Reduced graphene oxide decorated with Bi2O2.33 nanodots for superior lithium storage

Bismuth oxides are important battery materials owing to their ability to electrochemically react and alloy with Li,which results in a high capacity level,which substantially exceeds that of graphite anodes.However,this high Li-storage capability is often compromised by the poor electrochemical cyclability and rate capability of bismuth oxides.To address these challenges,in this study,we design a hybrid architecture composed of reduced graphene oxide (rGO) nanosheets decorated with ultrafine Bi2O2.33 nanodots (denoted as Bi2O2.33/rGO),based on the selective and controlled hydrolysis of a Bi precursor on graphene oxide and subsequent crystallization via solvothermal treatment.Because of its high conductivity,large accessible area,and inherent flexibility,the Bi2O2.33/rGO hybrid exhibits stable and robust Li storage (346 mA·h·g-1 over 600 cycles at 10 C),significantly outperforming previously reported Bi-based materials.This superb performance indicates that decorating rGO nanosheets with ultrafine nanodots may introduce new possibilities for the development of stable and robust metal-oxide electrodes.     

Surface Properties of Fe4N Compounds Layer on AISI 4340 Steel Modified by Pulsed Plasma Nitriding

In this work,the effect of nitriding current density on hardness,crystalline phase composition,layer thickness and corrosion rate of AISI 4340 steel has been studied.X-ray diffraction analysis shows that thin layers formed during nitriding process are constituted of y-Fe₄N for samples processed between 1 and 2.5 mA/cm². Thickness of nitrided layer increases proportionally to current density（0μm for 0.5 mA/cm2 to 1 5μm for 2.5 mA/cm²）.Plasma nitriding increased the surface hardness from 300 HV_50g for untreated sample,to around 800HV_50g for nitrided samples at 1 mA/cm².While the untreated samples exhibited a corrosion rate of 0.153 mm per year,the corrosion performance was improved up to 0.03 mm per year at current densities above 1 mA/cm2,which is about one fifth of the corrosion rate of the untreated sample.     

Stable Zinc Anodes Enabled by Zincophilic Cu Nanowire Networks

Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn²⁺concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^-2and 5 mAh cm^-2),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.     

Manipulating Interfacial Stability Via Absorption-Competition Mechanism for Long-Lifespan Zn Anode

The stability of Zn anode in various Znbased energy storage devices is the key problem to be solved.Herein,aromatic aldehyde additives are selected to modulate the interface reactions between the Zn anode and electrolyte.Through comprehensively considering electrochemical measurements,DFT calculations and FEA simulations,novel mechanisms of one kind of aromatic aldehyde,veratraldehyde in inhibiting Zn dendrite/by-products can be obtained.This additive prefers to absorb on the Zn surface than H₂O molecules and Zn²⁺,while competes with hydrogen evolution reaction and Zn plating/stripping proces s via redox reactions,thus preventing the decomposition of active H₂O near the interface and uncontrollable Zn dendrite growth via a synactic absorption-competition mechanism.As a result,Zn-Zn symmetric cells with the veratraldehyde additive realize an excellent cycling life of 3200 h under 1 mA cm^-2/1 mAh cm^-2and over 800 h even under 5 mA cm^-2/5 mAh cm^-2.Moreover,Zn-Ti and Zn-MnO₂cells with the veratraldehyde additive both obtain elevated performance than that with pure ZnSO₄electrolyte.Finally,two more aromatic aldehyde additives are chosen to prove their universality in stabilizing Zn anodes.     

NiCo2S4/N microspheres grown on N,S co-doped reduced graphene oxide as an efficient bifunctional electrocatalyst for overall water splitting in alkaline and neutral pH

It is of vital importance to design efficient and low-cost bifunctional catalysts for the electrochemical water splitting under alkaline and neutral pH conditions.In this work,we report an efficient and stable NiCo₂S₄/N,S co-doped reduced graphene oxide(NCS/NS-rGO)electrocatalyst for water splitting,in which NCS microspheres are composed of one-dimentional(1D)nanorods grown homogeneously on the surface of NS-rGOs).The synergetic effect,abundant active sites,and hybridization of NCS/NS-rGO endow their outstanding electrocatalytic performance for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in both alkaline and neutral conditions.Furthermore,NCS/NS-rGO employed as both anode and cathode in a two-electrode alkaline and neutral system electrolyzers deliver 10 mA/cm² with the low cell voltage of 1.58 V in alkaline and 1.91 V in neutral condition.These results illustrate the rational design of carbon-supported nickel-cobalt based bifunctional materials for practical water splitting over a wide pH range.     

Annealed microstructure dependent corrosion behavior of Ti-6Al-3Nb-2Zr-1 Mo alloy

Corrosion resistance of titanium(Ti)alloys is closely connected with their microstructure which can be adjusted and controlled via different annealing schemes.Herein,we systematically investigate the specific effects of annealing on the corrosion performance of Ti-6 Al-3 Nb-2 Zr-1 Mo(Ti80)alloy in 3.5 wt.%NaCl and 5 M HCl solutions,respectively,based on open circuit potential(OCP),potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),static immersion tests and surface analysis.Results indicate that increasing annealing tempe rature endows Ti80 alloy with a higher volume fraction ofβphase and finerαphase,which in turn improves its corrosion resistance.Surface characterization demonstrates thatβphase is more resistant to corrosion thanαphase owing to a higher content of Nb,Mo,and Zr in the former;additionally,the decreased thickness of a phase alleviates segregation of elements to further restrain the micro-galvanic couple effects betweenαandβphases.Meanwhile,the influential mechanisms of environmental conditions on corrosion of Ti80 alloy are discussed in detail.As the formation of a highly compact and stable oxide film on surface,annealed Ti80 alloys exhibit a low corrosion current density(10^-6A/cm²)and high polarization impedance(10⁶Ω·cm²)in 3.5 wt.%NaCl solution.However,they suffer severe corrosion in 5 M HCl solution,resulting from the breakdown of native oxide films(the conversion of TiO₂to aqueous Ti³⁺),active dissolution of substrate Ti to aqueous Ti³⁺and existence of micro-galvanic couple effects.Those findings could provide new insights to designing Ti alloys with high-corrosion resistance through microstructural optimization.     

SnO2-reduced graphene oxide nanoribbons as anodes for lithium ion batteries with enhanced cycling stability

A nanocomposite material of SnO2-reduced graphene oxide nanoribbons has been developed. In this composite, the reduced graphene oxide nanoribbons are uniformly coated by nanosized SnO2 that formed a thin layer of SnO2 on the surface. When used as anodes in lithium ion batteries, the composite shows outstanding electrochemical performance with the high reversible discharge capacity of 1,027 mAh/g at 0.1 A/g after 165 cycles and 640 mAh/g at 3.0 A/g after 160 cycles with current rates varying from 0.1 to 3.0 A/g and no capacity decay after 600 cycles compared to the second cycle at a current density of 1.0 A/g. The high reversible capacity, good rate performance and excellent cycling stability of the composite are due to the synergistic combination of electrically conductive reduced graphene oxide nanoribbons and SnO2, The method developed here is practical for the large-scale development of anode materials for lithium ion batteries.     

Improving the intrinsic electronic conductivity of NiMo04 anodes by phosphorous doping for high lithium storage

Heteroatom doping is one of the most promising strategies toward regulating intrinsically sluggish electronic conductivity and kinetic reaction of transition metal oxides for enhancing their lithium storage.Herein,we designed phosphorus-doped NiMo0₄ nanorods(P-NiMo0₄)by using a facile hydrothermal method and subsequent low-temperature phosphorization treatment.Phosphorus doping played an indispensable role in significantly improving electronic conductivity and the Li+diffusion kinetics of NiMo0₄ materials.Experimental investigation and density functional theory calculation demonstrated that phosphorus doping can expand the interplanar spacing and alter electronic structures of NiMo0₄ nanorods.Meanwhile,the introduced phosphorus dopant can generate some oxygen vacancies on the surface of NiMo0₄,which can accelerate Li+diffusion kinetics and provide more active site for lithium storage.As excepted,P-NiMo0₄ electrode delivered a high specific capacity(1,130 mA·g^-1 at 100 mA·g^-1 after 100 cycles),outstanding cycling durability(945 mA·g^-1 at 500 mA·g^-1 over 200 cycles),and impressive rate performance(640 mA·g^-1at 2,000mA·g^-1)for lithium ion batteries(LIBs).This work could provide a potential strategy for improving intrinsic conductivity of transition metal oxides as high-performance anodes for LIBs.     

Regulating Zn Deposition via an Artificial Solid–Electrolyte Interface with Aligned Dipoles for Long Life Zn Anode

Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^?2 with capacity of 1 mAh cm?2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^?1 after 300 cycles.     

Defects enriched hollow porous Co-N-doped carbons embedded with ultrafine CoFe/Co nanoparticles as bifunctional oxygen electrocatalyst for rechargeable flexible solid zinc-air batteries

The construction and design of highly efficient and inexpensive bifunctional oxygen electrocatalysts substitute for noble-metal-based catalysts is highly desirable for the development of rechargeable Zn-air battery(ZAB).In this work,a bifunctional oxygen electrocatalysts of based on ultrafine CoFe alloy(4-5 nm)dispersed in defects enriched hollow porous Co-N-doped carbons,made by annealing SiO2 coated zeolitic imidazolate framework-67(ZIF-67)encapsulated Fe ions.The hollow porous structure not only exposed the active sites inside ZIF-67,but also provided efficient charge and mass transfer.The strong synergetic coupling among high-density CoFe alloys and Co-N_x sites in Co,N-doped carbon species ensures high oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)activity.First-principles simulations reveal that the synergistic promotion effect between CoFe alloy and Co-N site effectively reduced the formation energy of from O^*to OH^*.The optimized CoFe-Co@PNC exhibits outstanding electrocatalytic stability and activity with the overpotential of only 320 mV for OER at 10 mA·cm^?2 and the half-wave potential of 0.887 V for ORR,outperforming that of most recent reported bifunctional electrocatalysts.A rechargeable ZAB constructed with CoFe-Co@PNC as the air cathode displays long-term cyclability for over 200 h and high power density(152.8 mW·cm^?2).Flexible solid-state ZAB with our CoFe-Co@PNC as the air cathode possesses a high open circuit potential(OCP)up to 1.46 V as well as good bending flexibility.This universal structure design provides an attractive and instructive model for the application of nanomaterials derived from MOF in the field of sustainable flexible energy applications device.     

A carbon-based 3D current collector with surface protection for Li metal anode

Lithium metal is considered the ideal anode material for Li-ion-based batteries because it exhibits the highest specific capacity and lowest redox potential for this type of cells.However,growth of Li dendrites,unstable solid electrolyte interphases,low Coulombic efficiencies,and safety hazards have significantly hindered the practical application of metallic Li anodes.Herein,we propose a three-dimensional (3D) carbon nanotube sponge (CNTS) as a Li deposition host.The high specific surface area of the CNTS enables homogenous charge distribution for Li nucleation and minimizes the effective current density to overcome dendrite growth.An additional conformal A12O3 layer on the CNTS coated by atomic layer deposition (ALD) robustly protects the Li metal electrode/electrolyte interface due to the good chemical stability and high mechanical strength of the layer.The Li@ALD-CNTS electrode exhibits stable voltage profiles with a small overpotential ranging from 16 to 30 mV over 100 h of cycling at 1.0 mA·cm-2.Moreover,the electrodes display a dendrite-free morphology after cycling and a Coulombic efficiency of 92.4％ over 80 cycles at 1.0 mA·cm-2 in an organic carbonate electrolyte,thus demonstrating electrochemical stability superior to that of planar current collectors.Our results provide an important strategy for the rational design of current collectors to obtain stable Li metal anodes.     

2-D/2-D heterostructured biomimetic enzyme by interfacial assembling Mn3(PO4)2 and MXene as a flexible platform for realtime sensitive sensing cell superoxide

It is critical for fabricating flexible biosensors with both high sensitivity and good selectivity to realize real-time monitoring superoxide anion(O₂^·?),a specific reactive oxygen species that plays critical roles in various biological processes.This work delicately designs a Mn₃(PO₄)₂/MXene heterostructured biomimetic enzyme by assembling two-dimensional(2-D)Mn₃(PO₄)₂ nanosheets with biomimetic activity and 2-D MXene nanosheets with high conductivity and abundant functional groups.The 2-D nature of the two components with strong interfacial interaction synergistically enables the heterostructure an excellent flexibility with retained 100%of the response when to reach a bending angle up to 180°,and 96%of the response after 100 bending/relaxing cycles.It is found that the surface charge state of the heterostructure promotes the adsorption of O₂^·?,while the high-energy active site improves electrochemical oxidation of O₂^·?.The Mn₃(PO₄)₂/MXene as a sensing platform towards O2??achieves a high sensitivity of 64.93μA·μM^?1·cm^?2,a wide detection range of 5.75 nM to 25.93μM,and a low detection limit of 1.63 nM.Finally,the flexible heterostructured sensing platform realizes real-time monitoring of O₂^·?in live cell assays,offering a promising flexible biosensor towards exploring various biological processes.     

Suitable lithium polysulfides diffusion and adsorption on CNTs@TiO2-bronze nanosheets surface for high-performance lithium-sulfur batteries

The shuttle effect of lithium polysulfides(UPSs)in lithium-sulfur batteries(LSBs)has been hampered their commercialization.Metal oxides as separator modifications can suppress the shuttle effect.Since there is no direct electron transport between metal oxides and UPSs,absorbed UPSs should be diffused from the surface of metal oxides to the carbon matrix to go through redox reactions.If diffusivity of UPSs from metal oxides surface to carbon substrate is poor,it would hinder the redox reactions of LiPSs.Nevertheless,researchers tend to focus on the adsorption and overlook the diffusion of UPSs.Herein,same morphology and different crystal phase of TiO₂ nanosheets grown on carbon nanotubes(CNTs@TiO₂-bronze and CNTs@TiO₂-anatase)have been designed via a simple approach.Compared with CNTs and CNTs@TiO₂-anatase composites,the battery with CNTs@TiO₂-bronze modified separator delivers higher specific capacities and stronger cycling stability,especially at high current rates(~472 mAh·g^-1 at 2.0 C after 1,000 cycles).Adsorption tests,density functional theory calculations and electrochemical performance evaluations indicate that suitable diffusion and adsorption for LiPSs on the CNTs@TiO₂-B surface can effectively capture LiPSs and promote the redox reaction,leading to the superior cycling performances.     

High power and stable P-doped yolk-shell structured Si@C anode simultaneously enhancing conductivity and Li+ diffusion kinetics

Silicon is a low price and high capacity ancxje material for lithium-ion batteries.The yolk-shell structure can effectively accommodate Si expansion to improve stability.However,the limited rate performance of Si anodes can't meet people's growing demand for high power density.Herein,the phosphorus-doped yolk-shell Si@C materials(P-doped Si@C)were prepared through carbon coating on P-doped Si/SiO_xmatrix to obtain high power and stable devices.Therefore,the as-prepared P-doped Si@C electrodes delivered a rapid increase in Coulombic efficiency from 74.4%to 99.6%after only 6 cycles,high capacity retention of-95%over 800 cycles at 4 A·g^-1,and great rate capability(510 mAh·g^-1at 35 A·g^-1).As a result,P-doped Si@C anodes paired with commercial activated carbon and LiFePO₄cathode to assemble lithium-ion capacitor(high power density of?61,080 W·kg^-1at 20 A·g^-1)and lithium-ion full cell(good rate performance with 68.3 mAh·g^-1at 5 C),respectively.This work can provide an effective way tofurther improve power density and stability for energy storage devices.     

Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries

Lithium(Li)metal with high theoretical capacity and low electrochemical potential is the most ideal anode for next-generation high-energy batteries.However,the practical implementation of Li anode has been hindered by dendritic growth and volume expansion during cycling,which results in low Coulombic efficiency(CE),short lifespan,and safety hazards.Here,we report a highly stable and dendrite-free Li metal anode by utilizing N-doped hollow porous bowl-like hard carbon/reduced graphene nanosheets(CB@rGO)hybrids as three-dimensional(3D)conductive and lithiophilic scaffold host.The lithiophilic carbon bowl(CB)mainly works as excellent guides during the Li plating process,whereas the rGO layer with high conductivity and mechanical stability maintains the integrity of the composite by confining the volume change in long-range order during cycling.Moreover,the local current density can be reduced due to the 3D conductive framework.Therefore,CB@rGO presents a low lithium metal nucleation overpotential of 18 mV,high CE of 98%,and stable cycling without obvious voltage fluctuation for over 600 cycles at a current density of 1 mA cm^-2.Our study not only provides a good CB@rGO host and pre-Lithiated CB@rGO composite anode electrode,but also brings a new strategy of designing 3D electrodes for those active materials suffering from severe volume expansion.     

Submicrometer-scale ZnO Composite Aggregate Arrays Photoanodes for Dye-sensitized Solar Cells

Submicrometer-scale ZnO composite aggregate arrays of nanorods and nanoparticles were prepared by simple wet-chemical route and studied as dye-sensitized solar cells（DSSCs）photoanodes.The ZnO composite aggregate arrays significantly improved the efficiency of DSSCs due to their relatively high surface area,fast electron transport,and enhanced light-scattering capability.A short current density(J_sc)of 11.7 mA/cm² and an overall solar-to-electric energy conversion efficiency（η）of 3.17%were achieved for the ZnO composite aggregate DSSCs,which were much higher than those obtained for the monodisperse aggregate DSSCs (J_sc=6.9 mA/cm²,η=1.51%)and ZnO nanorod array DSSCs(J_sc=4.2 mA/cm²,η=0.61%).     

Hydrophobic 1-octadecanethiol functionalized copper catalyst promotes robust high-current CO2 gas-diffusion electrolysis

The electrocatalytic reduction of CO₂ presents a promising strategy in addressing environmental and energy crisis.Significant progress has been achieved via CO₂ gas diffusion electrolysis,to react at high selectivity and high rate.However,the gas diffusion layer(GDL)of the gas diffusion electrode(GDE)still suffers from low tolerance and limited active sites.Here,the hydrophobic 1-octadecanethiol molecular was functionalized over the Cu catalyst layer of the GDE,which simultaneously stabilizes the GDL and exposes abundant active solid-liquid-gas three-phase interfaces.The resultant GDE exhibits multi-carbon(C₂₊)product selectivity over faradaic efficiency(FE)of 70.0%in the range of 100 to 800 mA·cm^-2,with the peak FE^c2+of 85.2%at 800 mA·cm^-2.Notably,the strengthened GDE could continuously drive high-current electrolysis for more than 100 h without flooding.This work opens a new way to improve CO₂ gas diffusion electrolysis via surface molecular engineering.     

High-Index Faceted Nanocrystals as Highly Efficient Bifunctional Electrocatalysts for High-Performance Lithium-Sulfur Batteries

Precisely regulating of the surface structure of crystalline materials to improve their catalytic activity for lithium polysulfides is urgently needed for high-performance lithium-sulfur(Li-S)batteries.Herein,high-index faceted iron oxide(Fe₂O₃)nanocrystals anchored on reduced graphene oxide are developed as highly efficient bifunctional electrocatalysts,effectively improving the electrochemical performance of Li-S batteries.The theoretical and experimental results all indicate that high-index Fe₂O₃crystal facets with abundant unsaturated coordinated Fe sites not only have strong adsorption capacity to anchor polysulfides but also have high catalytic activity to facilitate the redox transformation of polysulfides and reduce the decomposition energy barrier of Li₂S.The Li-S batteries with these bifunctional electrocatalysts exhibit high initial capacity of 1521 mAh g^-1at 0.1 C and excellent cycling performance with a low capacity fading of 0.025%per cycle during 1600 cycles at 2 C.Even with a high sulfur loading of 9.41 mg cm^-2,a remarkable areal capacity of 7.61 mAh cm^-2was maintained after 85 cycles.This work provides a new strategy to improve the catalytic activity of nanocrystals through the crystal facet engineering,deepening the comprehending of facet-dependent activity of catalysts in Li-S chemistry,affording a novel perspective for the design of advanced sulfur electrodes.     

Isolated ultrasmall Bi nanosheets for efficient CO2-to-formate electroreduction

Electrochemical reduction of CO₂ to valuable formate as liquid fuel is a promising way to alleviate the greenhouse effect.The edge active sites in bismuth(Bi)nanosheets play a critical role in the electrochemical reduction of CO₂ into formate,which enable the operation of CO₂ reduction with high cathodic energy efficiency,especially under large current densities of≥200 mA/cm².However,the undesirable reconstruction of small Bi nanosheets into large nanosheets leads to the decreasing of edge active sites during electrocatalysis.Here we report stable isolated ultrasmall bismuth nanosheets-synthesized by in-situ electrochemical transformation of ligands covered bismuth vanadate-on silver nanowires as an efficient electrocatalyst for CO₂-to-formate reduction.The cooperative electrocatalyst achieves a formate current density of 186 mA/cm² and a cathodic energy efficiency of 75%for formate,which is the only best compared to the literature results.Operand。Raman and morphologic measurements demonstrate that the excellent energy utilization of the electrocatalyst is originated from the rich edge active sites with Bi-O species of the ultrasmall Bi nanosheets.     

Electrolyte-mediated dense integration of graphene-MXene films for high volumetric capacitance flexible supercapacitors

High conductivity two-dimensional(2D)materials have been proved to be potential electrode materials for flexible supercapacitors because of its outstanding chemical and physical properties.However,electrodes based on 2D materials always suffer from limited electrolyte-accessible surface due to the restacking of the 2D sheets,hindering the full utilization of their surface area.In this regard,an electrolyte-mediated method is used to integrate dense structure reduced graphene oxide/MXene(RGM)-electrolyte composite films.In such composite films,reduced graphene oxide(RGO)and MXene sheets are controllable assembly in compact layered structure with electrolyte filled between the layers.The electrolyte layer between RGO and MXene sheets forms continuous ion transport channels in the composite films.Therefore,the RGM-electrolyte composite films can be used directly as self-supporting electrodes for supercapacitors without additional conductive agents and binders.As a result,the composite films demonstrate enhanced volumetric specific capacity,improved volumetric energy density and higher power density compared with both pure RGO electrode and porous composite electrode prepared by traditional methods.Specifically,when the mass ratio of MXene is 30%,the electrode delivers a volumetric specific capacity of 454.9 F·cm^?3 with a high energy density of 39.4 Wh·L^?1.More importantly,supercapacitors based on the composite films exhibit good flexibility electrochemical performance.The investigation provides a new approach to synthesize dense structure films based on 2D materials for application in high volumetric capacitance flexible supercapacitors.