Porous Graphene-Based Electrodes for Fiber-Shaped Supercapacitors with Good Electrical Conductivity

Graphene fibers(GFs)are ideal electrodes for f ibrous supercapacitors because of their excellent mechanical and electrical properties.However,the actual specific s urface area(SSA)of GFs is low due to the restacking of g raphene sheets,which limits the capacitance enhancement o f GFs.One of the effective ways to increase the SSA of GFs is to construct a porous fiber structure,but it disrupts t he conductive pathway and adversely affects the electrochemical(EC)performance of GFs.Therefore,a wet-spun porous GF electrode coated with polypyrrole(PPy)was reported in this paper.The resulting electrode exhibits an areal specific capacitance of 31.25 mF·cm^(-2)and a good c ycling stability with a capacitance retention rate of 95%after 5000 charge/discharge cycles.These indicate that porous structures and PPy coating can synergistically improve the EC performance of GFs.

Polyacrylonitrile/Graphene-Based Coaxial Fiber-Shaped Supercapacitors

Supercapacitors have huge potential applications in the field of wearable electronic devices,such as flexible displays,flexible biosensors and implantable multimedia devices,due to their high-power density,fast charge-discharge rates,long cycling life,and relatively simple configuration.In this paper,we demonstrated hierarchically porous and continuous reduced graphene oxide-polyacrylonitrile@polyacrylonitrile(rGO-PAN@PAN)coaxial fibers with certain strength,excellent electrochemical performance through coaxial wet spinning and thermal reduction.Coaxial fibers are carbonized at high temperature and have a graded porous structure with a conductivity of 1703 S/m.The areal specific capacitance of the supercapacitor assembled by polyvinyl alcohol/sulfuric acid(PVA/H_(2)SO_(4))gel electrolyte is 11.56 mF/cm^(2),and its energy density reaches 0.21 mW·h/cm3,showing good electrochemical performance.Graphene-based coaxial fibers prepared by wet spinning have a great prospect of application in electronic devices due to their excellent properties.

Fiber-shaped Supercapacitors:Advanced Strategies toward High-performances and Multi-functions

Fiber-shaped supercapacitors(FSSCs)show great potential in portable and wearable electronics due to their unique advantages of high safety,environmental friendliness,high performances,outstanding flexibility and integrability.They can directly act as the power sources or be easily integrated with other flexible devices to constitute self-powered and sustainable energy suppliers,providing excellent adaptability to irregular surfaces.This review mainly summarizes the recently reported works of FSSCs including preparation methods of various fiber electrodes,construction strategies of FSSCs and multi-functional device integrations,exploration of reaction mechanisms and strategies to improve the electrochemical performance and provision of suggestions on further designing and optimization of FSSCs.Meanwhile,it shares our perspectives on challenges and opportunities in this field,shedding light on the development of high-performance fiber-shaped supercapacitors with multifunctions.

Flexible fiber-shaped supercapacitors based on hierarchically nanostructured composite electrodes

A novel all-solid-state, coaxial, fiber-shaped asymmetric supercapacitor has been fabricated by wrapping a conducting carbon paper on a MnO2-modified nanoporous gold wire. This energy wire exhibits high capacitance of 12 mF.cm^-2 and energy density of 5.4 μW.h.cm^-2 with excellent cycling stability. Hierarchical nanostructures and coaxial architectural design facilitate effective contacts between the two core@sheath electrodes and active layers with high flexibility and high performance. This work provides the first example of coaxial fiber- shaped asymmetric supercapacitors with an operation voltage of 1.8 V, and holds great potential for future flexible electronic devices.

A stretchable,asymmetric,coaxial fiber-shaped supercapacitor for wearable electronics

Nano Research volume 13,pages1686–1692(2020)Cite this article 210 Accesses 1 Citations Metrics details Abstract Fiber-shaped supercapacitors(FSCs),owing to their high-power density and feasibility to be integrated into woven clothes,have drawn tremendous attentions as a key device for flexible energy storage.However,how to store more energy while withstanding various types of mechanical deformation is still a challenge for FSCs.Here,based on a magnetron sputtering method,different pseudocapacitive materials are conformally coated on self-supported carbon nanotube aligned films.This fabrication approach enables a stretchable,asymmetric,coaxial fiber-shaped supercapacitors with high performance.The asymmetric electrode configuration that consists of CNT@NiO@MnOx cathode and CNT@Fe2O3 anode successfully extends the FSC’s electrochemical window to 1.8 V in an aqueous electrolyte.As a result,a high specific capacitance of 10.4 F·cm^−3 is achieved at a current density of 30 mA·cm^−3 corresponding to a high energy density of 4.7 mWh·cm^−3.The mechanical stability of the stretchable FSC is demonstrated with a sustainable performance under strains up to 75%and a capacitance retention of 95%after 2,000 cycles under 75%strain.

Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan

With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required.However,the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan.It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors.Using'water in salt'electrolytes can effectively broaden their electrochemical windows,but this is at the expense of high cost,low ionic conductivity,and narrow temperature compatibility,compromising the electrochemical performance of the Zn-ion hybrid supercapacitors.Thus,designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary.We developed a dilute water/acetonitrile electrolyte(0.5 m Zn(CF_(3)SO_(3))_(2)+1 m LiTFSI-H_(2)O/AN)for Zn-ion hybrid supercapacitors,which simultaneously exhibited expanded electrochemical window,decent ionic conductivity,and broad temperature compatibility.In this electrolyte,the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI-anions.As a result,a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.

Cotton pads-derived carbon materials/reduced graphene oxide modified with polypyrrole for electrode of supercapacitors

This study investigates the influence of electropolymerization conditions on the deposition of polypyrrole(PPy)onto cotton-derived carbon fiber(CF)modified with reduced graphene oxide(rGO)for supercapacitors applications using an experimental/theorical approach.The surface modification of CF by rGO and/or by PPy electrodeposited at 10,25 and 50 mV s^(-1) was thoroughly examined physicochemical and electrochemically.Composite electrodes comprising CF-rGo-PPy,synthesized via electropolymerization at 25 mV s^(-1),demonstrated a remarkable increase in capacitance,showcasing~742 F g^(-1) compared to 153 F g^(-1) for CF.SEM,N_(2)-surface area,XPS,and TD-DFT approach revealed that the higher capacitance observed in CF-rGo-PPy electrodes underscores the influence of morphology and charged nitrogen species on the electrochemical performance of these modified electrodes.Notably,this electrode material achieves a specific capacitance retention of~96%of their initial capacitance after 10000 cycles at 0.5 A g^(-1) measured in a two-electrodes cell configuration.This work also discusses the influence of the scan rate used for pyrrole electropolymerization on the pseudocapacitance contribution of PPy and its possible effect on the porosity of the material.These results highlight the importance of appropriate electropolymerization conditions that allow obtaining the synergistic effect between CF,rGO and PPy.

Recent Research Progress of Paper-Based Supercapacitors Based on Cellulose

In recent years,paper-based functional materials have received extensive attention in the field of energy storage due to their advantages of rich and adjustable porous network structure and good flexibility.As an important energy storage device,paper-based supercapacitors have important application prospects in many fields and have also received extensive attention from researchers in recent years.At present,researchers have modified and regulated paper-based materials by different means such as structural design and material composition to enhance their electrochemical storage capacity.The development of paper-based supercapacitors provides an important direction for the development of green and sustainable energy.Therefore,it is of great significance to summarize the relevant work of paper-based supercapacitors for their rapid development and application.In this review,the recent research progress of paper-based supercapacitors based on cellulose was summarized in terms of various cellulose-based composites,preparation skills,and electrochemical performance.Finally,some opinions on the problems in the development of this field and the future development trend were proposed.It is hoped that this review can provide valuable references and ideas for the rapid development of paper-based energy storage devices.

An effective'salt in dimethyl sulfoxide/water'electrolyte enables high-voltage supercapacitor operated at-50℃

Compared with organic electrolytes,aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features,showcasing unique advantages in supercapacitors.However,challenges remain for low-salt aqueous electrolytes operating at high voltage and low temperature.Herein,we report a low-salt(0.87 m,m means mol kg^(-1))'salt in dimethyl sulfoxide/water'hybrid electrolyte with non-flammability via hybridizing aqueous electrolyte with an organic co-solvent of dimethyl sulfoxide(hydrogen bond acceptor).As a result,the 0.87 m hybrid electrolyte exhibits enhanced electrochemical stability,a freezing temperature below-50℃,and an outstanding ionic conductivity of 0.52mS cm~(-1)at-50℃.Dimethyl sulfoxide can anchor water molecules through intermolecular hydrogen bond interaction,effectively reinforcing the stability of water in the hybrid electrolyte.Furthermore,the interaction between dimethyl sulfoxide and water molecules diminishes the involvement of water in the generation of ordered ice crystals,finally facilitating the low-temperature performance of the hybrid electrolyte.When paired with the 0.87 m'salt in dimethyl sulfoxide/water'hybrid electrolyte,the symmetric supercapacitor presents a 2.0 V high operating voltage at 25℃,and can operate stably at-50℃.Importantly,the suppressed electrochemical reaction of water at-50℃further leads to the symmetric supercapacitor operated at a higher voltage of 2.6 V.This modification strategy opens an effective avenue to develop low-salt electrolytes for high-voltage and low-temperature aqueous supercapacitors.

Ti_(3)C_(2)T_(x) MXene/carbon composites for advanced supercapacitors:Synthesis,progress,and perspectives

MXenes are a family of two-dimensional(2D)layered transition metal carbides/nitrides that show promising potential for energy storage applications due to their high-specific surface areas,excellent electron conductivity,good hydrophilicity,and tunable terminations.Among various types of MXenes,Ti_(3)C_(2)T_(x) is the most widely studied for use in capacitive energy storage applications,especially in supercapacitors(SCs).However,the stacking and oxidation of MXene sheets inevitably lead to a significant loss of electrochemically active sites.To overcome such challenges,carbon materials are frequently incorporated into MXenes to enhance their electrochemical properties.This review introduces the common strategies used for synthesizing Ti_(3)C_(2)T_(x),followed by a comprehensive overview of recent developments in Ti_(3)C_(2)T_(x)/carbon composites as electrode materials for SCs.Ti_(3)C_(2)T_(x)/carbon composites are categorized based on the dimensions of carbons,including 0D carbon dots,1D carbon nanotubes and fibers,2D graphene,and 3D carbon materials(activated carbon,polymer-derived carbon,etc.).Finally,this review also provides a perspective on developing novel MXenes/carbon composites as electrodes for application in SCs.

Mechanical reliable,NIR light-induced rapid self-healing hydrogel electrolyte towards flexible zinc-ion hybrid supercapacitors with low-temperature adaptability and long service life

Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Ultraconformable Integrated Wireless Charging Micro-Supercapacitor Skin

Conformable and wire-less charging energy storage devices play important roles in enabling the fast development of wearable,non-contact soft electronics.However,current wire-less charging power sources are still restricted by limited flexural angles and fragile connection of components,resulting in the failure expression of performance and constraining their fur-ther applications in health monitoring wearables and moveable artificial limbs.Herein,we present an ultracompatible skin-like integrated wireless charging micro-supercapacitor,which building blocks(including electrolyte,electrode and substrate)are all evaporated by liquid precursor.Owing to the infiltration and permeation of the liquid,each part of the integrated device attached firmly with each other,forming a compact and all-in-one configuration.In addition,benefitting from the controllable volume of electrode solution precursor,the electrode thickness is easily regulated varying from 11.7 to 112.5μm.This prepared thin IWC-MSC skin can fit well with curving human body,and could be wireless charged to store electricity into high capacitive micro-supercapacitors(11.39 F cm-3)of the integrated device.We believe this work will shed light on the construction of skin-attachable electronics and irregular sensing microrobots.

Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and supercapacitors.To increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently required.The present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction process.The following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel cells.In turn,the numerical validation has demonstrated the powerful function of the joint time–frequency analysis.The thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

Room Temperature Synthesis of Vertically Aligned Amorphous Ultrathin NiCo-LDH Nanosheets Bifunctional Flexible Supercapacitor Electrodes

Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets vertically aligned on activated carbon cloth substrate,which was in situ transformed from Co-metal-organic framework materials nano-columns by a simple ion exchange process at room temperature.Due to the amorphous and vertically aligned ultrathin structure of NiCo-LDH,the NiCo-LDH/activated carbon cloth composites present high areal capacities of 3770 and 1480 mF cm^(-2)as cathode and anode at 2 mA cm^(-2),and 79.5%and 80%capacity have been preserved at 50 mA cm^(-2).In the meantime,they all showed excellent cycling performance with negligible change after>10000 cycles.By fabricating them into an asymmetric supercapacitor,the device achieves high energy densities(5.61 mWh cm^(-2)and 0.352 mW cm^(-3)).This work provides an innovative strategy for simplifying the design of supercapacitors as well as providing a new understanding of improving the rate capabilities/cycling stability of NiCo-LDH materials.

Preparation by Wet-spinning and Properties Polyaniline-Polyethersulfone Fibers for Flexible Supercapacitor Electrodes

Flexible PANI-Polyethersulfone (PES) fibers were fabricated using the wet-spinning technique.PANI particles were uniformly distributed within the matrix and micropores formed by the phase separation of PES,which prevented PANI particles aggregation and facilitated the formation of continuous ion transport channels.The experimental results reveals that the electrochemical performance of the fiber electrode material is optimal when the concentration of PES in the spinning solution is 15wt%.The assembled supercapacitor exhibits a commendable specific area capacitance of 162.75 mF·cm^(-2) at a current density of 0.5 mA·cm^(-2) and achieves an energy density of 14.47 mWh·cm^(-2) at a power density of 321.69 mW·cm^(-2).The capacitor retains 98.1% of its capacitance after 1 000 bending cycles.Therefore,the prepared fibers have good electrochemical properties and flexibility,and this simple and efficient preparation method is promising for the scalable production of flexible electrodes.

One-Step Scalable Fabrication of Nitrogen and Chlorine Co-doped Graphene by Electrochemical Exfoliation for High-Performance Supercapacitors

The stacking and aggregation of graphene nanosheets have been obstacles to their application as electrode materials for microelectronic devices.This study deploys a one-step,scalable,facile electrochemical exfoliation technique to fabricate nitrogen(N)and chlorine(Cl)co-doped graphene nanosheets(i.e.,N-Cl-G)via the application of constant voltage on graphite in a mixture of 0.1 mol/L H_(2)SO_(4)and 0.1 mol/L NH_(4)Cl without using dangerous and exhaustive operation.The introduction of Cl(with its large radius)and N,both with high electrical negativity,facilitates the modulation of the electronic structure of graphene and creation of rich structural defects in it.Consequently,in the as-constructed supercapacitors,N-Cl-G exhibits a high specific capacitance of 77 F/g at 0.2 A/g and remarkable cycling stability with 91.7%retention of initial capacitance after 20,000 cycles at 10 A/g.Furthermore,a symmetrical supercapacitor assembled with N-Cl-G as the positive and negative electrodes(denoted as N-Cl-G//N-Cl-G)exhibits an energy density of 3.38 Wh/kg at a power density of 600 W/kg and superior cycling stability with almost no capacitance loss after 5000 cycles at 5 A/g.This study provides a scalable protocol for the facile fabrication of high-performance co-doped graphene as an electrode material candidate for supercapacitors.

Flexible planar micro supercapacitor diode

Supercapacitor diode is a novel ion device that performs both supercapacitor energy storage and ion diode rectification functions.However,previously reported devices are limited by their large size and complex processes.In this work,we demonstrate a screen-printed micro supercapacitor diode(MCAPode)that based on the insertion of a finger mode with spinel ZnCo_(2)O_(4) as cathode and activated carbon as anode for the first time,and featuring an excellent area specific capacitance(1.21 mF cm^(-2)at 10 mV s^(-1))and high rectification characteristics(rectification ratioⅠof 11.99 at 40 mV s^(-1)).Taking advantage of the ionic gel electrolyte,which provides excellent stability during repeated flexing and at high temperatures.In addition,MCAPode exhibits excellent electrochemical performance and rectification capability in"AND"and"OR"logic gates.These findings provide practical solutions for future expansion of micro supercapacitor diode applications.

In-depth analysis of VARTM-based solid-state supercapacitors utilizing CNT-dispersed cobalt-bismuth-samarium ternary hydroxide on woven carbon fiber for enhanced energy storage

Multi-metal hydroxides possess unique physical and chemical properties,making them promising candidates for supercapacitor working electrodes.Enhancing their electrochemical performance can be achieved through a combination with carbon materials.In this study,we synthesized a composite material by hydrothermally dispersed 4,6,and 10 wt%carbon nanotubes(CNT)into ternary cobaltbismuth-samarium hydroxide(CoBiSm-TOH).These nanocomposites were employed as the material for the working electrode in a supercapacitor.The findings reveal that at 1.5 A/g,the specific capacitance of CNT3@CoBiSm-TOH,using a three-electrode system,was found to be 852.91 F/g,higher than that of CoBi-BOH,CoBiSm-TOH,CNT1@CoBiSm-TOH and CNT5@CoBiSm-TOH-measuring 699.69,750.34,789.54 and 817.79 F/g,respectively.Moreover,CNT3@CoBiSm-TOH electrodes exhibited a capacitance retention of around 88%over 10,000 cycles.To demonstrate practical applicability,CNT3@CoBiSm-TOH was grown on woven carbon fiber(WCF),and a solid-state supercapacitor device was developed using the VARTM(vacuum-assisted resin transfer molding).This device displayed a specific capacitance of 272.67 F/g at 2.25 A/g.Notably,it achieved a maximum energy density of 53.01 Wh/kg at a power density of 750 W/kg and sustained excellent cycle stability over 50,000 cycles,maintaining 70%of its initial capacitance.These results underscore the importance of interfacial nanoengineering and provide crucial insights for the development of future energy storage devices.

Design strategies and recent advancements of solid-state supercapacitor operating in wide temperature range

Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues under extreme conditions are the main challenges for the practical application.With the expansion of human activities,such as space missions,polar exploration,and so on,the investigation of SSC with wide temperature tolerance,high energy density,power density,and sustainability is highly desired.In this review,the effects of temperature on SSC are systematically illustrated and clarified,including the properties of the electrolyte,ion diffusion,and reaction dynamics of the supercapacitor.Subsequently,we summarize the recent advances in wide-temperature-range SSCs from the aspect of electrolyte modification,electrode design,and interface adjustment between electrode and electrolyte,especially with critical concerns on ionic conductivity and cycling stability.In the end,a perspective is presented,expecting to promote the practical application of the SSC in harsh conditions.