-lasting quest on alkaline stability and -OH conductivity dilemma in hydrocarbon-based PEMs is meticulously resolved via a bifunctional ion-conducting matrix. Preferential studies on hydrophilic domain distribution in sPPE suggest that, with high microphase homogeneity, higher specific capacity retentions are achievable during galvanostatic charge-discharge (GCD) analysis. Moreover, the low-capacity issues were overcome by improving the redoxolyte-membrane interface affinities incorporating bis-piperidinium-bearing graphene oxide (bis-QGO). Consequently, at 1.0 and 2.0 wt % intercalation of bis-QGO, the bifunctional polyelectrolyte membranes (BFPMs) impart lowest overpotentials of 93 mV (for BFPM-1.0) and ∼100 mV (for BFPM-2.0) which are ∼43 and 40% lower than that of Nafion-117 (i.e., ∼164 mV). Furthermore, the efficiency of BFPMs, viz., the Coulombic, voltage, and energy efficiencies, was ∼95-98%, ∼85%, and ≥80% at 20 mA cm-2, respectively. In long-cycling operations, the GCD profile evidenced ∼99% efficiency retention over 450 cycles and illustrated reproducible rate capability. Finally, the polarization studies of BFPMs revealed ∼54% higher peak power density (87.5 mW cm-2) delivery than Nafion-117 (∼57 mW cm-2). We believe that this strategic designing approach could offer newer and simple avenues to avail high-performance BFPMs at low intercalation loads for alkaline electrochemical energy storage and related applications.

Enhancement in the alkaline stability of poly(arylene ether ketone)-typed anion-exchange membranes via phenylene piperidinium blocks

In alkaline environments, the cationic groups and polymeric backbones of conventional poly(arylene ether ketone)-typed anion-exchange membranes (AEMs) tend to degrade. Herein, we report poly(phenylene piperidinium-co-arylene ether ketone)s (QPPPiAEK-x) with enhanced alkaline stability as potential AEM candidates. Specifically, a diphenyl piperidine precursor was synthesized and subjected to Ni(0)-catalyzed coupling polymerization with poly(arylene ether ketone) oligomers and followed by classic Menshutkin reaction. Membranes with an ion exchange capacity ranging from 1.85 to 2.24 meq g-1 showed high water uptakes (97.7%–159.2%) and high OH- conductivities at 80 °C (73.4–82.2 mS cm-1) but moderate swelling behaviors (i.e., in-plane swelling ratios of 28.0%–35.8%, and through-plane swelling ratios of 28.4%–56.2%). Morphological studies confirmed the presence of hydrophilic–hydrophobic microphase separation (ionic domain sizes of 17.9–22.3 nm) in all membranes, which was ascribed to the high feed content of phenylene piperidinium blocks. The H2/O2 single-cell test revealed the highest power output (187.7 mW cm-2) for the QPPPiAEK-2.0 membrane at 60 °C and 100% relative humidity. During the stability test, all membranes exhibited adequate ion conduction abilities. The most durable membrane retained 69.6% of its initial conductivity after 936 h in a 1 M NaOH solution at 80 °C. Results of ex-situ nuclear magnetic resonance spectroscopy revealed that approximately 9.7%–20.6% of cationic decomposition was the main degradation pathway for the QPPPiAEK-x ionomers, whereas 2.6%–4.4% accounted for the cleavage of backbones. Our study provides a promising methodology for fabricating alkali-stable AEMs for fuel cell applications.

The effect of high-temperature proton exchange membranes with microphase separation structure on phosphoric acid loss

Phosphoric acid (PA) leakage of PA-doped high-temperature proton exchange membranes (HT-PEMs) is pivotal for its practical application under working conditions. Here, to enhance the PA retention of HT-PEMs, the concept of microphase separation regulated by flexible long aliphatic side-chain was introduced into poly(isatin-co-p-terphenyl-imidazole) matrix (PITI-CmQ90) via direct superacid-catalyzed copolymerization from N-alkylated isatin monomer. The designed PITI-CmQ90 membranes illustrate obvious microphase separation and larger ionic domain confirmed via Small-angle X-ray scattering (SAXS) analysis suggesting wider proton transport channels. Notably, PA/PITI-C6Q90 membrane exhibits the best PA retention ability under relative humidity (RH) cycle tests at different temperatures, which mainly attributed to the excellent PA interaction through moderate ion aggregation in the microphase-separated PEM matrix verified by solid 31P NMR. As a result, the corresponding MEA displays the most durable single-cell performance under a step-V procedure from 1.0 V to 0.1 V cycle experiments at different temperatures. Therefore, the idea of microphase separation structure on PA retention mentioned in this work helps to study the ionic-pairs interactions from the perspective of membrane microstructure and provide a new strategy to enhance the durability of PEMs.

New insights into the molecular structure and dynamics of a recyclable and ionically crosslinked carboxylated nitrile rubber (XNBR)

Ionic crosslinking offers a route to rubber reprocessability due to ion pairs’ dynamism, with recent studies focusing on tensile properties recovery. However, this research aims to provide, for the first time, a comprehensive overview of the recyclability of carboxylated nitrile rubber (XNBR), spotlighting changes in molecular dynamics through multiple recycling cycles beyond tensile tests. A uniquely recyclable XNBR, incorporating ZnO as a multifunctional additive, was designed alongside a simple, scalable, two-step recycling process. Evidence of the delicate balance between crosslink density and molecular entanglements that affects the dynamics of the recycled material was found. Recycling also restricts the molecular dynamics near ionic domains; attributed to a higher crosslink density (from 3.69×10-5molcm−3 in the pristine sample to 6.00×10-5molcm−3 after the third cycle), caused by a decreased ionic clusters size (aggregation number drops from 12.2 to 6.9). Remarkably, negligible differences (<10%) in compressive fatigue behavior and an enhanced chemical resistance in different solvents (up to 350% increase in motor oil) were also observed, ensuring suitable performance in conditions closer to service. Overall, this study demonstrates the feasibility of XNBR recycling and provides a broad understanding of this material at the molecular level.