http://onlinelibrary.wiley.com/rss/journal/10.1002/(ISSN)1521-4095

Heterostructures have emerged as advanced electrocatalysts to convert earth-abundant simple molecules into high-value-added products. On the basis of atomistic understanding to accelerate the electrochemical processes, the architecture of heterostructured electrocatalysts is comprehensively discussed from the point of view of modulating electronic configuration and interface reactive microenvironment. The influence of rectification, space charge region, built-in electric field, synergistic interactions, lattice strain, and geometric effect is considered.

Electrocatalysts can efficiently convert earth-abundant simple molecules into high-value-added products. In this context, heterostructures, which are largely determined by the interface, have emerged as a pivotal architecture for enhancing the activity of electrocatalysts. In this review, the atomistic understanding of heterostructured electrocatalysts is considered, focusing on the reaction kinetic rate and electron configuration, gained from both empirical studies and theoretical models. We start from the fundamentals of the microkinetic model, adsorption energy theory, and electric double layer model. The importance of heterostructures to accelerate electrochemical processes via modulating electron configuration and interfacial reactive microenvironment is highlighted, by considering rectification, space charge region, built-in electric field, synergistic interactions, lattice strain, and geometric effect. We conclude this review by summarizing the challenges and perspectives in the field of heterostructured electrocatalysts, such as the determination of transition state energy, their dynamic evolution, refinement of the theoretical approaches, and the use of machine learning.

A halogen bond (XB)-enhanced strategy is proposed, where ─B(OH)I3 groups are incorporated into a highly integrated porous carbon/I2 cathode (HOCF–BIn) to extend interactions between ─B(OH)I3 and subsequent I2 molecules. The strong intermolecular forces in HOCF–BIn cathodes significantly enhance I2/I3 −/I− confinement, enabling exceptional cycling stability at I2 loadings of 1.8–6.2 mg cm−2.

The redox chemistries of iodine have attracted tremendous attention for charge storage owing to their high theoretical specific capacity and natural abundance. However, the practical capacity and cycle life are greatly limited by the active mass loss originating from the dissolved iodine species in either non-aqueous or aqueous batteries. Despite intensive progress in physical and physicochemical confinements of iodine species (I2/I3 −/I−), less attention has been paid to confining iodine species beyond the host–iodine interface, inhibiting further development of iodine cathodes with high I2 contents. Here a halogen bond (XB)– enhanced design concept is proposed between I2 molecules to achieve stable cycling performances, as exemplified by the Na–I2 battery. The enhanced XB is derived from the incorporation of –B(OH)I3 groups in highly integrated porous carbon/I2 cathode (HOCF–BIn), which can generate extended interactions between –B(OH)I3 and following I2 molecules. Due to the strong intermolecular force between I2 molecules, the HOCF–BIn cathodes exhibit substantially strengthened I2/I3 −/I− confinement, enabling outstanding cycling stability at I2 loading ranging from 1.8 to 6.2 mg cm−2. This findings demonstrate a functional group to manipulate XB chemistry within I2 molecules and polyiodides for stable and low-cost metal–iodine batteries.

The nanoplatform based on engineered attenuated OMVs has good biosafety and can cross the BBB and target GBM with the assistance of Angiopep-2. The co-delivery of doxorubicin and CD47-siRNA and the immunogenicity of OMVs synergistically overcome the intrinsic and adaptive immune resistance of GBM, which ultimately triggers a powerful antitumor immune response.

Apart from the blood-brain barrier (BBB), the efficacy of immunotherapy for glioblastoma (GBM) is limited by the presence of intrinsic and adaptive immune resistance, implying that co-delivery of various immunotherapeutic agents or simultaneous regulation of different cells is urgently needed. Bacterial outer membrane vesicles (OMVs) offer a unique advantage in the treatment of GBM, owing to their multifunctional properties as carriers and immune adjuvants and their ability to cross the BBB. However, traditional OMVs can lead to toxic side effects and disruption of tight junctions in the BBB. Therefore, to enhance the in vivo safety and targeting capability of OMVs, we introduced engineered OMVs to reduce toxicity and further constructed a modularly assembled nanoplatform by performing simple peptide modifications. This nanoplatform demonstrates satisfactory biosafety and is able to continuously cross the BBB and target GBM with the assistance of Angiopep-2. Subsequently, immunogenic substances on OMVs, along with carried small-interfering RNA (siRNA) and doxorubicin, can promote and enhance the reprogramming and phagocytic abilities of macrophages and microglia, respectively, and increase the immunogenicity of GBM, ultimately overcoming GBM immune resistance to enhance the efficacy of immunotherapy. This OMVs-based nanoplatform provides a new paradigm and insights into the development of immunotherapy for GBM.

This review probes recent advancements in PEMWEs for green hydrogen production from the perspective of acidic OER, identifies challenges related to corrosive environments and oxidative conditions, and proposes strategies to enhance the long-term stability of PEMWEs by addressing both catalyst and membrane electrode assembly deactivation.

Proton exchange membrane water electrolysis (PEMWE) represents a promising technology for renewable hydrogen production. However, the large-scale commercialization of PEMWE faces challenges due to the need for acid oxygen evolution reaction (OER) catalysts with long-term stability and corrosion-resistant membrane electrode assemblies (MEA). This review thoroughly examines the deactivation mechanisms of acidic OER and crucial factors affecting assembly instability in complex reaction environments, including catalyst degradation, dynamic behavior at the MEA triple-phase boundary, and equipment failures. Targeted solutions are proposed, including catalyst improvements, optimized MEA designs, and operational strategies. Finally, the review highlights perspectives on strict activity/stability evaluation standards, in situ/operando characteristics, and practical electrolyzer optimization. These insights emphasize the interrelationship between catalysts, MEAs, activity, and stability, offering new guidance for accelerating the commercialization of PEMWE catalysts and systems.

A sustainable Zn interfacial architecture is established, where a robust polyimide nanofilm is covalently anchored to the Zn substrate through electronegative F atoms. The strong covalent interactions provide excellent interfacial adhesion during repeated Zn/Zn2+ cycling. The remarkable resilience, modulus, and low creep of FPI film effectively resist the impact stress from electroplated Zn while maintaining structural integrity.

Artificial interfacial protective coatings (IPCs) on Zn anodes provide a viable solution for suppressing dendritic growth by spatially confining and homogenizing the Zn2+ flux. However, repeated Zn deformation during electroplating/stripping cycles can lead to the rupture or exfoliation of IPCs, as well as the formation of detrimental interfacial gaps. Herein, a highly durable IPC is developed on a Zn substrate using a mechanically robust fluorinated polyimide nanofilm (FPI). This unique FPI interphase forms strong covalent bonds with Zn through electronegative fluorine atoms, facilitating Zn plating/stripping while maintaining interfacial adhesion. The superior resilience, modulus, and low creep of the FPI film resist the impact stresses from electroplated Zn, ensuring structural integrity. With this FPI coating, the FPI-Cu||Zn half cells demonstrate high reversibility in Zn2+ electroplating/stripping over 4000 h, maintaining Coulombic efficiency above 99.33%. When coupled with a MnO2 cathode, the MnO2||FPI-Zn full cells exhibit a long lifespan, surpassing 5000 cycles, with a high specific capacity retention of 75.21%. This study highlights the importance of achieving a balance between the customized compatibility and mechanical properties of IPCs to modulate zinc interfacial chemistries.

An infrared-sensitive image sensor based on self-welded tellurium (Te) nanomesh is proposed, demonstrating advancements in flexible integration and scalable fabrication. By leveraging the unique photothermolelectric (PTE) operation, thermal-coupled bi-directional photoresponse is explored to illustrate the proof-of-principle in-sensor convolutional network for edge computing.

The inherent limitations of traditional von Neumann architectures hinder the rapid development of internet of things technologies. Beyond conventional, complementary metal-oxide-semiconductor technologies, imaging sensors integrated with near- or in-sensor computing architectures emerge as a promising solution. In this study, the multi-scale van der Waals (vdWs) interactions in 1D tellurium (Te) atomic chains are explored, leading to the deposition of a photothermoelectric (PTE) Te nanomesh on a polymeric polyimide substrate. The self-welding process enables the lateral vapor growth of a well-connected Te nanomesh with robust electrical and mechanical properties, including a PTE responsivity of ≈120 V W−1 in the infrared light regime. Leveraging the PTE operation, the thermal-coupled bi-directional photoresponse is investigated to demonstrate a proof-of-principle in-sensor convolutional network for edge computing. This work presents a scalable approach for assembling functional vdWs Te nanomesh and highlights its potential applications in PTE image sensing and convolutional processing.

A D–A–D type TADF molecule, TPA-DHAQ, is designed and synthesized by introducing an ESIPT-active molecule DHAQ as the acceptor unit, based on which the NIR TADF laser with a low threshold and high stability is successfully realized. In addition, a single-mode NIR TADF laser can be realized by adjusting the size of the resonator. This work provides a novel molecular design strategy to overcome the problem of poor stability of conventional NIR organic lasers.

Near-infrared (NIR) organic lasers have undergone rapid development in recent years, but still facing challenges in lowering the threshold and improving the stability. Herein, to overcome these challenges, a “two in one” strategy involving the integration of thermally activated delayed fluorescence (TADF) and excited-state intramolecular proton transfer (ESIPT) activity in a single molecule is proposed. Specifically, a donor–acceptor–donor type TADF material 2,6-bis[4-(diphenylamino)phenyl]-1,5-dihydroxyanthraquinone (TPA-DHAQ) with an ESIPT-active moiety as the acceptor, is designed and synthesized, based on which, a NIR organic laser at 820 nm with an exceptionally low threshold of 6.3 µJ cm−2 can be realized. Benefiting from the synergistic effect of the TADF property and the ESIPT process, the resulting organic laser showed excellent stability by maintaining the laser intensity at ≈80% of the initial value after 580 min of continuous excitation. Finally, by modulating the size of the resonator, a single-mode NIR laser is successfully realized. This work provides a novel molecular design strategy for the development of new TADF gain materials to overcome the problem of high threshold and poor stability of conventional NIR organic lasers, and shed light on the future development of NIR organic lasers.

Meter-scale MXene/GO@monstera nanocellulose core-shell nanofiber textiles are produced, integrating ultra-broadband EMI shielding covering GHz and THz bands, super-strong stealth properties within NIR and MIR ranges, and excellent multifunctionality, including heat resistance, flame retardant, joule heating, and stress sensing capabilities, which are promising for comprehensive electromagnetic defense in both military and civilian fields.

The rapid development of wireless communication and infrared (IR) detection technologies has generated an increasing demand for large-size high-performance wearable electromagnetic interference (EMI) shielding and IR stealth textiles. Herein, meter-scale MXene/graphene oxide (MG)@monstera nanocellulose (MC) core-shell nanofiber textiles are fabricated for the first time using a multi-stage cryogenic drying-assisted coaxial wet spinning assembly strategy, with MG as the conductive composite core and MC as the organic skeleton shell. The highly aligned shell and dense core endow the nanofibers with a great toughness of ≈39.6 MJ m−3, a strong strength >≈180 MPa, and a high conductivity of 6.4 × 103 S m−1. The textiles exhibit unprecedented ultra-broadband EMI shielding performance covering gigahertz and terahertz bands, with optimal shielding effectiveness up to 84 and 85 dB in the band of 8.2–26.5 GHz and 0.3–1.5 THz, respectively, at only 185 µm thick. Superb IR stealth performance in the near- and mid-IR ranges is also achieved, benefitting from their good heat resistance and low IR emissivity. Furthermore, the textiles also demonstrate excellent dyeability, flame retardancy, Joule heating, and stress-sensing properties. Such scalable prepared core-shell nanofiber textiles with superior comprehensive performance have broad application prospects in future smart wearable protective devices.

Novel polyimide-ionene hybrids that exhibit desirable alcohol processability, conductivity, transparency, and metal/semiconductor interface modification ability are furnished by melding pyromellitic diimides into ionene backbones. These merits render them universal cathode interlayer materials with outstanding thickness tolerance, leading to not only highly efficient and stable opaque devices but also high-performance semitransparent devices even when pairing with low-cost Cu electrodes.

The contradiction between high transmittance and favorable conductivity poses a great challenge in developing effective cathode interlayer (CIL) materials with sufficient thickness tolerance, which hinders the further advancement of organic solar cells (OSCs). Herein, a completely new class of alcohol processable polyimide-ionene hybrids (PIIHs) is proposed by melding pyromellitic diimide (PMD) subunits into imidazolium-based ionenes backbone covalently. These PIIHs, named PMD-DI and PMD-PD, boast high transparency, suitable energy levels, and decent conductivity. A higher PMD content endows PMD-PD with improved work function tunability, electrical properties, and crystallinity, enabling PMD-PD as CIL material with excellent thickness-insensitive characteristics, while simultaneously improving device stability significantly. Furthermore, PMD-PD also exhibits good compatibility with various electrodes and active layers, offering solar cell efficiencies of up to 19.91% and 19.29% with Ag and Cu cathodes, respectively. More importantly, the application of PMD-PD can improve the performance of semi-transparent OSCs without losing transmittance, thereby drastically enhancing the light utilization efficiency to 4.04% with an ultrathin, low-cost Cu cathode, that competes with leading optical modulation-free semitransparent OSCs with expensive Ag cathodes. This work opens a pathway to realize transparent and conductive interlayers by strategic molecular design, leading to highly efficient, stable, and cost-effective OSCs suitable for diverse applications.

Biological nanopores are highly promising tools for single-molecule biosensors, but the fragile supporting lipid membranes is a major bottleneck. An alternative hybrid membrane is presented, comprising phospholipids and block co-polymers, that can be functionalized by a broad variety of nanopores for single-molecule sensing. Crucially, the hybrid membrane provides substantially increased stability to harsh conditions, providing new opportunities for nanopore-based biosensors.

Biological nanopores are powerful tools for single-molecule detection, with promising potential as next-generation biosensors. A major bottleneck in nanopore analysis is the fragility of the supporting lipid membranes, that easily rupture after exposure to biological samples. Membranes comprising PMOXA-PDMS-PMOXA (poly(2-methyloxazoline-b-dimethylsiloxane-b-2-methyloxazoline)) or PBD-PEO (poly(1,2-butadiene)-b-poly(ethylene oxide)) polymers may form robust alternatives, but their suitability for the reconstitution of a broad range of nanopores has not yet been investigated. Here, PBD-PEO membranes are found to be highly robust toward applied voltages and human serum, while providing a poor environment for nanopore reconstitution. However, hybrid membranes containing a similar molar ratio of PBD11PEO8 polymers and diphytanoyl phosphatidylcholine (DPhPC) lipids show the best of both worlds: highly robust membranes suitable for the reconstitution of a wide variety of nanopores. Molecular dynamics simulations reveal that lipids form ≈12 nm domains interspersed by a polymer matrix. Nanopores partition into these lipid nanodomains and sequester lipids, possibly offering the same binding strength as in a native bilayer. Nanopores reconstituted in hybrid membranes yield efficient sampling of biomolecules and enable sensing of high concentrations of human serum. This work thus shows that hybrid membranes functionalized with nanopores allow single-molecule sensing, while forming robust interfaces, resolving an important bottleneck for novel nanopore-based biosensors.

Zinc anodes face severe instability under extreme conditions of high current density, high areal capacity, and high depth of discharge (DOD) due to severe concentration polarization caused by the imbalance between Zn2⁺ consumption and transfer rates. To overcome this, a nanofluid layer is introduced to rapidly absorb Zn2⁺ and regulate interfacial ion transport, effectively mitigating polarization and enabling stable zinc deposition. This work provides key insights into interfacial engineering for next-generation high-performance zinc metal batteries.

The commercialization of zinc metal batteries aims at high-rate capability and lightweight, which requires zinc anodes working at high current density, high areal capacity, and high depth of discharge. However, frequent zinc anode fades drastically under extreme conditions. Herein, it is revealed that the primary reason for the anode instability is the severe concentration polarization caused by the imbalanced consumption rate and transfer rate of Zn2+ under extreme conditions. Based on this finding, a nanofluid layer is constructed to rapidly absorb Zn2+ and mitigate the polarization induced by the nonlinear transport of interfacial ions. The modified zinc anode sustains at extreme conditions for over 1573 h (40 mA cm−2, 40 mAh cm−2, DOD = 75.97%) and 490 h (100 mA cm−2, 100 mAh cm−2, DOD = 90.91%), and achieving an unprecedented cumulative capacity of 62.92 Ah cm−2. This work offers both fundamental and practical insights for the interface design in energy storage devices.

This review aims to highlight the effect of electrolyte regulation on alleviating issues on the cathode side in aqueous ZIBs. The recent advances of electrolyte regulation strategies are present, with a comprehensive discussion and summary of regulation mechanisms, which can provide guidance to develop novel and multifunctional electrolytes for next-generation aqueous ZIBs.

Enhancing cathodic performance is crucial for aqueous zinc-ion batteries, with the primary focus of research efforts being the regulation of the intrinsic material structure. Electrolyte regulation is also widely used to improve full-cell performance, whose main optimization mechanisms have been extensively discussed only in regard to the metallic anode. Considering that ionic transport begins in the electrolyte, the modulation of the electrolyte must influence the cathodic performance or even the reaction mechanism. Despite its importance, the discussion of the optimization effects of electrolyte regulation on the cathode has not garnered the attention it deserves. To fill this gap and raise awareness of the importance of electrolyte regulation on cathodic reaction mechanisms, this review comprehensively combs the underlying mechanisms of the electrolyte regulation strategies and classifies the regulation mechanisms into three main categories according to their commonalities for the first time, which are ion effect, solvating effect, and interfacial modulation effect, revealing the missing puzzle piece of the mechanisms of electrolyte regulation in optimizing the cathode.

This study investigates bias-induced structural transformations in 1T-TiSe2 devices, focusing on the transition from the 1T metallic phase to the distorted 1Td phase and ultimately to an orthorhombic Ti9Se2 conducting phase. Using ex-situ and in-situ TEM, dynamic structural changes and insights into the effect of thickness on phase transitions, providing valuable information for CDW-based device applications, are revealed.

Metallic transition metal dichalcogenides (MTMDCs) are of significant attention for various electronic applications due to their anisotropic conductivity, high electron mobility, superconductivity, and charge-density-waves (CDW). Understanding the correlations between electronic properties and structural transformations is crucial. In this study, a bias-induced structural transformation in vertical CDW-based 1T-TiSe2 devices, transitioning from a 1T metallic phase to a distorted transition 1Td phase and subsequently to an orthorhombic Ti9Se2 conducting phase, is reported. Using ex-situ and in-situ biasing transmission electron microscopy, dynamic structural changes, while electron energy loss spectroscopy analysis revealed valence state modifications in Ti and Se within the Ti-rich layer after biasing, are observed. In addition, the effect of varying 1T-TiSe2 thickness on the maximum current value is investigated. These observations reveal that increased thickness requires higher voltage to induce phase transitions. These insights contribute to understanding the structural and electronic dynamics of 1T-TiSe2, highlighting its potential as a promising material for future CDW-based device applications.

Ultra-small silver nanoparticles are formed in situ and activated in an amidoxime-modified polymer of intrinsic microporosity to fabricate a metallic nanocomposite membrane for C2H4/C2H6 separation. The activated silver nanoparticles promote C2H4 transport and effectively enhance C2H4/C2H6 separation selectivity, resulting in an outstanding membrane separation performance with C2H4 permeability of 322.1 barrer and C2H4/C2H6 selectivity as high as 8.8.

The separation of C2H4 and C2H6 is a critical yet energy-intensive operation in the petrochemical industry. Gas separation membranes offer energy-efficient alternatives, but their effectiveness is hindered by the similar physical properties of C2H4 and C2H6. Here, a metallic nanocomposite membrane (MNM) comprising ultra-small Ag nanoparticles embedded in an amidoxime-modified polymer of intrinsic microporosity (AOPIM-1) is reported for highly efficient C2H4/C2H6 separation. The microporous structure of AOPIM-1, combined with anchoring groups (amidoxime groups) inside the microcavities, enables size-controlled growth of Ag nanoparticles with ‒≈3 nm diameter, which maximizes the contact with ethylene molecules. The amidoxime groups as electron acceptors effectively enrich the positive charge on the surface of Ag nanoparticles. The activated Ag form reversible complexes with ethylene molecules endowing them with preferential affinity over ethane. The resulting Ag nanocomposite membrane demonstrates a ≈10-fold increase in C2H4 permeability, reaching 322.1 barrer, and a ≈3-fold increase in C2H4/C2H6 selectivity, reaching 8.8. The comprehensive separation performance is superior over all the polymer membranes and mixed matrix membranes reported so far. The MNMs also demonstrate stable mixed gas separation performance under elevated feed gas pressures. This study provides valuable insights into designing and fabricating polymer membranes with high C2H4/C2H6 separation performance.

A Co single-atom catalyst (Co-N₄) enhances Cl₂ adsorption and lowers LiCl reaction barriers in Li-Cl₂ batteries. The Li-Cl₂@Co-NC battery exhibits >600 cycles at 1500 mA g⁻¹ at room temperature and 650 cycles at 500 mA g⁻¹ at −40 °C, with a 0.6 V reduction in polarization voltage. This strategy delivers high-performance Li-Cl₂ batteries with wide temperature adaptability.

Lithium-chlorine (Li-Cl2) secondary batteries are emerging as promising candidates for high-energy-density power sources and an extensive operational temperature range. However, conventional electrode materials suffer from weak adsorption for chlorine gas (Cl2) and low conversion efficiency of lithium chloride (LiCl), leading to significant loss of chlorine-based active materials. This issue hampers the cyclability of Li-Cl2 batteries. In this work, it is demonstrated that synergistic Cl2 adsorption on the electrode surface and the energy barrier for LiCl reactions are crucial for enhancing Cl2/LiCl conversion efficiency. Consequently, a cobalt (Co) single-atom site catalyst with a Co-N4 coordination environment has been developed, which significantly diminishes the transformation barrier of solid LiCl particles into Cl2 and concurrently enhances the chemical adsorption of Cl2, facilitating uniform nucleation of LiCl. As a result, the Li-Cl2@Co-NC battery developed has achieved a 0.6 V reduction in polarization voltage under high current densities, effectively addressing the issue of low conversion efficiency between Cl2 and LiCl. At room temperature, the Li-Cl2@Co-NC battery achieves over 600 cycles at 1500 mA g−1; At −40 °C, it reaches 650 cycles at 500 mA g−1. The research overcomes the cycle stability barrier in high-current Li-Cl2 batteries and offers a strategy for batteries with a wide temperature range and long cycle life.

An eutectogel (PSDIC-gel) with exceptional integrative properties is successfully developed by blending hydrophilic/hydrophobic polymerizable deep eutectic solvents, in which spontaneously forming dual ionic channels through in situ polymerization-induced phase separation. The transparent PSDIC-gel exhibits remarkable tensile strength, high toughness, excellent ionic conductivity, improved water tolerance, and rapid room temperature self-healing ability, thus, has wide application prospects in wearable electronics.

Eutectogels are emerging as the next-generation stretchable electronics due to their superior ionic conductivity, non-volatility, and cost-effectiveness. Nevertheless, most eutectogels suffer from weak mechanical strength and toughness and pronounced hygroscopicity. Herein, a strategy is proposed to fabricate phase-separated eutectogels with dual ionic channels (PSDIC-gel), which exhibit exceptional integrative properties, especially water resistance. By blending hydrophilic/hydrophobic polymerizable deep eutectic solvents, dual ionic channels spontaneously form via polymerization-induced phase separation. The hydrophilic poly(acrylic acid) (PAA) phase containing Li+-channels, rich in hydrogen bonding and ion-dipole interactions, provides mechanical strength and conductivity. The hydrophobic poly(hexafluorobutyl acrylate) (PHFBA) phase incorporating cholinium cation (Ch+) channels enhances toughness, conductivity, and water resistance. Adjusting the phase ratio yields a microphase-separated transparent eutectogel with high tensile strength (6.03 MPa), toughness (16.18 MJ m−3), excellent ionic conductivity (1.6 × 10−3 S m−1), strong substrate adhesion, and rapid room-temperature self-healing. Solid-state NMR reveals the conductive mechanism and the phase-separated structure featuring dual ionic channels in PSDIC-gels, advancing the understanding of complex ionic interactions at the atomic level. The PSDIC-gel enables a flexible triboelectric nanogenerator for accurate real-time self-powered human motion sensing. This work advances eutectogel design through structure-property engineering, offering a universal strategy to reconcile mechanical robustness, environmental suitability, and ionic conductivity for wearable electronics.

Stereoisomerism engineering plays a crucial role in tailoring the properties of vicinal dichloronorbornene (PDCNB), with profound effects in backbone spacing, π-stacking, barrier height, and trap states, empowering PDCNB with superior capacitive performance that outperforms existing polymers and nanocomposites in capacitive energy storage at 250 °C.

The emergence of high-density electronics in aerospace and renewable energies demands high temperature dielectrics. Molecular engineering represents a vital strategy for designing dielectric polymers, yet the influence of stereochemistry remains untapped. Herein, by designing halogen substituents of an aromatic pendant attached to a bicyclic mainchain, vicinal polydichloronorbornene (PDCNB) with a high glass-transition temperature (T g) of 263 °C is obtained. Further study unveils the profound effect of stereochemistry on the properties of exo- and endo-PDCNB. Both isomers show identical high T g and bandgap (4.3 eV), imparting PDCNBs with remarkable capacitive energy storage, outperforming existing polymers and nanocomposites with two orders of magnitude lower conduction at an ultra-high temperature of 250 °C. Moreover, the effect of stereoisomerism is manifested in the differences in backbone spacing, π-stacking, barrier height, and trap states, and the resulting distinct high field performance. Exo-PDCNB displays an extremely low conduction of 6.8 × 10−14 S m⁻1 at 200 mV m⁻1 and maintains a record charge-discharge efficiency of 82% at 450 mV m⁻1, while endo-PDCNB exhibits a high breakdown strength of 600 mV m⁻1 with a remarkable discharged density of 4.47 J cm⁻3, all at 250 °C. This study unleashes a stereochemistry-based strategy with vicinal dichloro substitution to further boost the T g of polynorbornene for ultra-high-temperature applications.

A flexible wearable ternary gel thermocell (TGTC) by integrating a thermosensitive crystallizing agent, and supporting electrolyte into a natural nanocellulose hydrogel matrix is designed and constructed, which exhibits a remarkable thermopower, an optimized effective ionic conductivity, anti-drying, freezing resistance, and mechanical robustness. This work provides a versatile strategy for developing TGTC, contributing to advancements in low-grade energy harvesting and wearable electronics for the Internet of Things era.

Gel thermocells (GTCs) provide a safe, facile, and scalable solution for harvesting waste heat to power ubiquitous electronics. However, achieving a harmonious integration of high power density, wide-temperature-range stability, and mechanical robustness in GTCs remains a significant challenge. In this work, a novel ternary gel thermocell (TGTC) is proposed and fabricated by integrating ferro/ferricyanide (Fe(CN)6 3−/4−) redox couples, thermosensitive crystallizing agents guanidinium chloride (GdmCl), and supporting electrolytes lithium chloride (LiCl) into natural nanocellulose hydrogels to enhance overall performance. GdmCl selectively induces Fe(CN)6 4− crystallization, increasing the concentration difference of redox pairs, resulting in improving thermopower and significantly increased fiber friction, while LiCl rapidly balances charges through electromigration promoting efficient ion transport and reconstructing hydrogen bond networks, contributing to an excellent output power density and the capture of water molecules, which are further elucidated by simulations, achieving synchronous enhancement of anti-drying, anti-freezing and mechanical properties. Consequently, the TGTC achieves a remarkable thermopower of 3.42 mV K−1, a maximum power density of 2.8 mW m−2 K−2, multiple continuous stable cycles at −20 °C, and an impressive strength of 3.06 MPa. Notably, this study elucidates the design principles and underlying mechanisms of ternary gel electrolytes, offering a practical strategy for advancing GTC technology.

Herein, in a bold departure from convention, the Ouzo effect is pioneeringly utilized to design surfactant-free microemulsion electrolyte (SFMEE), creating the first application of water-in-oil type Möbius polarity topological solvation in zinc-ion batteries. This approach enables dual regulation of both the solvent environment and the solvation structure, thereby enhancing battery performance.

Zinc-ion batteries (ZIBs) have promising prospects in energy storage field, but the water molecules in aqueous electrolytes significantly compromise the stability of the anode and cathode interfaces and hinder the low-temperature performance. Herein, water-in-oil type Möbius polarity topological solvation composed of oil, water, and amphiphilic salt are first-ever pioneered, forming the surfactant-free microemulsion electrolyte (SFMEE). This water-in-oil type Möbius solvation structure, characterized by its distinct inner and outer layers and a polarity inversion feature, successfully connects the non-polar phase with the polar phase, eliminating the need for surfactants to reduce costs and system complexity. The amphiphilic anion of salt creates a polarity singularity and stabilizes the polarity-reversed encapsulation. The outer oil layer disrupts the cohesive polarity network of water and constructs a polarity-reversed cage to restrict water. A series of SFMEE combinations are investigated and then directly applied to ZIBs, confirming excellent universality and durability of this design. The Zn||NVO (NaV₃O₈·1.5H₂O) cells using SFMEE can stably cycle for 4000 cycles with a capacity of 125 mAh g−1 and 86.8% capacity retention. This discovery of Möbius solvation structure unlock unprecedented levels of electrolyte design and illuminate the development of next-generation high-performance energy storage systems.