Controlled Growth of Porous α‐Fe2O3 Branches on β‐MnO2 Nanorods for Excellent Performance in Lithium‐Ion Batteries

Hierarchical nanocomposites rationally designed in component and structure, are highly desirable for the development of lithium‐ion batteries, because they can take full advantages of different components and various structures to achieve superior electrochemical properties. Here, the branched nanocomposite with β‐MnO₂ nanorods as the back‐bone and porous α‐Fe₂O₃ nanorods as the branches are synthesized by a high‐temperature annealing of FeOOH epitaxially grown on the β‐MnO₂ nanorods. Since the β‐MnO₂ nanorods grow along the four‐fold axis, the as‐produced branches of FeOOH and α‐Fe₂O₃ are aligned on their side in a nearly four‐fold symmetry. This synthetic process for the branched nanorods built by β‐MnO₂/α‐Fe₂O₃ is characterized. The branched nanorods of β‐MnO₂/α‐Fe₂O₃ present an excellent lithium‐storage performance. They exhibit a reversible specific capacity of 1028 mAh g^?1 at a current density of 1000 mA g^?1 up to 200 cycles, much higher than the building blocks alone. Even at 4000 mA g^?1, the reversible capacity of the branched nanorods could be kept at 881 mAh g^?1. The outstanding performances of the branched nanorods are attributed to the synergistic effect of different components and the hierarchical structure of the composite. The disclosure of the correlation between the electrochemical properties and the structure/component of the nanocomposites, would greatly benefit the rational design of the high‐performance nanocomposites for lithium ion batteries, in the future.     

Sub‐10 nm Wide Cellulose Nanofibers for Ultrathin Nanoporous Membranes with High Organic Permeation

There are increasing requirements for highly efficient and solvent‐resistant nanoporous membranes in various separation processes. Traditional membranes usually have a poor solvent resistance and a thick skin layer leading to a low permeation flux. Currently, the major challenge lies in fabrication of ultrathin few‐nanometers‐pore membranes for fast organic filtration. Herein, a facile approach is presented to prepare ultrafine cellulose nanofibers for fabrication of ultrathin nanoporous membranes. The obtained nanofibers have a uniform diameter of 7.5 ± 2.5 nm and are homogeneously dispersed in aqueous solutions that are favorable to the fabrication of ultrathin nanoporous membranes. The resulting cellulose nanoporous membranes have an adjustable thickness down to 23 nm and pore sizes ranging from 2.5 to 12 nm. They allow fast permeation of water and organics during pressure‐driven filtration. Typically, the 30 nm thick membrane has high fluxes of 1.14 and 3.96 × 10⁴ L h^?1 m^?2 bar^?1 for pure water and acetone respectively. Furthermore, the as‐prepared cellulose nanofibers are easily employed to produce a novel syringe filter with sub‐10 nm pores that have a wide application in fast separation and purification of nanoparticles on few‐nanometers scale.     

Sustainable Separators for High‐Performance Lithium Ion Batteries Enabled by Chemical Modifications

Natural polymer nanofibers are attractive sustainable raw materials to fabricate separators for high‐performance lithium ion batteries (LIBs). Unfortunately, complicated pore‐forming processes, low ionic conductivity, and relatively low mechanical strength of previously reported natural polymer nanofiber‐based separators severely limit their performances and applications. Here, a chemical modification strategy to endow high performance to natural polymer nanofiber‐based separators is demonstrated by grafting cyanoethyl groups on the surface of chitin nanofibers. The fabricated cyanoethyl‐chitin nanofiber (CCN) separators not only exhibit much higher ionic conductivity but also retain excellent mechanical strength in comparison to unmodified chitin nanofiber separators. Through density function theory calculations, the mechanism of high Li⁺ ion transport in the CCN separator is unraveled as weakening of the binding of Li⁺ ions over that of PF₆^? ions with chitin, via the cyanoethyl modification. The LiFePO₄/Li₄Ti₅O₁₂ full cells using CCN separators show much better rate capability and enhanced capacity retention compared to the cell using commercial polypropylene (PP) separators. Beyond this, the CCN separator can work very well even at an elevated temperature of 120 °C in the LiFePO₄/Li cell. The proposed strategy chemical modification of natural polymer nanofibers will open a new avenue to fabricate sustainable separators for LIBs with superior performance.     

High Pseudocapacitance from Ultrathin V2O5 Films Electrodeposited on Self‐Standing Carbon‐Nanofiber Paper

An ultrathin V₂O₅ layer was electrodeposited by cyclic voltammetry on a self‐standing carbon‐nanofiber paper, which was obtained by stabilization and heat‐treatment of an electrospun polyacrylonitrile (PAN)‐based nanofiber paper. A very‐high capacitance of 1308 F g^?1 was obtained in a 2 M KCl electrolyte when the contribution from the 3 nm thick vanadium oxide was considered alone, contributing to over 90% of the total capacitance (214 F g^?1) despite the low weight percentage of the V₂O₅ (15 wt%). The high capacitance of the V₂O₅ is attributed to the large external surface area of the carbon nanofibers and the maximum number of active sites for the redox reaction of the ultrathin V₂O₅ layer. This ultrathin layer is almost completely accessible to the electrolyte and thus results in maximum utilization of the oxide (i.e., minimization of dead volume). This hypothesis was experimentally evaluated by testing V₂O₅ layers of different thicknesses.     

Triphenylphosphonium‐Conjugated Poly(ε‐caprolactone)‐Based Self‐Assembled Nanostructures as Nanosized Drugs and Drug Delivery Carriers for Mitochondria‐Targeting Synergistic Anticancer Drug Delivery

For mitochondria‐targeting delivery, a coupling reaction between poly(ε‐caprolactone) diol (PCL diol) and 4‐carboxybutyltriphenylphosphonium (4‐carboxybutyl TPP) results in the synthesis of amphiphilic TPP‐PCL‐TPP (TPCL) polymers with a bola‐like structure. In aqueous environments, the TPCL polymer self‐assembled via cosolvent dispersion and film hydration, resulting in the formation of cationic nanoparticles (NPs) less than 50 nm in size with zeta‐potentials of approximately 40 mV. Interestingly, different preparation methods for TPCL NPs result in various morphologies such as nanovesicles, nanofibers, and nanosheets. In vitro cytotoxicity results with TPCL NPs indicate IC₅₀ values of approximately 10–60 μg mL^?1, suggesting their potential as anticancer nanodrugs. TPCL NPs can be loaded both with hydrophobic doxorubicin (Dox) and its hydrophilic salt form (Dox·HCl), and their drug loading contents are approximately 2–10 wt% depending on the loading method and the hydrophilicity/hydrophobicity of the drugs. Although Dox·HCl exhibits more cellular and nuclear uptake, resulting in greater antitumor effects than Dox, most drug‐loaded TPCL NPs exhibit higher mitochondrial uptake and approximately 2–7‐fold higher mitochondria‐to‐nucleus preference than free drugs, resulting in superior (approximately 7.5–18‐fold) tumor‐killing activity for most drug‐loaded TPCL NPs compared with free drugs. In conclusion, TPCL‐based nanoparticles have potential both as antitumor nanodrugs themselves and as nanocarriers for chemical therapeutics.     

High‐Performance CO2 Capture through Polymer‐Based Ultrathin Membranes

Thin film composite (TFC) membranes have attracted great research interest for a wide range of separation processes owing to their potential to achieve excellent permeance. However, it still remains challenging to fully exploit the superiority of thin selective layers when mitigating the pore intrusion phenomenon. Herein, a facile and generic interface‐decoration‐layer strategy collaborating with molecular‐scale organic–inorganic hybridization in the selective layer to obtain a high‐performance ultrathin film composite (UTFC) membrane for CO₂ capture is reported. The interface‐decoration layer of copper hydroxide nanofibers (CHNs) enables the formation of an ultrathin selective layer (≈100 nm), achieving a 2.5‐fold increase in gas permeance. The organic part in the molecular‐scale hybrid material contributes to facilitating CO₂‐selective adsorption while the inorganic part assists in maintaining robust membrane structure, thus remarkably improving the selectivity toward CO₂. As a result, the as‐prepared membrane shows a high CO₂ permeance of 2860 GPU, superior to state‐of‐the‐art polymer membranes, with a CO₂/N₂ selectivity of 28.2. The synergistic strategy proposed here can be extended to a wide range of polymers, holding great potential to produce high‐efficiency ultrathin membranes for molecular separation.     

Controlled Synthesis of Ag2S,Ag2Se,and Ag Nanofibers by Using a General Sacrificial Template and Their Application in Electronic Device Fabrication

Nanofiber bundles of Ag₂S, Ag₂Se, and Ag have been successfully synthesized by making use of Ag₂C₂O₄ template nanofiber bundles, utilizing both anion‐exchange and redox reactions. The obtained bundles were polycrystalline nanofibers composed of nanoparticles in which the precursor morphology was well‐preserved, indicating that Ag₂C₂O₄ nanofiber bundles acted as a general sacrificial template for the synthesis of silver‐based semiconductor and metal nanofibers. Dispersing media and transforming reactants were found to be key factors influencing the chemical transformation in the system. In particular, separate single‐crystalline Ag nanofibers were obtained via a nontemplate route when ascorbic acid was used as a relatively weak reductant. An electrical transfer and switching device was built with the obtained Ag₂S and Ag nanofiber bundles, utilizing the unique ion‐conductor nature of Ag₂S and revealing their potential applications in electronics.     

Hydrogen Selective NH2‐MIL‐53(Al) MOF Membranes with High Permeability

Hydrogen‐based energy is a promising renewable and clean resource. Thus, hydrogen selective microporous membranes with high performance and high stability are demanded. Novel NH₂‐MIL‐53(Al) membranes are evaluated for hydrogen separation for this goal. Continuous NH₂‐MIL‐53(Al) membranes have been prepared successfully on macroporous glass frit discs assisted with colloidal seeds. The gas sorption ability of NH₂‐MIL‐53(Al) materials is studied by gas adsorption measurement. The isosteric heats of adsorption in a sequence of CO₂ > N₂ > CH₄ ≈ H₂ indicates different interactions between NH₂‐MIL‐53(Al) framework and these gases. As‐prepared membranes are measured by single and binary gas permeation at different temperatures. The results of singe gas permeation show a decreasing permeance in an order of H₂ > CH₄ > N₂ > CO₂, suggesting that the diffusion and adsorption properties make significant contributions in the gas permeation through the membrane. In binary gas permeation, the NH₂‐MIL‐53(Al) membrane shows high selectivity for H₂ with separation factors of 20.7, 23.9 and 30.9 at room temperature (288 K) for H₂ over CH₄, N₂ and CO₂, respectively. In comparison to single gas permeation, a slightly higher separation factor is obtained due to the competitive adsorption effect between the gases in the porous MOF membrane. Additionally, the NH₂‐MIL‐53(Al) membrane exhibits very high permeance for H₂ in the mixtures separation (above 1.5 × 10^?6 mol m^?2 s^?1 Pa^?1) due to its large cavity, resulting in a very high separation power. The details of the temperature effect on the permeances of H₂ over other gases are investigated from 288 to 353 K. The supported NH₂‐MIL‐53(Al) membranes with high hydrogen separation power possess high stability, resistance to cracking, temperature cycling and show high reproducibility, necessary for the potential application to hydrogen recycling.     

Synthesis of Optical‐Quality Single‐Crystal β‐BaB2O4 Microwires and Nanowires

The synthesis of optical quality β‐barium borate microwires and nanowires (MNWs) is reported using an organic‐free hydrothermal method with BaCl₂·6H₂O, NaOH, and H₃BO₃ as source materials, and assisted with post‐annealing. As‐synthesized MNWs, with diameters ranging from 500 nm to 2 μm and lengths up to several hundred micrometers, show good optical‐waveguiding capabilities. Based on evanescent coupling between a single BBO MNW waveguide and a fiber taper, propagation losses of 0.30 dB μm^?1 (at 532 nm) and 0.21 dB μm^?1 (at 671 nm) are evaluated, respectively. An evident second‐harmonic generation (SHG) signal at 532 nm with a measured conversion efficiency of about 8.4% is observed when excited by waveguided 1064 nm, picosecond laser pulses within a BBO MNW with a length of the order of 100 μm. The dependence of the SHG conversion efficiency on the MNW diameter is also investigated. These results show a much‐higher SHG efficiency for BBO single‐crystal MNWs compared with bulk crystal, which suggests potential applications in future micro‐/nanoscale nonlinear optical applications such as optical modulation and frequency conversion.     

Inserting Sn Nanoparticles into the Pores of TiO2−x–C Nanofibers by Lithiation

Tin holds promise as an anode material for lithium‐ion batteries (LIBs) because of its high theoretical capacity, but its cycle life is limited by structural degradation. Herein, a novel approach is exploited to insert Sn nanoparticles into the pores of highly stable titanium dioxide–carbon (TiO_2?x–C) nanofiber substrates that can effectively localize the postformed smaller Sn nanoparticles, thereby address the problem of structural degradation, and thus achieve improved anode performance. During first lithiation, a Li_4.4Sn alloy is inserted into the pores surrounding the initial Sn nanoparticles in TiO_2?x–C nanofibers by its large volume expansion. Thereafter, the original Sn nanoparticle with a diameter of about 150 nm cannot be recovered by the delithiation because of the surface absorption between inserted Sn nanoparticles and the TiO_2?x–C substrate, resulting in many smaller Sn nanoparticles remaining in the pores. Batteries containing these porous TiO_2?x–C–Sn nanofibers exhibit a high capacity of 957 mAh g^?1 after 200 cycles at 0.1 A g^?1 and can cycle over 10 000 times at 3 A g^?1 while retaining 82.3% of their capacity, which represents the longest cycling life of Sn‐based anodes for LIBs so far. This interesting method can provide new avenues for other high‐capacity anode material systems that suffer from significant volume expansion.     

Approaching the Downsizing Limit of Maricite NaFePO4 toward High‐Performance Cathode for Sodium‐Ion Batteries

Maricite NaFePO₄ nanodots with minimized sizes (≈1.6 nm) uniformly embedded in porous N‐doped carbon nanofibers (designated as NaFePO₄@C) are first prepared by electrospinning for maximized Na‐storage performance. The obtained flexible NaFePO₄@C fiber membrane adherent on aluminum foil is directly used as binder‐free cathode for sodium‐ion batteries, revealing that the ultrasmall nanosize effect as well as a high‐potential desodiation process can transform the generally perceived electrochemically inactive maricite NaFePO₄ into a highly active amorphous phase; meanwhile, remarkable electrochemical performance in terms of high reversible capacity (145 mA h g^?1 at 0.2 C), high rate capability (61 mA h g^?1 at 50 C), and unprecedentedly high cyclic stability (≈89% capacity retention over 6300 cycles) is achieved. Furthermore, the soft package Na‐ion full battery constructed by the NaFePO₄@C nanofibers cathode and the pure carbon nanofibers anode displays a promising energy density of 168.1 Wh kg^?1 and a notable capacity retention of 87% after 200 cycles. The distinctive 3D network structure of very fine NaFePO₄ nanoparticles homogeneously encapsulated in interconnected porous N‐doped carbon nanofibers, can effectively improve the active materials' utilization rate, facilitate the electrons/Na⁺ ions transport, and strengthen the electrode stability upon prolonged cycling, leading to the fascinating Na‐storage performance.     

Pseudocapacitive Trimetal Fe0.8CoMnO4 Nanoparticles@Carbon Nanofibers as High‐Performance Sodium Storage Anode with Self‐Supported Mechanism

Trimetal Fe_0.8CoMnO₄ (FCMO) nanocrystals with a diameter of about 50 nm perfectly embedded in N doped‐carbon composite nanofibers (denoted as FCMO@C) are successfully prepared through integrating double‐nozzle electrospinning with a drying and calcination process. The as‐prepared FCMO@C nanofibers maintain a high reversible capacity of 420 mAh g^?1 and about 90% capacity retention after 200 cycles at 0.1 A g^?1. For a long‐term cycle, the FCMO@C electrode exhibits excellent cycling stability (87% high capacity retention at 1 A g^?1 after 950 cycles). Kinetic analysis demonstrates that the electrochemical characteristics of the FCMO@C corresponds to the pseudocapacitive approach in charge storage as an anode for sodium ion batteries, which dominantly attributes the credit to FCMO nanocrystals to shorten the migration distance of Na⁺ ions and the nitrogen‐doped carbon skeleton to enhance the electronic transmission and favorably depress the volume expansion during the repeated insertion/extraction of Na⁺ ions. More significantly, a self‐supported mechanism via continuous electrochemical redox reaction of Fe, Co, and Mn can effectively relieve the volume change during charge and discharge. Therefore, this work can provide a new avenue to improve the sodium storage performance of the oxide anode materials.     

Hierarchical Porous Te@ZnCo2O4 Nanofibers Derived from Te@Metal‐Organic Frameworks for Superior Lithium Storage Capability

1D hierarchical porous nanocomposites with tailored chemical composition are gaining popularity in lithium‐ion batteries. Here, with core@shell Te@ZIF‐8 (Zn, Co) nanofibers as a starting point, rational designed porous Te@ZnCo₂O₄ nanocomposite has been fabricated by a simple morphology‐maintained and calcination‐induced oxidative decomposition process, with the purpose of simultaneously settling the pulverization and conductivity issues of transition metal oxides. This is the first time to integrate Te and ZnCo₂O₄ into one architecture at nanometer level. The Te@ZnCo₂O₄ nanofibers combine both advantages of Te such as excellent electrical conductivity and ZnCo₂O₄ with high capacity as well as take full use of their synergistic effect. With the favorable 1D porous structure and the unique composition, this novel Te@ZnCo₂O₄ nanofiber manifests strong ability to improve the lithium storage performances with a high specific capacity of 1364 mA h g^?1 in the initial discharge and a reversible capacity of 956 mA h g^?1 after 100 cycles. When increased the current density to 2000 mA g^?1, the capacity still remains as 307 mA h g^?1, demonstrating superior rate capability. Furthermore, this general strategy can be extended to construct other core@shell Te@MOFs composites.     

Controlled Synthesis of Ultrathin 2D β‐In2S3 with Broadband Photoresponse by Chemical Vapor Deposition

β‐In₂S₃ is a natural defective III–VI semiconductor attracting considerable interests but lack of efficient method for its 2D form fabrication. Here, for the first time, this paper reports controlled synthesis of ultrathin 2D β‐In₂S₃ flakes via a facile space‐confined chemical vapor deposition method. The natural defects in β‐In₂S₃ crystals, clearly revealed by optical spectra and optoelectronic measurement, strongly modulate the (opto)‐electronic of as‐fabricated β‐In₂S₃ and render it a broad detection range from visible to near‐infrared. Particularly, the as‐fabricated β‐In₂S₃ photodetector shows a high photoresponsivity of 137 A W^?1, a high external quantum efficiency of 3.78 × 10⁴%, and a detectivity of 4.74 × 10¹⁰ Jones, accompanied with a fast rise and decay time of 6 and 8 ms, respectively. In addition, an interesting linear response to the testing power intensities range is observed, which can also be understood by the presence of natural defects. The unique defective structure and intrinsic optical properties of β‐In₂S₃, together with its controllable growth, endow it with great potential for future applications in electronics and optoelectronics.     

Angular‐Shaped 4,9‐Dialkyl α‐ and β‐Naphthodithiophene‐Based Donor–Acceptor Copolymers: Investigation of Isomeric Structural Effects on Molecular Properties and Performance of Field‐Effect Transistors and Photovoltaics

Two angular‐shaped 4,9‐didodecyl α‐aNDT and 4,9‐didodecyl β‐aNDT isomeric structures have been regiospecifically designed and synthesized. The distannylated α‐aNDT and β‐aNDT monomers are copolymerized with the Br‐DTNT monomer by the Stille coupling to furnish two isomeric copolymers, PαNDTDTNT and PβNDTDTNT, respectively. The geometric shape and coplanarity of the isomeric α‐aNDT and β‐aNDT segments in the polymers play a decisive role in determining their macroscopic device performance. Theoretical calculations show that PαNDTDTNT possesses more linear polymeric backbone and higher coplanarity than PβNDTDTNT. The less curved conjugated main chain facilitates stronger intermolecular π–π interactions, resulting in more redshifted absorption spectra of PαNDTDTNT in both solution and thin film compared to the PβNDTDTNT counterpart. 2D wide‐angle X‐ray diffraction analysis reveals that PαNDTDTNT has more ordered π‐stacking and lamellar stacking than PβNDTDTNT as a result of the lesser curvature of the PαNDTDTNT backbone. Consistently, PαNDTDTNT exhibits a greater field effect transistor hole mobility of 0.214 cm² V^?1 s^?1 than PβNDTDTNT with a mobility of 0.038 cm² V^?1 s^?1. More significantly, the solar cell device incorporating the PαNDTDTNT:PC₇₁BM blend delivers a superior power conversion efficiency (PCE) of 8.01% that outperforms the PβNDTDTNT:PC₇₁BM‐based device with a moderate PCE of 3.6%.     

Original Fuel‐Cell Membranes from Crosslinked Terpolymers via a “Sol–gel” Strategy

Hybrid organic/inorganic membranes that include a functionalized (‐SO₃H), interconnected silica network, a non‐porogenic organic matrix, and a ‐SO₃H‐functionalized terpolymer are synthesized through a sol–gel‐based strategy. The use of a novel crosslinkable poly(vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene sulfonyl fluoride)‐ter‐vinyltriethoxysilane) (poly(VDF‐ter‐PFSVE‐ter‐VTEOS)) terpolymer allows a multiple tuning of the different interfaces to produce original hybrid membranes with improved properties. The synthesized terpolymer and the composite membranes are characterized, and the proton conductivity of a hybrid membrane in the absence of the terpolymer is promising, since 8 mS cm^?1 is reached at room temperature, immersed in water, with an experimental ion‐exchange‐capacity (IEC_exp) value of 0.4 meq g^?1. Furthermore, when the composite membranes contain the interfaced terpolymer, they exhibit both a higher proton conductivity (43 mS cm^?1 at 65 °C under 100% relative humidity) and better stability than the standard hybrid membrane, arising from the occurrence of a better interface between the inorganic silica and the poly[(vinylidene fluoride)‐co‐hexafluoropropylene] (poly(VDF‐co‐HFP)) copolymer network. Accordingly, the hybrid SiO₂‐SO₃H/terpolymer/poly(VDF‐co‐HFP) copolymer membrane has potential use as an electrolyte in a polymer‐electrolyte‐membrane fuel cell operating at intermediate temperatures.     

Chemically Resistant,Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand

Metal‐organic gels (MOGs) appear as a blooming alternative to well‐known metal‐organic frameworks (MOFs). Porosity of MOGs has a microstructural origin and not strictly crystalline like in MOFs; therefore, gelation may provide porosity to any metal‐organic system, including those with interesting properties but without a porous crystalline structure. The easy and straightforward shaping of MOGs contrasts with the need of binders for MOFs. In this contribution, a series of MOGs based on the assembly of 1D‐coordination polymer nanofibers of formula [M(DTA)]_n (M^II: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli‐responsive electrical conductivity are brought together. The strength of the M? S bond confers an unusual chemical resistance, withstanding exposure to acids, alkalis, and mild oxidizing/reducing chemicals. Supercritical drying of MOGs provides ultralight metal‐organic aerogels (MOAs) with densities as low as 0.03 g cm^?3 and plastic/brittle behavior depending on the nanofiber aspect ratio. Conductivity measurements reveal a semiconducting behavior (10^?12 to 10^?7 S cm^?1 at 298 K) that can be improved by doping (10^?5 S cm^?1). Moreover, it must be stressed that conductivity of MOAs reversibly increases (up to 10^?5 S cm^?1) under the presence of acetic acid.     

Properties of Flame Sprayed Ce0.8Gd0.2O1.9‐δ Electrolyte Thin Films

Thin films of Ce_0.8Gd_0.2O_1.9‐δ (CGO) are deposited by flame spray deposition with a deposition rate of about 30 nm min^?1. The films (deposited at 200 °C) are dense, smooth, and particle‐free and show a biphasic amorphous/nanocrystalline microstructure. Isothermal grain growth and microstrain are determined as a function of dwell time and temperature and correlated to the electrical conductivity. CGO films annealed for 10 h at 600 °C present the best electrical conductivity of 0.46 S m^?1 measured at 550 °C. Reasons for the superior performance of films annealed at low temperature over higher‐temperature‐treated samples are discussed and include grain‐size evolution, microstrain relaxation, and chemical decomposition. Nanoindentation measurements are conducted on the CGO thin films as a function of annealing temperature to determine the hardness and elastic modulus of the films for potential application as free‐standing electrolyte membranes in low‐temperature micro‐SOFCs (solid oxide fuel cells).     

All‐Solid‐State Asymmetric Supercapacitors with Metal Selenides Electrodes and Ionic Conductive Composites Electrolytes

All‐solid‐state flexible asymmetric supercapacitors (ASCs) are developed by utilization of graphene nanoribbon (GNR)/Co_0.85Se composites as the positive electrode, GNR/Bi₂Se₃ composites as the negative electrode, and polymer‐grafted‐graphene oxide membranes as solid‐state electrolytes. Both GNR/Co_0.85Se and GNR/Bi₂Se₃ composite electrodes are developed by a facile one‐step hydrothermal growth method from graphene oxide nanoribbons as the nucleation framework. The GNR/Co_0.85Se composite electrode exhibits a specific capacity of 76.4 mAh g^?1 at a current density of 1 A g^?1 and the GNR/Bi₂Se₃ composite electrode exhibits a specific capacity of 100.2 mAh g^?1 at a current density of 0.5 A g^?1. Moreover, the stretchable membrane solid‐state electrolytes exhibit superior ionic conductivity of 108.7 mS cm^?1. As a result, the flexible ASCs demonstrate an operating voltage of 1.6 V, an energy density of 30.9 Wh kg^?1 at the power density of 559 W kg^?1, and excellent cycling stability with 89% capacitance retention after 5000 cycles. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate high performance flexible all‐solid‐state ASCs for energy storage.     

Hierarchical Engineering of Porous P2‐Na2/3Ni1/3Mn2/3O2 Nanofibers Assembled by Nanoparticles Enables Superior Sodium‐Ion Storage Cathodes

Layered transition metal oxides (TMOs) are appealing cathode candidates for sodium‐ion batteries (SIBs) by virtue of their facile 2D Na⁺ diffusion paths and high theoretical capacities but suffer from poor cycling stability. Herein, taking P2‐type Na_2/3Ni_1/3Mn_2/3O₂ as an example, it is demonstrated that the hierarchical engineering of porous nanofibers assembled by nanoparticles can effectively boost the reaction kinetics and stabilize the structure. The P2‐Na_2/3Ni_1/3Mn_2/3O₂ nanofibers exhibit exceptional rate capability (166.7 mA h g^?1 at 0.1 C with 73.4 mA h g^?1 at 20 C) and significantly improved cycle life (≈81% capacity retention after 500 cycles) as cathode materials for SIBs. The highly reversible structure evolution and Ni/Mn valence change during sodium insertion/extraction are verified by in operando X‐ray diffraction and ex situ X‐ray photoelectron spectroscopy, respectively. The facilitated electrode process kinetics are demonstrated by an additional study using the electrochemical measurements and density functional theory computations. More impressively, the prototype Na‐ion full battery built with a Na_2/3Ni_1/3Mn_2/3O₂ nanofibers cathode and hard carbon anode delivers a promising energy density of 212.5 Wh kg^?1. The concept of designing a fibrous framework composed of small nanograins offers a new and generally applicable strategy for enhancing the Na‐storage performance of layered TMO cathode materials.