All‑Covalent Organic Framework Nanofilms Assembled Lithium‑Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Mechanically flexible reduced graphene oxide/carbon composite films for high-performance quasi-solid-state lithium-ion capacitors

Practical applications of diverse flexible wearable electronics require electrochemical energy storage(EES)devices with multiple configurations.Moreover,to fabricate flexible EES devices with high energy density and stability,organic integration from electrode design to device assembly is required.To address these challenges,a free-standing reduced graphene oxide(rGO)/carbon film with a unique sandwich structure has been designed via the assistance of vacuum-assistant filtration for lithium-ion capacitors(LICs).The graphene acts as not only a binder to construct a three-dimensional conductive network but also an active material to provide additional capacitive lithium storage sites,thus enabling fast ion/electron transport and improving the capacity.The designed rGO/hard carbon(rGO/HC)and rGO/activated carbon(rGO/AC)free-standing films exhibit enhanced specific capacities(513.7 mA h g^(-1)for rGO/HC and 102.8 mA h g^(-1)for rGO/AC)and excellent stability.Moreover,the integrated flexible quasi-solid-state rGO/AC//rGO/HC LIC devices possess a maximum energy density of 138.3 Wh kg^(-1),a high power density of 11 kW kg^(-1),and improved cycling performance(84.4%capacitance maintained after 10,000 cycles),superior to the AC//HC LIC(43.5%retention).Such a strategy enlightens the development of portable flexible LICs.

Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Electrostatic Interaction-directed Construction of Hierarchical Nanostructured Carbon Composite with Dual Electrical Conductive Networks for Zinc-ion Hybrid Capacitors with Ultrastability

Metal-organic framework(MOF)-derived carbon composites have been considered as the promising materials for energy storage.However,the construction of MOF-based composites with highly controllable mode via the liquid-liquid synthesis method has a great challenge because of the simultaneous heterogeneous nucleation on substrates and the self-nucleation of individual MOF nanocrystals in the liquid phase.Herein,we report a bidirectional electrostatic generated self-assembly strategy to achieve the precisely controlled coatings of single-layer nanoscale MOFs on a range of substrates,including carbon nanotubes(CNTs),graphene oxide(GO),MXene,layered double hydroxides(LDHs),MOFs,and SiO_(2).The obtained MOF-based nanostructured carbon composite exhibits the hierarchical porosity(V_(meso)/V_(micro)∶2.4),ultrahigh N content of 12.4 at.%and"dual electrical conductive networks."The assembled aqueous zinc-ion hybrid capacitor(ZIC)with the prepared nanocarbon composite as a cathode shows a high specific capacitance of 236 F g^(-1)at 0.5 A g^(-1),great rate performance of 98 F g^(-1)at 100 A g^(-1),and especially,an ultralong cycling stability up to 230000 cycles with the capacitance retention of 90.1%.This work develops a repeatable and general method for the controlled construction of MOF coatings on various functional substrates and further fabricates carbon composites for ZICs with ultrastability.

Interlayer and intralayer co-modified flexible V_(2)CT_(X) MXene@SWCNT films for high-power Li-ion capacitors

As an emerging member of the two-dimensional(2D)material family,V_(2)CT_(X)MXene shows great potential in the application of lithium-ion capacitors(LICs)due to its unique structure and excellent electrical conductivity.However,severe nanosheets stacking and intra-layer transport barriers have limited the further development of V_(2)CT_(X)MXene-based materials.Herein,we prepared Kions and–O functional group co-modified V_(2)CT_(X)MXene(VCT-K)and further incorporated it with single-walled carbon nanotube(SWCNT),obtaining freestanding V_(2)CT_(X)composite films(VCT-K@C)with the 3D conductive network.Significantly,K+ions were introduced into V_(2)CT_(X)MXene to stabilize the interlayer structure and prevent the aggregation of nanosheets,the terminal group of–O was controllably modified on the surface of MXene to improve the Li+ions storage reversible capacities and the SWCNT acted as the bridge between MXene nanosheets to opens up the channels for ion/electron transportation in the longitudinal direction.Benefited from the synergistic effect of VCT-K and SWCNT,the VCT-K@C exhibits superior reversible specific capacities of 671.8 mA h g^(-1)at 0.1 A g^(-1)and 318 mA h g^(-1)at 1.0 A g^(-1).Furthermore,the assembled LICs with VCT-K@C anode coupling activated carbon(AC)cathode deliver an outstanding power density of 19.0 kW kg^(-1)at 67.4 Wh kg^(-1),a high energy density of 140.5 Wh kg^(-1)at 94.8 W kg^(-1)and a stable capacitance retention of 86%after 6000 cycles at 10 A g^(-1).Such unique structures and excellent electrochemical properties are expected to pave the way for the large-scale application in LICs of MXene-based materials.

Significantly Improved High-Temperature Energy Storage Performance of BOPP Films by Coating Nanoscale Inorganic Layer

Biaxially oriented polypropylene(BOPP)is one of the most commonly used commercial capacitor films,but its upper operating temperature is below 105℃due to the sharply increased electrical conduction loss at high temperature.In this study,growing an inorganic nanoscale coating layer onto the BOPP film's surface is proposed to suppress electrical conduction loss at high temperature,as well as increase its upper operating temperature.Four kinds of inorganic coating layers that have different energy band structure and dielectric property are grown onto the both surface of BOPP films,respectively.The effect of inorganic coating layer on the high-temperature energy storage performance has been systematically investigated.The favorable coating layer materials and appropriate thickness enable the BOPP films to have a significant improvement in high-temperature energy storage performance.Specifically,when the aluminum nitride(AIN)acts as a coating layer,the AIN-BOPP-AIN sandwich-structured films possess a discharged energy density of 1.5 J cm^(-3)with an efficiency of 90%at 125℃,accompanying an outstandingly cyclic property.Both the discharged energy density and operation temperature are significantly enhanced,indicating that this efficient and facile method provides an important reference to improve the high-temperature energy storage performance of polymer-based dielectric films.

Flexible, Transparent and Conductive Metal Mesh Films with Ultra‑High FoM for Stretchable Heating and Electromagnetic Interference Shielding

Despite the growing demand for transparent conductive films in smart and wearable electronics for electromagnetic interference(EMI)shielding,achieving a flexible EMI shielding film,while maintaining a high transmittance remains a significant challenge.Herein,a flexible,transparent,and conductive copper(Cu)metal mesh film for EMI shielding is fabricated by self-forming crackle template method and electroplating technique.The Cu mesh film shows an ultra-low sheet resistance(0.18Ω□^(-1)),high transmittance(85.8%@550 nm),and ultra-high figure of merit(>13,000).It also has satisfactory stretchability and mechanical stability,with a resistance increases of only 1.3%after 1,000 bending cycles.As a stretchable heater(ε>30%),the saturation temperature of the film can reach over 110°C within 60 s at 1.00 V applied voltage.Moreover,the metal mesh film exhibits outstanding average EMI shielding effectiveness of 40.4 dB in the X-band at the thickness of 2.5μm.As a demonstration,it is used as a transparent window for shielding the wireless communication electromagnetic waves.Therefore,the flexible and transparent conductive Cu mesh film proposed in this work provides a promising candidate for the next-generation EMI shielding applications.

OptoGPT: A foundation model for inverse design in optical multilayer thin film structures

Optical multilayer thin film structures have been widely used in numerous photonic applications.However,existing inverse design methods have many drawbacks because they either fail to quickly adapt to different design targets,or are difficult to suit for different types of structures,e.g.,designing for different materials at each layer.These methods also cannot accommodate versatile design situations under different angles and polarizations.In addition,how to benefit practical fabrications and manufacturing has not been extensively considered yet.In this work,we introduce OptoGPT(Opto Generative Pretrained Transformer),a decoder-only transformer,to solve all these drawbacks and issues simultaneously.

Numerical and experimental study on the falling film flow characteristics with the effect of co-current gas flow in hydrogen liquefaction process

Liquid hydrogen storage and transportation is an effective method for large-scale transportation and utilization of hydrogen energy. Revealing the flow mechanism of cryogenic working fluid is the key to optimize heat exchanger structure and hydrogen liquefaction process(LH2). The methods of cryogenic visualization experiment, theoretical analysis and numerical simulation are conducted to study the falling film flow characteristics with the effect of co-current gas flow in LH2spiral wound heat exchanger.The results show that the flow rate of mixed refrigerant has a great influence on liquid film spreading process, falling film flow pattern and heat transfer performance. The liquid film of LH2mixed refrigerant with column flow pattern can not uniformly and completely cover the tube wall surface. As liquid flow rate increases, the falling film flow pattern evolves into sheet-column flow and sheet flow, and liquid film completely covers the surface of tube wall. With the increase of shear effect of gas-phase mixed refrigerant in the same direction, the liquid film gradually becomes unstable, and the flow pattern eventually evolves into a mist flow.

Highly Flexible Graphene-Film-Based Rectenna for Wireless Energy Harvesting

Herein,we report the design,fabrication,and performance of two wireless energy harvesting devices based on highly flexible graphene macroscopic films(FGMFs).We first demonstrate that benefiting from the high conductivity of up to 1×10^(6)S m^(-1)and good resistive stability of FGMFs even under extensive bending,the FGMFs-based rectifying circuit(GRC)exhibits good flexibility and RF-to-DC efficiency of 53%at 2.1 GHz.Moreover,we further expand the application of FGMFs to a flexible wideband monopole rectenna and a 2.45 GHz wearable rectenna for harvesting wireless energy.The wideband rectenna at various bending conditions produces a maximum conversion efficiency of 52%,46%,and 44%at the 5th Generation(5G)2.1 GHz,Industrial Long-Term Evolution(LTE)2.3 GHz,and Scientific Medical(ISM)2.45 GHz,respectively.A 2.45 GHz GRC is optimized and integrated with an AMC-backed wearable antenna.The proposed 2.45 GHz wearable rectenna shows a maximum conversion efficiency of 55.7%.All the results indicate that the highly flexible graphene-film-based rectennas have great potential as a wireless power supplier for smart Internet of Things(loT)applications.

Alternatingly stacked thin film electrodes-based compact aqueous hybrid electrochemical capacitors for hundred-volts AC line filtering

Filtering capacitor with compact configuration and a wide range of operating voltage has been attracting increasing attention for the smooth conversion of the electric signal in modern circuits.Lossless integration of capacitor units can be regarded as one of the efficient ways to achieve a wider voltage range,which has not yet been fully conquered due to the lack of rational designs of the electrode structure and integration technology.This study presents an alternatingly stacked assemble technology to conveniently fabricate compact aqueous hybrid integrated filtering capacitors on a large scale,in which a unit consists of rGO/MXene composite film as a negative electrode and PEDOT:PSS based film as a positive electrode.Benefiting from the synergistic effect of rGO and MXene components,and morphological characteristics of PEDOT:PSS,the capacitor unit exhibits outstanding AC line filtering with a large areal specific energy density of 1,015 μF V^(2)cm^(-2)(0.28 μW h cm^(-2)) at 120 Hz.After rational integration,the assembled capacitors present compact/lightweight configuration and lossless frequency response,as reflected by almost constant resistor-capacitor time constant of 0.2 ms and dissipation factor of 15% at120 Hz,identical to those of the single capacitor unit.Apart from standing alone steadily on a flower,a small volume(only 8.1 cm^(3)) of the integrated capacitor with 70 units connected in series achieves hundred-volts alternating current line filtering,which is superior to most reported filtering capacitors with sandwich configuration.This study provides insight into the fabrication and application of compact/ultralight filtering capacitors with lossless frequency response,and a wide range of operating voltage.

High Density 3D Carbon Tube Nanoarray Electrode Boosting the Capacitance of Filter Capacitor

Electric double-layer capacitors(EDLCs)with fast frequency response are regarded as small-scale alternatives to the commercial bulky aluminum electrolytic capacitors.Creating carbon-based nanoarray electrodes with precise alignment and smooth ion channels is crucial for enhancing EDLCs’performance.However,controlling the density of macropore-dominated nanoarray electrodes poses challenges in boosting the capacitance of line-filtering EDLCs.Herein,a simple technique to finely adjust the vertical-pore diameter and inter-spacing in three-dimensional nanoporous anodic aluminum oxide(3D-AAO)template is achieved,and 3D compactly arranged carbon tube(3D-CACT)nanoarrays are created as electrodes for symmetrical EDLCs using nanoporous 3D-AAO template-assisted chemical vapor deposition of carbon.The 3D-CACT electrodes demonstrate a high surface area of 253.0 m^(2) g^(−1),a D/G band intensity ratio of 0.94,and a C/O atomic ratio of 8.As a result,the high-density 3D-CT nanoarray-based sandwich-type EDLCs demonstrate a record high specific areal capacitance of 3.23 mF cm^(-2) at 120 Hz and exceptional fast frequency response due to the vertically aligned and highly ordered nanoarray of closely packed CT units.The 3D-CT nanoarray electrode-based EDLCs could serve as line filters in integrated circuits,aiding power system miniaturization.

Coupling of Adhesion and Anti‑Freezing Properties in Hydrogel Electrolytes for Low‑Temperature Aqueous‑Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety,mechanical and thermal stability and easy-to-direct stacking.Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness,high conductivity and intrinsic flexibility.However,the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors.Here,we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance.The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode.Meanwhile,the cooperative solvation of ZnCl2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures.More significantly,the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance,delivering high-energy density of 39 Wh kg^(-1)at-60°C with capacity retention of 98.7%over 10,000 cycles.With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte,the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at-60°C.This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

Author Correction to “Enhanced Property of Thin Cuprous Oxide Film Prepared through Green Synthetic Route”

This correction adds some information to our publication[Chin.J.Chem.Phys.32,365–372(2019)]that we previously missed to include.Our previous work published in[Appl.Catal.B Env-iron.186,10(2016)]was based on the same sample series but with the focus of explaining the interplay between the catalytic behavior and properties of the cuprous thin films.A superior catalytic performance was demonstrated when water was added in the deposition process[1](see Ref.[47]in our publication corrected here).

Centimeter-Scale Above-Room-Temperature Ferromagnetic Fe_(3)GaTe_(2)Thin Films by Molecular Beam Epitaxy

Fe_(3)GaTe_(2),as a layered ferromagnetic material,has a Curie temperature(T_(c))higher than room temperature,making it the key material in next-generation spintronic devices.To be used in practical devices,large-sized high-quality Fe_(3)GaTe_(2)thin films need to be prepared.Here,the centimeter-scale thin film samples with high crystal quality and above-room-temperature ferromagnetism with strong perpendicular magnetic anisotropy were prepared by molecular beam epitaxy technology.Furthermore,the Tc of the samples raises as the film thickness increases,and reaches 367K when the film thickness is 60 nm.This study provides material foundations for the new generation of van der Waals spintronic devices and paves the way for the commercial application of Fe_(3)GaTe_(2).

Defect engineering on BiFeO_(3) through Na and V codoping for aqueous Na-ion capacitors

Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.

Furfural residues derived nitrogen-sulfur co-doped sheet-like carbon: An excellent electrode for dual carbon lithium-ion capacitors

The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.

The application of metal-organic frameworks and their derivatives for lithium-ion capacitors

There is an urgent need for lithium-ion capacitors(LICs)that have both high energy and high power densities to meet the continuously growing energy storage demands.LICs effectively balance the high energy density of traditional rechargeable batteries with the superior power density and long life of supercapacitors(SCs).Nevertheless,the development of LICs is still hampered by limited kinetic processes and capacity mismatch between the cathode and anode.Metal-organic frameworks(MOFs)and their derivatives have received significant attention because of their extensive specific surface area,different pore structures and topologies,and customizable functional sites,making them compelling candidate materials for achieving high-performance LICs.MOF-derived carbons,known for their exceptional electronic conductivity and large surface area,provide improved charge storage and rapid ion transport.MOF-derived transition metal oxides contribute to high specific capacities and improved electrochemical stability.Additionally,MOF-derived metal compounds/carbons provide combined effects that increase both the capacitive and Faradaic reactions,leading to a superior overall performance.The review begins with an overview of the fundamental principles of LICs,followed by an exploration of synthesis strategies and ligand selection for MOF-based composite materials.It then analyzes the advantages of original MOFs and their derived materials,such as carbon materials and metal compounds,in enhancing LIC performance.Finally,the review discusses the major challenges faced by MOFs and their derivatives in LIC applications and offers future research directions and recommendations.

Ultrathin Limit on the Anisotropic Superconductivity of Single-Layered Cuprate Films

Exploring dimensionality effects on cuprates is important for understanding the nature of high-temperature superconductivity.By atomically layer-by-layer growth with oxide molecular beam epitaxy,we demonstrate that La_(2−x)Sr_(x)CuO_(4)(x=0.15)thin films remain superconducting down to 2 unit cells of thickness but quickly reach the maximum superconducting transition temperature at and above 4 unit cells.By fitting the critical magnetic field(μ0H_(c2)),we show that the anisotropy of the film’s superconductivity increases with decreasing film thickness,indicating that the superconductivity of the film gradually evolves from weak three-to two-dimensional character.These results are helpful to gain more insight into the nature of high-temperature superconductivity with dimensionality.

Effect of drying methods on perovskite films and solar cells

The high efficiency,solution processibility,and flexibility of perovskite solar cells make them promising candidates for the photovoltaic industry[1−8].The deposition method is one of the most critical factors that affect the performance of perovskite films.Various deposition methods have been developed to make perovskite films,including spin-coating,slotdie coating.