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.

Peripheral octamethyl-substituted nickel(Ⅱ)-phthalocyanine-decorated carbon-nanotube electrodes for high-performance all-solid-state flexible symmetric supercapacitors

Construction of advanced electrode materials with unique performance for supercapacitors(SCs)is essential to achieving high implementation in the commercial market.Here,we report a novel peripheral octamethyl-substituted nickel(Ⅱ)phthalocyanine(Ni Me_(2)Pc)-based nanocomposite as the electrode material of all-solid-state SCs.The highly redox-active NiMe_(2)Pc/carboxylated carbon nanotube(CNTCOOH)dendritic nanocomposite provides rapid electron/electrolyte ion-transport pathways and exhibits excellent structural stability,resulting in high-capacity activity and impressive cycling stability.The composite prepared with the optimized weight ratio of Ni Me_(2)Pc:CNT-COOH(6:10)showed the highest specific capacitance of 330.5 F g^(-1)at 0.25 A g^(-1).The constructed NiMe_(2)Pc/CNT-COOH-based all-solid-state symmetric SC device showed excellent performance with a maximum energy density of 22.8 Wh kg^(-1)and outstanding cycling stability(111.6%retained after 35,000 cycles).Moreover,flexible carbon cloth significantly enhanced the energy density of the NiMe_(2)Pc/CNT-COOH all-solid-state symmetric device to 52.1 Wh kg^(-1)with 95.4%capacitance retention after 35,000 cycles,and it could be applied to highperformance flexible electronics applications.These findings provide a novel strategy to design phthalocyanine-based electrode materials for next-generation flexible SC devices.

Surface-engineered binder-free PEDOT shielded nickel magnesium selenide nanosheet arrays electrode for ultralong-life flexible quasi-solid-state hybrid supercapacitors

Together with the development of high-performance advanced electronics,flexible supercapacitors(SCs)with tailored nanostructures have great attraction.Electrochemically deposited nanosheet arrays of nickel magnesium selenide(NixMg3-xSe4,NMgS)with high capacitance provide high potentials as a positive electrode in flexible SCs.To further enhance their electrochemical properties and long-term cycling stability,a promising strategy of surface engineering with conducting polymer poly(3,4-ethylenedioxythiophene)(PEDOT)is proposed.The present work proposes the construction of PEDOT shielded NMgS(P@NMgS-2)on a flexible carbon cloth substrate via a hierarchical electrodeposition technique.Benefitting from the synergistic effect,the P@NMgS-2 exhibits an excellent areal capacitance value of 1440 mF cm^(-2)at 4 mA cm^(-2).A novel shape-adaptable polymer gel electrolyte-assisted flexible quasi-solid-state hybrid SC(FQHSC)device constructed with P@NMgS-2 as a positive electrode and activated carbon as a negative electrode demonstrates the maximum power and energy density values of 14.13 mW cm^(-2)and 0.18 mWh cm^(-2),respectively,followed by outstanding cycling stability(∼100%capacitance retention over 50,000 cycles).Furthermore,the FQHSC device successfully powered electronic devices with no serious degradation upon bending and twisting for wearable electronic applications.

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.

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.

Conducting polymer hydrogel materials for high-performance flexible solid-state supercapacitors

Different from solid electrodes, conducting polymer hydrogel electrodes swollen with water and ions,can reach contact with the electrolyte solution at the molecular level, which will result in more efficient electrochemical process of supercapacitors. Besides, the inherent soft nature of hydrogel material offers the electrode superior flexibility,which benefits to gain high flexibility for devices. Here, this perspective briefly introduces the current research progress in the field of conducting polymer hydrogel electrodes-based flexible solid-state supercapacitor and gives an outlook on the future trend of research.

Wet-spun poly(ionic liquid)-graphene hybrid fibers for high performance all-solid-state flexible supercapacitors

It is crucial to develop flexible and wearable electronic devices that have attracted tremendous interest due to their merits on compactness,flexibility and high capacitive properties.Herein we report the continuously ordered macroscopic poly(ionic liquid)-graphene fibers by wet spinning method via liquid crystal assembly for supercapacitor application.The fabricated all-solid-state supercapacitors exhibited a high areal capacitance(268.2 mF cm 2)and volumetric capacitance(204.6 F cm 3)with an outstanding areal energy density(9.31μWh cm-2)and volumetric energy density(8.28 mWh cm-3).The fiber supercapacitors demonstrated exceptional cycle life for straight electrodes of about 10,000 cycles(94.2%capacitance retention)and flexibility at different angles(0°,45°,90°,180°)along with a good flexible cycling stability after 6000 cycles(92.7%capacitance retention).To date,such a novel poly(ionic liquid)-graphene fiber supercapacitors would be a new platform in real-time flexible electronics.

All-solid-state flexible asymmetric supercapacitors with high energy and power densities based on NiCo_2S_4@MnS and active carbon

Electrode material based on a novel core–shell structure consisting of NiCoS（NCS） solid fiber core and Mn S（MS） sheet shell（NCS@MS） in situ grown on carbon cloth（CC） has been successfully prepared by a simple sulfurization-assisted hydrothermal method for high performance supercapacitor. The synthesized NiCoS@Mn S/CC electrode shows high capacitance of 1908.3 F gat a current density of 0.5 A gwhich is higher than those of NiCoSand Mn S at the same current density. A flexible all-solid-state asymmetric supercapacitor（ASC） is constructed by using NiCoS@Mn S/CC as positive electrode, active carbon/CC as negative electrode and KOH/poly（vinyl alcohol）(PVA) as electrolyte. The optimized ASC shows a maximum energy density of 23.3 Wh kgat 1 A g, a maximum power density of about7.5 kw kgat 10 A gand remarkable cycling stability. After 9000 cycles, the ASC still exhibited67.8% retention rate and largely unchanged charge/discharge curves. The excellent electrochemical properties are resulted from the novel core–shell structure of the NiCoS@Mn S/CC electrode, which possesses both high surface area for Faraday redox reaction and superior kinetics of charge transport. The NiCoS@Mn S/CC electrode shows a promising potential for energy storage applications in the future.

Low-cost and low-density carbonized facial tissue supported uniform NiCo_(2)S_(4)nanotubes for high capacity flexible solid-state supercapacitors

Recently,rapid development of intelligent wearable electronic equipment has triggered great needs for flexible and lightweight portable energy storage systems.Here,we demonstrate a low-cost($0.5 m^(-2))and low density carbonized facial tissue paper(FCP)for high-conductive NiCo_(2)S_(4)nanotubes assisted novel ultra-flexible solid-state supercapacitors(SSCs).The hydrothermal synthesized FCP-900@NiCo_(2)S_(4)electrodes in this paper only have a density of 5 mg cm^(-2)and show large specific capacitance of 3115 mF cm^(-2)at 2 mA cm^(-2).Based on the high performance of FCP-900@NiCo_(2)S_(4)electrodes,the as assembled SSCs can deliver an energy density of 1.2 mWh cm^(-3),high power density of 58.16 mW cm-3.It also shows great bending-state capacitive performance with high capacitance retention after 5000 cycles,providing a new opportunity for developing high-performance flexible wearable energy storage devices.

Carbon-Based Flexible and All-Solid-State Micro-supercapacitors Fabricated by Inkjet Printing with Enhanced Performance

By means of inkjet printing technique, flexible and all-solid-state micro-supercapacitors(MSCs) were fabricated with carbon-based hybrid ink composed of graphene oxide(GO,98.0vol.%) ink and commercial pen ink(2.0vol.%). A small amount of commercial pen ink was added to effectively reduce the agglomeration of theGO sheets during solvent evaporation and the following reduction processes in which the presence of graphite carbon nanoparticles served as nano-spacer to separate GO sheets. The printed device fabricated using the hybrid ink,combined with the binder-free microelectrodes and interdigital microelectrode configuration, exhibits nearly 780%enhancement in areal capacitance compared with that of pure GO ink. It also shows excellent flexibility and cycling stability with nearly 100% retention of the areal capacitance after 10,000 cycles. The all-solid-state device can be optionally connected in series or in parallel to meet the voltage and capacity requirements for a given application.This work demonstrates a promising future of the carbonbased hybrid ink for directly large-scale inkjet printing MSCs for disposable energy storage devices.

Configuration-dependent stretchable all-solid-state supercapacitors and hybrid supercapacitors

Given the rise in the popularity of wearable electronics that are able to deform into desirable configurations while maintaining electrochemical functionality,stretchable and flexible(hybrid)supercapacitors(SCs)have become increasingly of interest as innovative energy storage devices.Their outstanding power density,long lifetime with low capacitance loss,and appropriate energy density,in particular in hybrid cases make them ideal candidates for flexible electronics.The aim of this review paper is to provide an in-depth discussion of these stretchable and flexible SCs ranging from fabrication to electro-mechanical properties.This review paper begins with a short overview of the fundamentals of charge storage mechanisms and different types of multivalent metal-ion hybrid SCs.The research methods leading up to the current state of these stretchable and flexible SCs are then presented.This is followed by an in-depth presentation of the challenges associated with the fabrication methods for different configurations.Proposed novel strategies to maximize the elastic and electrochemical properties of stretchable/flexible or quasi-solid-state SCs are classified and the pros and cons associated with each are shown.The advances in mechanical properties and the expected advancements for the future of these SCs are discussed in the last section.

Recent progress in flexible Zn-ion hybrid supercapacitors: Fundamentals, fabrication designs, and applications

One of the most exciting new developments in energy storage technology is flexible Zn-ion hybrid supercapacitors(f-ZIHSCs),which combine the high energy of Zn-ion batteries with high-power supercapacitors to satisfy the needs of portable flexible electronics.However,the development of f-ZHSCs is still in its infancy,and there are numerous barriers to overcome before they can be widely implemented for practical applications.This review gives an up-to-date description of recent achievements and underlying concepts in energy storage mechanisms of f-ZIHSCs and emphasizes the critical role of cathode,anode,and electrolyte materials systems in speeding the prosperity of f-ZIHSCs.The innovative nanostructured-based cathode materials for f-ZIHSCs include carbon(e.g.,porous carbon,heteroatom-doped carbon,biomass-derived porous carbon,graphene,etc.),metal-oxides,MXenes,and metal/covalentorganic frameworks,and other materials(e.g.,activated carbon,phosphorene,etc.)are mainly focused.Afterward,the latest developments in flexible anode and electrolyte frameworks and impacts of electrolyte compositions on the electrochemical properties of f-ZIHSC are elaborated.Subsequently,the advancements based on fabrication designs,including quasi-solid-state,micro,fiber-shaped,and all climate-changed f-ZIHSCs,are discussed in detail.Lastly,a summary of current challenges and recommendations for the future progress of advanced f-ZIHSC are addressed.This review article is anticipated to further understand the viable strategies and achievable approaches for assembling high-performance f-ZIHSCs and boost the technical revolutions on cathode,anode,and electrolytes for f-ZIHSC devices.

NH_(3)‑Induced In Situ Etching Strategy Derived 3D‑Interconnected Porous MXene/Carbon Dots Films for High Performance Flexible Supercapacitors

2D MXene(Ti_(3)CNT_(x))has been considered as the most promising electrode material for flexible supercapacitors owing to its metallic conductivity,ultra-high capacitance,and excellent flexibility.However,it suffers from a severe restacking problem during the electrode fabrication process,limiting the ion transport kinetics and the accessibility of ions in the electrodes,especially in the direction normal to the electrode surface.Herein,we report a NH_(3)-induced in situ etching strategy to fabricate 3D-interconnected porous MXene/carbon dots(p-MC)films for high-performance flexible supercapacitor.The pre-intercalated carbon dots(CDs)first prevent the restacking of MXene to expose more inner electrochemical active sites.The partially decomposed CDs generate NH_(3)for in situ etching of MXene nanosheets toward 3D-interconnected p-MC films.Benefiting from the structural merits and the 3D-interconnected ionic transmission channels,p-MC film electrodes achieve excellent gravimetric capacitance(688.9 F g^(-1)at 2 A g^(-1))and superior rate capability.Moreover,the optimized p-MC electrode is assembled into an asymmetric solid-state flexible supercapacitor with high energy density and superior cycling stability,demonstrating the great promise of p-MC electrode for practical applications.

A flexible solid-state supercapacitor based on graphene/polyaniline paper electrodes

The direct coating of graphene sheets obtained by electrochemical exfoliation on commercial paper renders the preparation of highly conductive flexible paper substrate for subsequent deposition of polyaniline (PANi) nanorods via electrochemical polymerization. The deposit ion of PANi can be well-controlled by adjusting the electrochemical polymerization time, leading to the formation of PANi coated graphene paper (PANi-GP). The as-prepared electrode exhibited high areal capacitance of 176 mF cm^-2 in three-electrode system at a current density of 0.2 mA cm^-2 which is around 10 times larger than that of pris-tine graphene paper due to the pseudocapacitive behavior of PANi. In-situ Raman test was used to determine the molecular changes during redox process of PANi. More importantly, all-solid-state symmetric capacitor assembled with two PANi-GP electrodes in a polymer electrolyte delivered an areal capacitanee of 123 mF cm^-2, corresponding to an areal energy density of 17.1 μWh cm^-2 and an areal power density of 0.25 mW cm^-2. The symmetric capacitor held a capacitive retention of 74.8% after 500 bending tests from 0 to 120°, suggesting the good flexibility and mechanical stability. These results showed the great promising application in flexible energy-storage devices.

Flexible quasi-solid-state dual-ion asymmetric supercapacitor based on Ni（OH）2 and Nb2O5 nanosheet arrays

Increasing the energy density, power density as well as widening the operation voltage are essential to electrochemical capacitors to meet the practical energy demands. Herein, a novel flexible quasi-solid-state dual-ion asymmetric supercapacitor(ASC) with Ni(OH)2 and Nb2O5 nanosheets directly grown on stainless steel mesh is developed. In the dual-ion ASC, Nb2O5 negative and Ni(OH)2 positive electrodes react with Li+ and OH- respectively in alkaline gel electrolyte to store energy, which is quite different from conventional alkali metal ion SCs and alkaline SCs. The as-assembled flexible device has an extended working voltage of 1.7 V and delivers a capacity of 5.37 mAh cm-2, a maximum energy density and power density of 0.52 mWh cm-3 and 170 mW cm-3 , respectively. The device maintains around 60% capacity retention after long cycling up to 1000 cycles. Moreover, our device can light up a LED light efficiently upon fast charging. The proposed quasi-solid-state dual-ion ASC has potential applications in future portable electronics and flexible energy storage devices.

In-Situ Annealed Ti_(3)C_(2)T_(x) MXene Based All-Solid-State Flexible Zn-Ion Hybrid Micro Supercapacitor Array with Enhanced Stability

Zn-ion hybrid supercapacitors(SCs)are considered as promising energy storage owing to their high energy density compared to traditional SCs.How to realize the miniaturization,patterning,and flexibility of the Zn-ion SCs without affecting the electrochemical performances has special meanings for expanding their applications in wearable integrated electronics.Ti_(3)C_(2)T_(x) cathode with outstanding conductivity,unique lamellar structure and good mechanical flexibility has been demonstrated tremen-dous potential in the design of Zn-ion SCs,but achieving long cycling stability and high rate stability is still big challenges.Here,we proposed a facile laser writing approach to fabricate patterned Ti_(3)C_(2)T_(x)-based Zn-ion micro-supercapacitors(MSCs),followed by the in-situ anneal treatment of the assembled MSCs to improve the long-term stability,which exhibits 80%of the capacitance retention even after 50,000 charge/discharge cycles and superior rate stability.The influence of the cathode thickness on the electrochemical performance of the MSCs is also studied.When the thickness reaches 0.851μm the maximum areal capacitance of 72.02 mF cm^(−2)at scan rate of 10 mV s^(−1),which is 1.77 times higher than that with a thickness of 0.329μm(35.6 mF cm^(−2)).Moreover,the fab-ricated Ti_(3)C_(2)T_(x) based Zn-ion MSCs have excellent flexibility,a digital timer can be driven by the single device even under bending state,a flexible LED displayer of“TiC”logo also can be easily lighted by the MSC arrays under twisting,crimping,and winding conditions,demonstrating the scalable fabrication and application of the fabricated MSCs in portable electronics.

Flexible free-standing graphene-like film electrode for supercapacitors by electrophoretic deposition and electrochemical reduction

Electrophoretic deposition in conjunction with electrochemical reduction was used to make flexible free-standing graphene-like films. Firstly, graphene oxide （GO） film was deposited on graphite substrate by electrophoretic deposition method, and then reduced by subsequent electrochemical reduction of GO to obtain reduced GO （ERGO） film with high electrochemical performance. The morphology, structure and electrochemical performance of the prepared graphene-like film were confirmed by SEM, XRD and FT-IR. These unique materials were found to provide high specific capacitance and good cycling stability. The high specific capacitance of 254 F/g was obtained from cyclic voltammetry measurement at a scan rate of 10 mV/s. When the current density increased to 83.3 A/g, the specific capacitance values still remained 132 F/g. Meanwhile, the high powder density of 39.1 kW/kg was measured at energy density of 11.8 W-h/kg in 1 mol/L H2SO4 solution. Furthermore, at a constant scan rate of 50 mV/s, 97.02% of its capacitance was retained for 1000 cycles. These promising results were attributed to the unique assembly structure of graphene film and low contact resistance, which indicated their potential application to electrochemical capacitors.

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.

Graphene-Polymer Nanocomposites and Roll-to-Roll (R2R) Compatible Flexible Solid-State Supercapacitor Based on Graphene Nanoplatelets and Ionic Liquid-Polymer Gel

We present the electrical and supercapacitive performance of graphene nanoplatelets in polymer nanocomposites and flexible solid state electrical double layer capacitors (EDLC) respectively. Graphene-doped poly (3,4-ethylenedioxythiophene) (PEDOT) coated polyethylene terephthalate (PET) and glass exhibited transmittance above 95% and electrical conductivity of 2.70 × 10ˉ1 S·cmˉ1 and 9.01 × 10ˉ1 S·cmˉ1 respectively. Graphene loaded polymethyl methacrylate (PMMA) and polystyrene (PS) nanocomposites showed electrical conductivity as high as 2.11 × 10ˉ1 S·cmˉ1 at low loadings of 2 wt%. The use of graphene was necessitated by the need to increase the EDLC capacitance and energy density since it provides high effective surface area. The polymer gel membrane made from polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP) and the Ionic Liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate exhibited high porosity which made it suitable for use as separator in the EDLC. The highest recorded specific capacitance was 133.82 F/g which can be attributed to the porosity of the IL containing PVDF-co-HFP membrane and the large surface area of the graphene electrodes. At an operating voltage of 3.5 V the energy density was found to be 56.92 Wh·Kgˉ1. All chemicals were research grade and were obtained from Sigma Aldrich.

Preparation of vanadium-based electrode materials and their research progress in solid-state flexible supercapacitors

Solid-state flexible supercapacitors(SCs)have many advantages of high specific capacitance,excellent flexibility,fast charging and discharging,high power density,environmental friendliness,high safety,light weight,ductility,and long cycle stability.They are the ideal choice for the development of flexible energy storage technology in the future,and provide a good prospect for energy storage applications.At present,solid-state flexible SCs are widely used for portable electronic equipment and wearable energy storage equipment,the research of them has become the focus of a growing number of researchers.Electrode material is the key part of SCs and always determines the electrochemical performance of SCs.It has been a hotspot and focus of research.Vanadium-based compounds are considered to be a promising electrode material for SCs because of variable valence,open structure,high theoretical capacity,and low price.Therefore,this study first gives an overview of solid-state flexible SCs,then reviews the current research status of vanadium-based electrode materials in solid-state flexible SCs,and proposes some strategies to solve some problems of vanadium-based electrode materials.