Oxygen-Bridged Cu Binuclear Sites for Efficient Electrocatalytic CO2 Reduction to Ethanol at Ultralow Overpotential.

Electrocatalytic CO2 reduction (CO2RR) to alcohols offers a promising strategy for converting waste CO2 into valuable fuels/chemicals but usually requires large overpotentials. Herein, we report a catalyst comprising unique oxygen-bridged Cu binuclear sites (CuOCu-N4) with a Cu···Cu distance of 3.0-3.1 Å and concomitant conventional Cu-N4 mononuclear sites on hierarchical nitrogen-doped carbon nanocages (hNCNCs). The catalyst exhibits a state-of-the-art low overpotential of 0.19 V (versus reversible hydrogen electrode) for ethanol and an outstanding ethanol Faradaic efficiency of 56.3% at an ultralow potential of -0.30 V, with high-stable Cu active-site structures during the CO2RR as confirmed by operando X-ray adsorption fine structure characterization. Theoretical simulations reveal that CuOCu-N4 binuclear sites greatly enhance the C-C coupling at low potentials, while Cu-N4 mononuclear sites and the hNCNC support increase the local CO concentration and ethanol production on CuOCu-N4. This study provides a convenient approach to advanced Cu binuclear site catalysts for CO2RR to ethanol with a deep understanding of the mechanism.

A MOF-Gel Based Separator for Suppressing Redox Mediator Shuttling in Li-O2 Batteries.

Redox mediators (RMs) are widely utilized in the electrolytes of Li-O2 batteries to catalyze the formation/decomposition of Li2O2, which significantly enhances the cycling performance and reduces the charge overpotential. However, RMs have a shuttle effect by migrating to the Li anode side and inducing Li metal degradation through a parasitic reaction. Herein, a metal-organic framework gel (MOF-gel) separator is proposed to restrain the shuttling of RMs. Compared to traditional MOF nanoparticles, MOF gels form uniform and dense films on the separators. When using Ru(acac)3 (ruthenium acetylacetonate) as an RM, the MOF-gel separator suppresses the shuttling of Ru(acac)3 toward the Li anode side and significantly enhances the performance of Li-O2 batteries. Specifically, Li-O2 batteries exhibit an ultralong cycling life (410 cycles) at a current density of 0.5 A g-1. Moreover, the batteries using the MOF-gel/celgard separator exhibit significantly improved cycling performance (increase by ≈1.6 times) at a high current density of 1.0 A g-1 and a decreased charge/discharge overpotential. This result is expected to guide future development of battery separators and the exploration of redox mediators.

Solution-Processed 1D Wurtzite ZnS Nanostructures with Controlled Crystallographic Orientation and Tunable Band-Edge Emission.

1D compound semiconductor nanomaterials possess unique physicochemical properties that strongly depend on their size, composition, and structures. ZnS has been widely investigated as one of the most important semiconductors, and the control of crystallographic orientation of 1D ZnS nanostructures is still challenging and crucial to exploring their anisotropic properties. Herein, a solution-processed strategy is developed to synthesize 1D wurtzite (w-)ZnS nanostructures with the specific <002> and <210> orientations by co-decomposing the copper dibutyldithiocarbamate {[(C4 H9 )2 NCS2 ]2 Cu, i.e., R2 Cu} and zinc dibutyldithiocarbamate (R2 Zn) precursors in the mixed solvents of oleylamine and 1-dodecanethoil. A solution-solid-solid (SSS)-Oriented growth mechanism is proposed, which includes oriented nucleation dominated and SSS growth dominated stages. The crystallographic orientation mainly depends on the interfacial energy and ligand effect. The 1D w-ZnS nanostructures with controlled crystallographic orientation display unique morphologies, i.e., <002>-oriented w-ZnS nanorod enclosed with {110} facets while <210>-oriented w-ZnS nanobelt enclosed with wide (002) and narrow (110) facets. The bandgap of 1D w-ZnS nanostructures can be tuned from 3.94 to 3.82 eV with the crystallographic growth direction varied from <002> to <210>, thus leading to the tunable band-edge emission from ≈338 to ≈345 nm.

Constructing Gold Single-Atom Catalysts on Hierarchical Nitrogen-Doped Carbon Nanocages for Carbon Dioxide Electroreduction to Syngas.

Precious-metal single-atom catalysts (SACs), featured by high metal utilization and unique coordination structure for catalysis, demonstrate distinctive performances in the fields of heterogeneous and electrochemical catalysis. Herein, gold SACs are constructed on hierarchical nitrogen-doped carbon nanocages (hNCNC) via a simple impregnation-drying process and first exploited for electrocatalytic carbon dioxide reduction reaction (CO2RR) to produce syngas. The as-constructed Au SAC exhibits the high mass activity of 3319 A g-1 Au at -1.0 V (vs reversible hydrogen electrode, RHE), much superior to the Au nanoparticles supported on hNCNC. The ratio of H2/CO can be conveniently regulated in the range of 0.4-2.2 by changing the applied potential. Theoretical study indicates such a potential-dependent H2/CO ratio is attributed to the different responses of HER and CO2RR on Au single-atom sites coordinating with one N atom at the edges of micropores across the nanocage shells. The catalytic mechanism of the Au active sites is associated with the smooth switch between twofold and fourfold coordination during CO2RR, which much decreases the free energy changes of the rate-determining steps and promotes the reaction activity.

Correlation between Heteroatom Coordination and Hydrogen Evolution for Single-site Pt on Carbon-based Nanocages.

The electrocatalytic performance of single-site catalysts (SSCs) is closely correlated with the electronic structure of metal atoms. Herein we construct a series of Pt SSCs on heteroatom-doped hierarchical carbon nanocages, which exhibit increasing hydrogen evolution reaction (HER) activities along S-doped, P-doped, undoped and N-doped supports. Theoretical simulation indicates a multi-H-atom adsorption process on Pt SSCs due to the low coordination, and a reasonable descriptor is figured out to evaluate the HER activities. Relative to C-coordinated Pt, N-coordinated Pt has higher reactivity due to the electron transfer of N-to-Pt, which enriches the density of states of Pt 5d orbital near the Fermi level and facilitates the capturing of protons, just the opposite to the situations for P- and S-coordinated ones. The stable N-coordinated Pt originates from the kinetic stability throughout the multi-H-atom adsorption process. This finding provides a significant guidance for rational design of advanced Pt SSCs on carbon-based supports.

High-Dispersive Pd Nanoparticles on Hierarchical N-Doped Carbon Nanocages to Boost Electrochemical CO2 Reduction to Formate at Low Potential.

Electrochemical CO2 reduction reaction (CO2 RR) to value-added chemicals/fuels is an effective strategy to achieve the carbon neutral. Palladium is the only metal to selectively produce formate via CO2 RR at near-zero potentials. To reduce cost and improve activity, the high-dispersive Pd nanoparticles on hierarchical N-doped carbon nanocages (Pd/hNCNCs) are constructed by regulating pH in microwave-assisted ethylene glycol reduction. The optimal catalyst exhibits high formate Faradaic efficiency of >95% within -0.05-0.30 V and delivers an ultrahigh formate partial current density of 10.3 mA cm-2 at the low potential of -0.25 V. The high performance of Pd/hNCNCs is attributed to the small size of uniform Pd nanoparticles, the optimized intermediates adsorption/desorption on modified Pd by N-doped support, and the promoted mass/charge transfer kinetics arising from the hierarchical structure of hNCNCs. This study sheds light on the rational design of high-efficient electrocatalysts for advanced energy conversion.

Enhancing cation storage performance of layered double hydroxides by increasing the interlayer distance.

Layered double hydroxides (LDH) can be transformed from alkaline supercapacitor material into metal-cation storage cathode working in neutral electrolytes through electrochemical activation. However, the rate performance for storing large cations is restricted by the small interlayer distance of LDH. Herein, the interlayer distance of NiCo-LDH is expanded by replacing the interlayer nitrate ions with 1,4-benzenedicarboxylic anions (BDC), leading to the enhanced rate performance for storing large cations (Na+, Mg2+, and Zn2+), whereas almost the unchanged one for storing small-radius Li+ ions. The improved rate performance of the BDC-pillared LDH (LDH-BDC) stems from the reduced charge-transfer and Warburg resistances during charge/discharge due to the increased interlayer distance, as revealed by in situ electrochemical impedance spectra. The asymmetric zinc-ion supercapacitor assembled with LDH-BDC and activated carbon presents high energy density and cycling stability. This study demonstrates an effective strategy to improve the large cation storage performance of LDH electrodes by increasing the interlayer distance.

The Composite-Template Method to Construct Hierarchical Carbon Nanocages for Supercapacitors with Ultrahigh Energy and Power Densities.

3D hierarchical carbon nanocages (hCNC) are becoming new platforms for advanced energy storage and conversion due to their unique structural characteristics, especially the combination of multiscale pore structure with high conductivity of sp2 carbon frameworks, which can promote the mass/charge synergetic transfer in various electrochemical processes. Herein, the MgO@ZnO composite-template method is developed to construct hCNC and nitrogen-doped hCNC (hNCNC), which integrates the advantages of the in situ MgO template method and ZnO self-sacrificing template method. The hierarchical MgO template provides the scaffold for depositing carbon nanocages, while the self-sacrificing ZnO template helps create abundant micropores while promoting the graphitization degree, so that the microstructures of the products are effectively regulated. The optimized hCNC and hNCNC have an increased specific surface area and conductivity, which can further boost the mass/charge synergetic transfer. As the electrode materials of supercapacitors, the optimal hCNC(hNCNC) exhibits a high specific capacitance of 281(348) F g-1 in KOH and 276(297) F g-1 in EMIMBF4 electrolytes at 1 A g-1 . The ultrahigh energy and power densities are realized, accompanied by a high-rate capability and long cycling stability. The record-high energy densities of 141.8-71.4 Wh kg-1 are achieved in EMIMBF4 at power densities of 10.0-250.4 kW kg-1 .

Vertically Grown Few-Layer MoS2 Nanosheets on Hierarchical Carbon Nanocages for Pseudocapacitive Lithium Storage with Ultrahigh-Rate Capability and Long-Term Recyclability.

Molybdenum disulfide (MoS2 ) is an intensively studied anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity, but it is still confronted by severe challenges of unsatisfactory rate capability and cycle life. Herein, few-layer MoS2 nanosheets, vertically grown on hierarchical carbon nanocages (hCNC) by a facile hydrothermal method, introduce pseudocapacitive lithium storage owing to the highly exposed MoS2 basal planes, enhanced conductivity, and facilitated electrolyte access arising from good hybridization with hCNC. Thus, the optimized MoS2 /hCNC exhibits reversible capacities of 1670 mAh g-1 at 0.1 A g-1 after 50 cycles, 621 mAh g-1 at 5.0 A g-1 after 500 cycles, and 196 mAh g-1 at 50 A g-1 after 2500 cycles, which are among the best for MoS2 -based anode materials. The specific power and specific energy, which can reach 16.1 kW kg electrode - 1 and 252.8 Wh kg electrode - 1 after 3000 cycles, respectively, indicate great potential in high-power and long-life LIBs. These findings suggest a promising strategy for exploring advanced anode materials with high reversible capacity, high-rate capability, and long-term recyclability.

From Carbon-Based Nanotubes to Nanocages for Advanced Energy Conversion and Storage.

Carbon-based nanomaterials have been the focus of research interests in the past 30 years due to their abundant microstructures and morphologies, excellent properties, and wide potential applications, as landmarked by 0D fullerene, 1D nanotubes, and 2D graphene. With the availability of high specific surface area (SSA), well-balanced pore distribution, high conductivity, and tunable wettability, carbon-based nanomaterials are highly expected as advanced materials for energy conversion and storage to meet the increasing demands for clean and renewable energies. In this context, attention is usually attracted by the star material of graphene in recent years. In this Account, we overview our studies on carbon-based nanotubes to nanocages for energy conversion and storage, including their synthesis, performances, and related mechanisms. The two carbon nanostructures have the common features of interior cavity, high conductivity, and easy doping but much different SSAs and pore distributions, leading to different performances. We demonstrated a six-membered-ring-based growth mechanism of carbon nanotubes (CNTs) with benzene precursor based on the structural similarity of the benzene ring to the building unit of CNTs. By this mechanism, nitrogen-doped CNTs (NCNTs) with homogeneous N distribution and predominant pyridinic N were obtained with pyridine precursor, providing a new kind of support for convenient surface functionalization via N-participation. Accordingly, various transition-metal nanoparticles were directly immobilized onto NCNTs without premodification. The so-constructed catalysts featured high dispersion, narrow size distribution and tunable composition, which presented superior catalytic performances for energy conversions, for example, the oxygen reduction reaction (ORR) and methanol oxidation in fuel cells. With the advent of the new field of carbon-based metal-free electrocatalysts, we first extended ORR catalysts from the electron-rich N-doped to the electron-deficient B-doped sp2 carbon. The combined experimental and theoretical study indicated the ORR activity originated from the activation of carbon π electrons by breaking the integrity of π conjugation, despite the electron-rich or electron-deficient nature of the dopants. With this understanding, metal-free electrocatalysts were further extended to the dopant-free defective carbon nanomaterials. Moreover, we developed novel 3D hierarchical carbon-based nanocages by the in situ MgO template method, which featured coexisting micro-meso-macropores and much larger SSA than the nanotubes. The unique 3D architecture avoids the restacking generally faced by 2D graphene due to the intrinsic π-π interaction. Consequently, the hierarchical nanocages presented superior performances not only as new catalyst supports and metal-free electrocatalysts but also as electrode materials for energy storage. State-of-the-art supercapacitive performances were achieved with high energy density and power density, as well as excellent rate capability and cycling stability. The large interior space of the nanocages enabled the encapsulation of high-loading sulfur to alleviate polysulfide dissolution while greatly enhancing the electron conduction and Li-ion diffusion, leading to top level performance of lithium-sulfur battery. These results not only provide unique carbon-based nanomaterials but also lead to in-depth understanding of growth mechanisms, material design, and structure-performance relationships, which is significant to promote their energy applications and also to enrich the exciting field of carbon-based nanomaterials.

Sulfur and Nitrogen Codoped Carbon Tubes as Bifunctional Metal-Free Electrocatalysts for Oxygen Reduction and Hydrogen Evolution in Acidic Media.

The technological combination of fuel cells with water electrolysis is an ideal approach to address the problems of growing energy needs and environmental pollution, in which exploring cheap and stable electrocatalysts is the main challenge. Sulfur and nitrogen codoped carbon tubes (SNCTs), prepared by annealing the mixture of amorphous carbonaceous tubes and cysteine, are found to be active bifunctional metal-free electrocatalysts for both oxygen reduction and hydrogen evolution in acidic medium. The optimized SNCT catalyst exhibits a record high onset potential of 851 mV (vs. RHE) for oxygen reduction and concurrent a low overpotential of 76 mV for hydrogen evolution, with superior stability and low cost. The SNCT electrocatalyst could have great potential in proton exchange membrane fuel cells and water splitting devices.

Multiple-Step Humidity-Induced Single-Crystal to Single-Crystal Transformations of a Cobalt Phosphonate: Structural and Proton Conductivity Studies.

Humidity-induced multiple-step single-crystal to single-crystal (SC-SC) transformations are observed in the cobalt phosphonate (NH4)3[Co2(bamdpH)2(HCOO)(H2O)2] (1), where bamdpH4 is (benzylazanediyl)bis(methylene)diphosphonic acid, [C6H5CH2N(CH2PO3H2)2]. Under high-humidity conditions (95% RH), compound 1 experiences hydrolysis at 60 °C which is accompanied by the transformation from a double-chain structure of compound 1 into a single-chain structure of [Co(bamdpH2)(H2O)2]·2H2O (2). When the humidity is below 10% RH, part of the lattice water in compound 2 can be released, forming a third phase, [Co(bamdpH2)(H2O)2]·H2O (3). The structural transformation processes have been monitored by infrared and proton conductivity measurements.

Unconventional O-H···C Hydrogen Bonding and Effects of Conformational Changes on Infrared Spectroscopy of o-Cresol in Solutions.

The unconventional O-H···C intramolecular hydrogen bonding and the effect of conformational changes on IR spectra of o-cresol in aqueous solutions were investigated by using molecular dynamics (MD) simulations, density functional theory (DFT), and experiments. A facial rotational isomerization between global minimum with trans conformation and the cis isomer is predicted to take place in gas phase with a low barrier of about 3.7 kcal/mol through a vertical-like transition state. Upon solvation in aqueous solution, the contents of energetically high-lying vertical and cis conformations of neutral o-cresol are increased to 19% and 57%, respectively, in comparison with those (vertical, 0%; cis, 27%) in vacuum. The IR spectra of aqueous solution are closely related to the relative population of the different conformations, especially for the cis conformation with hydroxyl group facing to alkyl group. The appearance of cis conformations and unconventional O-H···C intramolecular hydrogen bond (HB) caused the low-frequency shift in OH stretching vibration of the IR spectra, which was also correlated with cation-like charge distribution and the decrease in s-component of oxygen hybridization orbital. However, the intermolecular HB between the o-cresol and surrounding water (o-cresol) molecules gave rise to more evident shifts in IR spectra than that caused by the intramolecular HB contributions in cis isomer. Further identification of intramolecular HB effect is performed through the comparison of spectrum changes that occurs on passing from aqueous solution to less interacting (carbon tetrachloride and cyclohexane) solvents. The absence of the intermolecular HB interaction between o-cresol and carbon tetrachloride (and cyclohexane) solvents leads to the weaker intensity and narrower width of OH stretching vibration region (around 3407 cm-1) in the IR spectra than that in aqueous solution.

Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes?

Two kinds of boron and nitrogen co-doped carbon nanotubes (CNTs) dominated by bonded or separated B and N are intentionally prepared, which present distinct oxygen reduction reaction (ORR) performances. The experimental and theoretical results indicate that the bonded case cannot, while the separated one can, turn the inert CNTs into ORR electrocatalysts. This progress demonstrates the crucial role of the doping microstructure on ORR performance, which is of significance in exploring the advanced C-based metal-free electrocatalysts.

Photothermal-Responsive Intelligent Hybrid of Hierarchical Carbon Nanocages Encapsulated by Metal-Organic Hydrogels for Sensitized Photothermal Therapy.

Hierarchical carbon nanocages as emerging nanomaterials have a great potential for photothermal therapy due to their unique porous structure, high specific surface area, and excellent photothermal property. Herein, a hierarchical nitrogen-doped carbon nanocage (hNCNC) is introduced as a second near-infrared photothermal agent, and then functionalizes it with metal-organic hydrogel (MOG) to form a thermal-responsive switch for sensitized photothermal therapy. Upon 1064 nm light irradiation, the hNCNCs exhibit a remarkable photothermal conversion efficiency of 65.9% owing to a high near-infrared extinction coefficient. Meanwhile, due to the hierarchical structure, hNCNCs show 60.2% (wt./wt.) loading efficiency of quercetin, a heat shock protein (Hsp70) inhibitor. Through thermal-driven dry-gel transformation, the coating MOGs intelligently release the encapsulated quercetin for sensitizing cancer cells to heat. Based on the synergistic effect of hyperthermia elevation and thermal-driven drug release, the dual thermal utilization platform achieves effective photothermal tumor ablation in vivo under low concentration of hNCNCs and mild irradiation, which provides a new diagram of intelligent responsive photothermal agents for enhanced photothermal therapy.

High-Rate Lithium-Selenium Batteries Boosted by a Multifunctional Janus Separator Over a Wide Temperature Range of -30 °C to 60 °C.

Lithium-selenium batteries are characterized by high volumetric capacity comparable to Li-S batteries, while ≈1025 times higher electrical conductivity of Se than S is favorable for high-rate capability. However, they also suffer from the "shuttling effect" of lithium polyselenides (LPSes) and Li dendrite growth. Herein, a multifunctional Janus separator is designed by coating hierarchical nitrogen-doped carbon nanocages (hNCNC) and AlN nanowires on two sides of commercial polypropylene (PP) separator to overcome these hindrances. At room temperature, the Li-Se batteries with the Janus separator exhibit an unprecedented high-rate capability (331 mAh g-1 at 25 C) and retain a high capacity of 408 mAh g-1 at 3 C after 500 cycles. Moreover, the high retained capacities are achieved over a wide temperature range from -30 °C to 60 °C, showing the potential application under extreme environments. The excellent performances result from the "1+1>2" synergism of suppressed LPSes shuttling by chemisorption and electrocatalysis of hNCNC on the cathode side and suppressed Li-dendrite growth by thermally conductive AlN-network on the anode side, which can be well understood by the "Bucket Effect". This Janus separator provides a general strategy to develop high-performance lithium-chalcogen (Se, S, SeS2 ) batteries.

Loss-free pulverization by confining copper oxide inside hierarchical nitrogen-doped carbon nanocages toward superb potassium-ion batteries.

Taking the advantages of hierarchical nitrogen-doped carbon nanocages (hNCNCs) with nanocavities for encapsulation and multiscale micro-meso-macropores/high conductivity for mass/electron synergistic transportation, a conversion-type CuO anode material is confined inside hNCNCs for potassium storage. The so-obtained yolk-shelled CuO@hNCNC hybrids have tunable CuO contents in the range of 11.7-63.7 wt%. The unique architecture leads to the loss-free pulverization of the active components during charge/discharge, which increases the surface-controlled charge storage, shortens the K+ solid diffusion lengths with an enlarged K+ diffusion coefficient, and meanwhile enhances the rate capability and durability. Consequently, the optimized CuO@hNCNC delivers a high specific capacity of 498 mA h g-1 at 0.1 A g-1 and 194 mA h g-1 at 10.0 A g-1 based on the total mass of CuO@hNCNC, and a long-term stability. The capacity based on the CuO active component reaches a record-high 522 mA h g-1 at 1.0 A g-1 after 2000 cycles, which is ca. 2.5 times the state-of-the-art value in the literature. The evolution of the cycling performance with CuO loading is well understood based on the loss-free pulverization. This study demonstrates a new strategy to turn the generally harmful pulverization of active components into a beneficial factor for K+ storage, which paves the way for exploring high-performance anodes for rechargeable batteries.

Hierarchical Dual Single-Atom Catalysts with Coupled CoN4 and NiN4 Moieties for Industrial-Level CO2 Electroreduction to Syngas.

Renewable-driven electrochemical CO2 reduction reaction (CO2RR) to syngas is an encouraging alternative strategy to traditional fossil fuel-based syngas production, and the development of industrial-level electrocatalysts is vital. Herein, based on theoretical optimization of metal species, hierarchical CoxNi1-x-N-C dual single-atom catalyst (DSAC) with individual NiN4 (CO preferential) and CoN4 (H2 preferential) moieties was constructed by a two-step pyrolysis route. The Co0.5Ni0.5-N-C exhibits a stable CO Faradaic efficiency of 50 ± 5% and an industrial-level current density of 101-365 mA cm-2 in an ultrawide potential window of -0.5 to -1.1 V. The CO/H2 ratio of syngas can be conveniently tuned by regulating the Co/Ni ratio. The coupled effect of NiN4 and CoN4 moieties under a local high-pH microenvironment is responsible for the regulation of the CO/H2 selectivity and yield for the CoxNi1-x-N-C catalyst, which is not present in the mixed Co-N-C and Ni-N-C catalyst. This study provides a promising DSAC strategy for achieving industrial-level syngas production via CO2RR.

Thermally Conductive AlN-Network Shield for Separators to Achieve Dendrite-Free Plating and Fast Li-Ion Transport toward Durable and High-Rate Lithium-Metal Anodes.

Lithium-metal anodes suffer from inadequate rate and cycling performances for practical application mainly due to the harmful dendrite growth, especially at high currents. Herein a facile construction of the porous and robust network with thermally conductive AlN nanowires onto the commercial polypropylene separator by convenient vacuum filtration is reported. The so-constructed AlN-network shield provides a uniform thermal distribution to realize homogeneous Li deposition, super electrolyte-philic channels to enhance Li-ion transport, and also a physical barrier to resist dendrite piercing as the last fence. Consequently, the symmetric Li|Li cell presents an ultralong lifetime over 8000 h (20 mA cm-2 , 3 mAh cm-2 ) and over 1000 h even at an unprecedented high rate (80 mA cm-2 , 80 mAh cm-2 ), which is far surpassing the corresponding performances reported to date. The corresponding Li|LiFePO4 cell delivers a high specific capacity of 84.3 mAh g-1 at 10 C. This study demonstrates an efficient approach with great application potential toward durable and high-power Li-metal batteries and even beyond.

Insight into the decay mechanism of cycling capacitance for layered double hydroxides at subnanometer scale.

The application of layered double hydroxides (LDHs) in supercapacitors is encouraged by their high capacitances but still limited by deficient cycling stability. The remarkable capacitance decay of LDHs during cycling mainly results from the narrowing of the interlayer distance due to the interlayer anion replacement. A polymer encapsulation strategy is developed to improve the cycling stability of LDHs by inhibiting the anion exchange, opening a new avenue to develop stable LDH-based supercapacitor materials.