Superhigh and Robust Ion Selectivity in Membranes Assembled with Monolayer Clay Nanosheets

It is crucial to control the ion transport in membranes for various technological applications such as energy storage and conversion. The emerging functional two-dimensional (2D) nanosheets such as graphene oxide and MXenes show great potential for constructing ordered nanochannels, but the assembled membranes suffer from low ion selectivity and stability. Here a class of robust charge-selective membranes with superhigh cation/anion selectivity, which are assembled with monolayer nanosheets of cationic/anionic clays that inherently have permanent and uniform charges on each layer is reported. The transport number of cations/anions of cationic vermiculite nanosheet membranes (VNMs)/anionic Co-Al layered double hydroxide (CoAl-LDH) nanosheet membranes is over 0.90 in different NaCl concentration gradients, outperforming all the reported ion-selective membranes. Importantly, this excellent ion selectivity can persist at high-concentration salt solutions, under acidic and alkaline conditions, and for a wide range of ions of different sizes and charges. By coupling a pair of cation-selective vermiculite membrane and anion-selective CoAl-LDH membrane, a reverse electrodialysis device which shows an output power density of 0.7 W m⁻² and energy conversion efficiency of 45.5% is constructed. This work provides a new strategy to rationally design high-performance ion-selective membranes by using 2D nanosheets with inherent surface charges for controllable ion-transport applications.     

Bioinspired Ultrastrong Solid Electrolytes with Fast Proton Conduction along 2D Channels

Solid electrolytes have attracted much attention due to their great prospects in a number of energy‐ and environment‐related applications including fuel cells. Fast ion transport and superior mechanical properties of solid electrolytes are both of critical significance for these devices to operate with high efficiency and long‐term stability. To address a common tradeoff relationship between ionic conductivity and mechanical properties, electrolyte membranes with proton‐conducting 2D channels and nacre‐inspired architecture are reported. An unprecedented combination of high proton conductivity (326 mS cm^?1 at 80 °C) and superior mechanical properties (tensile strength of 250 MPa) are achieved due to the integration of exceptionally continuous 2D channels and nacre‐inspired brick‐and‐mortar architecture into one materials system. Moreover, the membrane exhibits higher power density than Nafion 212 membrane, but with a comparative weight of only ≈0.1, indicating potential savings in system weight and cost. Considering the extraordinary properties and independent tunability of ion conduction and mechanical properties, this bioinspired approach may pave the way for the design of next‐generation high‐performance solid electrolytes with nacre‐like architecture.     

IrPd Nanoalloy-Structured Bifunctional Electrocatalyst for Efficient and pH-Universal Water Splitting

The lack of high efficiency and pH-universal bifunctional electrocatalysts for water splitting to hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) hinders the large-scale production of green hydrogen. Here, an IrPd electrocatalyst supported on ketjenblack that exhibits outstanding bifunctional performance for both HER and OER at wide pH conditions is presented. The optimized IrPd catalyst exhibits a specific activity of 4.46 and 3.98 A mg_Ir⁻¹ in the overpotential of 100 and 370 mV for HER and OER, respectively, in alkaline conditions. When applied to the anion exchange membrane electrolyzer, the Ir₄₄Pd₅₆/KB catalyst shows a stability of >20 h at a current of 250 mA cm⁻² for water decomposition, indicating promising prospects for practical applications. Beyond offering an advanced electrocatalyst, this work also guides the rational design of desirable bifunctional electrocatalysts for HER and OER by regulating the microenvironments and electronic structures of metal catalytic sites for diverse catalysis.     

Microfabricated Ion-Selective Transistors with Fast and Super-Nernstian Response

Transistor-based ion sensors have evolved significantly, but the best-performing ones rely on a liquid electrolyte as an internal ion reservoir between the ion-selective membrane and the channel. This liquid reservoir makes sensor miniaturization difficult and leads to devices that are bulky and have limited mechanical flexibility, which is holding back the development of high-performance wearable/implantable ion sensors. This work demonstrates microfabricated ion-selective organic electrochemical transistors (OECTs) with a transconductance of 4 mS, in which a thin polyelectrolyte film with mobile sodium ions replaces the liquid reservoir. These devices are capable of selective detection of various ions with a fast response time (≈1 s), a super-Nernstian sensitivity (85 mV dec⁻¹), and a high current sensitivity (224 µA dec⁻¹), comparing favorably to other ion sensors based on traditional and emerging materials. Furthermore, the ion-selective OECTs are stable with highly reproducible sensitivity even after 5 months. These characteristics pave the way for new applications in implantable and wearable electronics.     

A DNA‐Threaded ZIF‐8 Membrane with High Proton Conductivity and Low Methanol Permeability

Natural biomolecules have potential as proton‐conducting materials, in which the hydrogen‐bond networks can facilitate proton transportation. Herein, a biomolecule/metal–organic framework (MOF) approach to develop hybrid proton‐conductive membranes is reported. Single‐strand DNA molecules are introduced into DNA@ZIF‐8 membranes through a solid‐confined conversion process. The DNA‐threaded ZIF‐8 membrane exhibits high proton conductivity of 3.40 × 10^?4 S cm^?1 at 25 °C and the highest one ever reported of 0.17 S cm^?1 at 75 °C, under 97% relatively humidity, attributed to the formed hydrogen‐bond networks between the DNA molecules and the water molecules inside the cavities of the ZIF‐8, but very low methanol permeability of 1.25 × 10^?8 cm² s^?1 due to the small pore entrance of the DNA@ZIF‐8 membranes. The selectivity of the DNA@ZIF‐8 membrane is thus significantly higher than that of developed proton‐exchange membranes for fuel cells. After assembling the DNA@ZIF‐8 hybrid membrane into direct methanol fuel cells, it exhibits a power density of 9.87 mW cm^?2 . This is the first MOF‐based proton‐conductivity membrane used for direct methanol fuel cells, providing bright promise for such hybrid membranes in this application.     

Self‐Healing Proton‐Exchange Membranes Composed of Nafion–Poly(vinyl alcohol) Complexes for Durable Direct Methanol Fuel Cells

Proton‐exchange membranes (PEMs) that can heal mechanical damage to restore original functions are important for the fabrication of durable and reliable direct methanol fuel cells (DMFCs). The fabrication of healable PEMs that exhibit satisfactory mechanical stability, enhanced proton conductivity, and suppressed methanol permeability via hydrogen‐bonding complexation between Nafion and poly(vinyl alcohol) (PVA) followed by postmodification with 4‐carboxybenzaldehyde (CBA) molecules is presented. Compared with pure Nafion, the CBA/Nafion–PVA membranes exhibit enhanced mechanical properties with an ultimate tensile strength of ≈20.3 MPa and strain of ≈380%. The CBA/Nafion–PVA membrane shows a proton conductivity of 0.11 S cm^?1 at 80 °C, which is 1.2‐fold higher than that of a Nafion membrane. The incorporated PVA gives the CBA/Nafion–PVA membranes excellent proton conductivity and methanol resistance. The resulting CBA/Nafion–PVA membranes are capable of healing mechanical damage of several tens of micrometers in size and restoring their original proton conductivity and methanol resistance under the working conditions of DMFCs. The healing property originates from the reversibility of hydrogen‐bonding interactions between Nafion and CBA‐modified PVA and the high chain mobility of Nafion and CBA‐modified PVA.     

Thin Film Composite Membranes as a New Category of Alkaline Water Electrolysis Membranes

Alkaline water electrolysis (AWE) is considered a promising technology for green hydrogen (H₂) production. Conventional diaphragm-type porous membranes have a high risk of explosion owing to their high gas crossover, while nonporous anion exchange membranes lack mechanical and thermochemical stability, limiting their practical application. Herein, a thin film composite (TFC) membrane is proposed as a new category of AWE membranes. The TFC membrane consists of an ultrathin quaternary ammonium (QA) selective layer formed via Menshutkin reaction-based interfacial polymerization on a porous polyethylene (PE) support. The dense, alkaline-stable, and highly anion-conductive QA layer prevents gas crossover while promoting anion transport. The PE support reinforces the mechanical and thermochemical properties, while its highly porous and thin structure reduces mass transport resistance across the TFC membrane. Consequently, the TFC membrane exhibits unprecedentedly high AWE performance (1.16 A cm⁻² at 1.8 V) using nonprecious group metal electrodes with a potassium hydroxide (25 wt%) aqueous solution at 80 °C, significantly outperforming commercial and other lab-made AWE membranes. Moreover, the TFC membrane demonstrates remarkably low gas crossover, long-term stability, and stack cell operability, thereby ensuring its commercial viability for green H₂ production. This strategy provides an advanced material platform for energy and environmental applications.     

Micrometer‐Sized Porous Fe2N/C Bulk for High‐Areal‐Capacity and Stable Lithium Storage

High‐capacity anodes of lithium‐ion batteries generally suffer from poor electrical conductivity, large volume variation, and low tap density caused by prepared nanostructures, which make it an obstacle to achieve both high‐areal capacity and stable cycling performance for practical applications. Herein, micrometer‐sized porous Fe₂N/C bulk is prepared to tackle the aforementioned issues, and thus realize both high‐areal capacity and stable cycling performance at high mass loading. The porous structure in Fe₂N/C bulk is beneficial to alleviate the volumetric change. In addition, the N‐doped carbon conducting networks with high electrical conductivity provide a fast charge transfer pathway. Meanwhile, the micrometer‐sized Fe₂N/C bulk exhibits a higher tap density than that of commercial graphite powder (1.03 g cm^?3), which facilitates the preparation of thinner electrode at high mass loadings. As a result, a high‐areal capacity of above 4.2 mA h cm^?2 at 0.45 mA cm^?2 is obtained at a high mass loading of 7.0 mg cm^?2 for LIBs, which still maintains at 2.59 mA h cm^?2 after 200 cycles with a capacity retention of 98.8% at 0.89 mA cm^?2.     

Chitosan-Linked Dual-Sulfonate COF Nanosheet Proton Exchange Membrane with High Robustness and Conductivity

2D materials that can provide long-range ordered channels in thin-film form are highly desirable for proton exchange membranes (PEMs). Covalent organic framework nanosheets (CONs) are promising 2D materials possessing intrinsic porosity and high processability. However, the potential of CONs in PEMs is limited by loose sheet stacking and interfacial grain boundary, which lead to unsatisfied mechanical property and discontinuous conduction pathway. Herein, chitosan (CS), a natural polymer with rich  NH₂ groups, is designed as the linker of dual-sulfonate CONs (CON-2(SO₃H)) to obtain CON-2(SO₃H)-based membrane. Ultrathin CON-2(SO₃H) with high crystallinity and large lateral size is synthesized at water–octanoic acid interface. The high flexibility of CS chains and their electrostatic interactions with  SO₃H groups of CON-2(SO₃H) enable effective connection of CON-2(SO₃H), thus endowing membrane dense structure and exceptional stability. The stacked CON-2(SO₃H) constructs regular hydrophilic nanochannels containing high-density  SO₃H groups, and the electrostatic interactions between CON-2(SO₃H) and CS form interfacial acid–base pairs transfer channels. Consequently, CON-2(SO₃H)@CS membrane simultaneously achieves superior proton conductivity of 353 mS cm⁻¹ (under 80 °C hydrated condition) and tensile strength of 95 MPa. This work highlights the advantages of proton-conducting porous CON-2(SO₃H) in advanced PEMs and paves a way in fabricating robust CON-based membranes for various applications.     

Capillary Evaporation on High-Dense Conductive Ramie Carbon for Assisting Highly Volumetric-Performance Supercapacitors

Conductive biomass carbon possesses unique properties of excellent conductivity and outstanding thermal stability, which can be widely used as conductive additive. However, building the high-dense conductive biomass carbon with highly graphitized microcrystals at a lower carbonization temperature is still a major challenge because of structural disorder and low crystallinity of source material. Herein, a simple capillary evaporation method to efficiently build the high-dense conductive ramie carbon (hd-CRC) with the higher tap density of 0.47 cm³ g⁻¹ than commercialized Super-C45 (0.16 cm³ g⁻¹) is reported. Such highly graphitized microcrystals of hd-CRC can achieve the high electrical conductivity of 94.55 S cm⁻¹ at the yield strength of 92.04 MPa , which is higher than commercialized Super-C45 (83.92 S cm⁻¹ at 92.04 MPa). As a demonstration, hd-CRC based symmetrical supercapacitors possess a highly volumetric energy density of 9.01 Wh L⁻¹ at 25.87 kW L⁻¹, much more than those of commercialized Super-C45 (5.06 Wh L⁻¹ and 19.30 kW L⁻¹). Remarkably, the flexible package supercapacitor remarkably presents a low leakage current of 10.27 mA and low equivalent series resistance of 3.93 mΩ. Evidently, this work is a meaningful step toward high-dense conductive biomass carbon from traditional biomass graphite carbon, greatly promoting the highly-volumetric–performance supercapacitors.     

Ni Single Atoms Embedded in Graphene Nanoribbon Sieves for High-Performance CO2 Reduction to CO

Ni single-atom catalysts (SACs) are appealing for electrochemical reduction CO₂ reduction (CO₂RR). However, regulating the balance between the activity and conductivity remains a challenge to Ni SACs due to the limitation of substrates structure. Herein, the intrinsic performance enhancement of Ni SACs anchored on quasi-one-dimensional graphene nanoribbons (GNRs) synthesized is demonstrated by longitudinal unzipping carbon nanotubes (CNTs). The abundant functional groups on GNRs can absorb Ni atoms to form rich Ni–N₄–C sites during the anchoring process, providing a high intrinsic activity. In addition, the GNRs, which maintain a quasi-one-dimensional structure and possess a high conductivity, interconnect with each other and form a conductive porous framework. The catalyst yields a 44 mA cm⁻² CO partial current density and 96% faradaic efficiency of CO (FE_CO) at −1.1 V vs RHE in an H-cell. By adopting a membrane electrode assembly (MEA) flow cell, a 95% FE_CO and 2.4 V cell voltage are achieved at 200 mA cm⁻² current density. This work provides a rational way to synthesize Ni SACs with a high Ni atom loading, porous morphology, and high conductivity with potential industrial applications.     

Uniform Zinc Deposition Regulated by a Nitrogen-Doped MXene Artificial Solid Electrolyte Interlayer

The dendrite growth and side reactions of zinc metal anode in mildly acidic electrolytes seriously hinder the practical application of aqueous zinc–ion battery. To address these issues, an artificial protective layer of nitrogen-doped MXene (NMX) is used to protect the zinc anode. The NMX protective layer has high conductivity and uniformly distributed zincophilic sites, which can not only homogenize the local electric field on the electrode interface but also accelerate the kinetics for Zn deposition. As a result, the NMX protective layer induces uniform zinc deposition and reduces the overpotential of the electrode. Encouragingly, this NMX-protected Zn anode can cycle stably for 1900 h at 1 mA cm⁻² and 1 mAh cm⁻². In asymmetric cells, it achieves high cycle reversibility with an average Coulomb efficiency of 99.79% for 4800 cycles at 5 mA cm⁻².     

Construction of Synchronous-Deposition K Metal Anodes Via Modulation of Ion/Electron Transport Kinetics for High-Rate and Low-Temperature K Metal Batteries

The construction of conductive scaffolds is demonstrated to be an ideal strategy to alleviate the volume expansion and dendrite growth of K metal anodes. Nevertheless, the heterogeneous top–bottom deposition behavior caused by incompatible electronic/ionic conductivity of three-dimensional (3D) skeleton severely hinders its application. Here, a K₂Se/Cu conducting layer is fabricated on the Cu foam so as to enhance ionic transport and weaken electronic conductivity of the skeleton. Then, an excellent simultaneous deposition behavior of K metal inside the host is obtained for the first time via tuning fast ionic transport and low electronic conductivity. The simultaneous deposition mode can not only utilize the entire 3D structure to accommodate the volume expansion during K deposition but also avoid the formation of K dendrites at high current and ultra-low temperature. Consequently, the symmetric cells present a long cycle lifespan over 1000 h with a low deposition overpotential of 80 mV at 1 mA cm⁻². Furthermore, the full cell matching with the perylene-tetracarboxylic dianhydride (PTCDA) cathode presents an outstanding cycle lifespan over 600 cycles at 5 C at -20°C. The proposed simultaneous deposition strategy provides a new design direction for the construction of dendrite-free K metal anodes.     

Fabrication of a Cation Exchange Membrane with Largely Reduced Anion Permeability for Advanced Aqueous K-ion Battery in an Alkaline-Neutral Electrolyte Decoupling System

Herein, an efficient method to prepare sulfonated polyether ether ketone (SPEEK) based cation exchange membranes (CEMs) is developed, where polyethersulfone (PES) is used as an additive. The optimized membrane of 30 wt.%PES/SPEEK-M exhibits a rather low anion permeability and a high ionic conductivity of 9.52 mS cm⁻¹ together with low volume swelling in water. Meanwhile, tensile strength of the membrane is as high as 31.4 MPa with a tensile strain of 162%. As separators for aqueous K-ion batteries (AKIBs) with decoupled gel electrolytes (Zn anode in alkaline and Prussian blue (FeHCF) cathode in neutral). Discharge voltage of the AKIB can reach 2.3 V. Meanwhile, Zn dendrites can be effectively suppressed in the gel anolyte. Specific capacities of the FeHCF cathode are 116.7 mAh g⁻¹ at 0.3 A g⁻¹ (close to its theoretical value), and 95.0 mAh g⁻¹ at 1.0 A g⁻¹, indicating good rate performance. Capacity retention of the cathode is as high as 91.2% after 1000 cycles’ cycling owing to the well remained neutral environment of the catholyte. There is almost no pH change for the catholyte after cycling, indicating good anion-blocking or cation-selecting ability of the 30 wt.%PES/SPEEK-M, much better than other membranes.     

3-Methyltrimethylammonium poly(2,6-dimethyl-1,4-phenylene oxide) based anion exchange membrane for alkaline polymer electrolyte fuel cells

Hydroxyl ion (OH^?) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl substitution and homogeneously quaternized to form an anion exchange membrane (AEM). ¹H NMR and FT-IR studies reveal successful incorporation of the above groups in the polymer backbone. The membrane is characterized for its ion exchange capacity and water uptake. The membrane formed by these processes show good ionic conductivity and when used in fuel cell exhibited an enhanced performance in comparison with the state-of-the-art commercial AHA membrane. A peak power density of 111 mW/cm² at a load current density of 250 mA/cm² is obtained for PPO based membrane in APEFCs at 30 °C.     

全钒液流电池用新型全氟磺酸离子交换膜制备及性能研究

通过溶液流延成膜法制备了具有不同离子交换容量(IEC)的全氟磺酸(PFSA)离子交换膜,并测试了其吸水率、电导率、钒离子(Ⅴ(Ⅳ))透过率和选择性系数。研究发现,具有高IEC值的PFSA离子交换膜具有相对较低的Ⅴ(Ⅳ)离子透过率和较高的质子电导率。其中IEC值为1.10mmol/g的PFSA离子交换膜对Ⅴ(Ⅳ)离子具有最高的选择性,其选择性系数为Nafion 117膜的2.97倍。     

A Carbonyl Compound‐Based Flexible Cathode with Superior Rate Performance and Cyclic Stability for Flexible Lithium‐Ion Batteries

A sulfur‐linked carbonyl‐based poly(2,5‐dihydroxyl‐1,4‐benzoquinonyl sulfide) (PDHBQS) compound is synthesized and used as cathode material for lithium‐ion batteries (LIBs). Flexible binder‐free composite cathode with single‐wall carbon nanotubes (PDHBQS–SWCNTs) is then fabricated through vacuum filtration method with SWCNTs. Electrochemical measurements show that PDHBQS–SWCNTs cathode can deliver a discharge capacity of 182 mA h g⁻¹ (0.9 mA h cm⁻²) at a current rate of 50 mA g⁻¹ and a potential window of 1.5 V–3.5 V. The cathode delivers a capacity of 75 mA h g⁻¹ (0.47 mA h cm⁻²) at 5000 mA g⁻¹, which confirms its good rate performance at high current density. PDHBQS–SWCNTs flexible cathode retains 89% of its initial capacity at 250 mA g⁻¹ after 500 charge–discharge cycles. Furthermore, large‐area (28 cm²) flexible batteries based on PDHBQS–SWCNTs cathode and lithium foils anode are also assembled. The flexible battery shows good electrochemical activities with continuous bending, which retains 88% of its initial discharge capacity after 2000 bending cycles. The significant capacity, high rate performance, superior cyclic performance, and good flexibility make this material a promising candidate for a future application of flexible LIBs.     

Amphiphilically Modified Porous Polymeric Nanosandwich-Based Membranes for Rapid and Efficient Water Treatment

Low removal efficiency, long treatment time, and high energy consumption hinder advanced and eco-friendly use of traditional adsorbents and separation membranes. Here, a class of amphiphilically modified 2D porous polymeric nanosandwich is designed and is subsequently assembled into adsorptive membranes. The 2D nanosandwich is gifted with high porosity and excellent pore accessibility, demonstrating rapid adsorption kinetics. The as-assembled membrane integrates unimpeded interlayer channels and well-developed, amphiphilic, and highly accessible intralayer nanopores, leading to ultrafast water permeation (1.2 × 10⁴ L m⁻² h⁻¹ bar⁻¹), high removal efficiency, and easy regeneration. The family of the membrane can be expanded by changing amphiphilic functional groups, further providing treatment of a wide-spectrum of pollutants, including aromatic compounds, pesticide, and pharmaceuticals. It is believed that the novel amphiphilically modified adsorptive membrane offers a distinct water treatment strategy with ultrahigh water permeation and efficient pollutants removal performances, and provides a multiple-in-one solution to the detection and elimination of pollutants.     

Effective Suppression of Lithium Dendrite Growth Using a Flexible Single‐Ion Conducting Polymer Electrolyte

A novel single‐ion conducting polymer electrolyte (SIPE) membrane with high lithium‐ion transference number, good mechanical strength, and excellent ionic conductivity is designed and synthesized by facile coupling of lithium bis(allylmalonato) borate (LiBAMB), pentaerythritol tetrakis (2‐mercaptoacetate) (PETMP) and 3,6‐dioxa‐1,8‐octanedithiol (DODT) in an electrospun poly(vinylidienefluoride) (PVDF) supporting membrane via a one‐step photoinitiated in situ thiol–ene click reaction. The structure‐optimized LiBAMB‐PETMP‐DODT (LPD)@PVDF SIPE shows an outstanding ionic conductivity of 1.32 × 10^?3 S cm^?1 at 25 °C, together with a high lithium‐ion transference number of 0.92 and wide electrochemical window up to 6.0 V. The SIPE exhibits high tensile strength of 7.2 MPa and elongation at break of 269%. Due to these superior performances, the SIPE can suppress lithium dendrite growth, which is confirmed by galvanostatic Li plating/stripping cycling test and analysis of morphology of Li metal electrode surface after cycling test. Li|LPD@PVDF|Li symmetric cell maintains an extremely stable and low overpotential without short circuiting over the 1050 h cycle. The Li|LPD@PVDF|LiFePO₄ cell shows excellent rate capacity and outstanding cycle performance compared to cells based on a conventional liquid electrolyte (LE) with Celgard separator. The facile approach of the SIPE provides an effective and promising electrolyte for safe, long‐life, and high‐rate lithium metal batteries.     

Dense-Packed RuO2 Nanorods with In Situ Generated Metal Vacancies Loaded on SnO2 Nanocubes for Proton Exchange Membrane Water Electrolyzer with Ultra-Low Noble Metal Loading

Proton exchange membrane water electrolyzer (PEMWE) is a green hydrogen production technology that can be coupled with intermittent power sources such as wind and photoelectric power. To achieve cost-effective operations, low noble metal loading on the anode catalyst layer is desired. In this study, a catalyst with RuO₂ nanorods coated outside SnO₂ nanocubes is designed, which forms continuous networks and provides high conductivity. This allows for the reduction of Ru contents in catalysts. Furthermore, the structure evolutions on the RuO₂ surface are carefully investigated. The etched RuO₂ surfaces are seen as the consequence of Co leaching, and theoretical calculations demonstrate that it is more effective in driving oxygen evolution. For electrochemical tests, the catalysts with 23 wt% Ru exhibit an overpotential of 178 mV at 10 mA cm⁻², which is much higher than most state-of-art oxygen evolution catalysts. In a practical PEMWE, the noble metal Ru loading on the anode side is only 0.3 mg cm⁻². The cell achieves 1.61 V at 1 A cm⁻² and proper stability at 500 mA cm⁻², demonstrating the effectiveness of the designed catalyst.