Recent progress of self-supported air electrodes for flexible Zn-air batteries

Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among them,flexible solid-state zinc-air batteries have received widespread attention because of their high energy density,good safety,and stability.Efficient bifunctional oxygen electrocatalysts are the primary consideration in the development of flexible solid-state zinc-air batteries,and self-supported air cathodes are strong candidates because of their advantages including simplified fabrication process,reduced interfacial resistance,accelerated electron transfer,and good flexibility.This review outlines the research progress in the design and construction of nanoarray bifunctional oxygen electrocatalysts.Starting from the configuration and basic principles of zinc-air batteries and the strategies for the design of bifunctional oxygen electrocatalysts,a detailed discussion of self-supported air cathodes on carbon and metal substrates and their uses in flexible zinc-air batteries will follow.Finally,the challenges and opportunities in the development of flexible zinc-air batteries will be discussed.

Heteroatom anchors Fe-Mn dual-atom catalysts with bi-functional oxygen catalytic activity for low-temperature rechargeable flexible Zn-air batteries

M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.

Recent advances in flexible batteries:From materials to applications

Along with the rapid development of flexible and wearable electronic devices,there have been a strong demand for flexible power sources,which has in turn triggered considerable efforts on the research and development of flexible batteries.An ideal flexible battery would have not only just high electrochemical performance but also excellent mechanical deformabilities.Therefore,battery constituent components,chemistry systems,device configurations,and practical applications are all pivotal aspects that should be thoroughly considered.Herein,we systematically and comprehensively review the fundamentals and recent progresses of flexible batteries in terms of these important aspects.Specifically,we first discuss the requirements for constituent components,including the current collector,electrolyte,and separator,in flexible batteries.We then elucidate battery chemistry systems that have been studied for various flexible batteries,including lithium-ion batteries,non-lithium-ion batteries,and high-energy metal batteries.This is followed by discussions on the device configurations for flexible batteries,including onedimensional fiber-shaped,two-dimensional film-shaped,and three-dimensional structural batteries.Finally,we summarize recent efforts in exploring practical applications for flexible batteries.Current challenges and future opportunities for the research and development of flexible batteries are also discussed.

Self-supported metal(Fe, Co, Ni)-embedded nitrogen-doping carbon nanorod framework as trifunctional electrode for flexible Zn-air batteries and switchable water electrolysis

To meet the practical demand of wearable/portable electronics, developing high-efficiency and durable multifunctional catalyst and in-situ assembling catalysts into electrodes with flexible features are urgently needed but challenging. Herein, we report a simple route to fabricate bendable multifunctional electrodes by in-situ carbonization of metal ion absorbed polyaniline precursor. Alloy nanoparticles encapsulated in graphite layer are uniformly distributed in the N-doping carbon nanorod skeleton. Profiting from the favorable free-standing structure and the cooperative effect of metallic nanoparticles, graphitic layer and N doped-carbon architecture, the trifunctional electrodes exhibit prominent activities and stability toward HER, OER and ORR. Notably, due to the protection of carbon layer, the electrocatalysts show the reversible catalytic HER/OER properties. The overall water splitting device can continuously work for 12 h under frequent exchanges of cathode and anode. Importantly, the bendable metal air batteries fabricated by self-supported electrode not only displays the outstanding battery performance,achieving a decent peak power density(125 mW cm^(-2)) and exhibiting favorable charge-discharge durability of 22 h, but also holds superb flexible stability. Specially, a lightweight self-driven water splitting unit is demonstrated with stable hydrogen production.

A review on system and materials for aqueous flexible metal-air batteries

The exploration of aqueous flexible metal-air batteries with high energy density and durability has attracted many research efforts with the demand for portable and wearable electronic devices.Aqueous flexible metal-air batteries feature Earth-abundant materials,environmental friendliness,and operational safety.Each part of one metal-air battery can significantly affect the overall performance.This review starts with the fundamental working principles and the basic battery configurations and then highlights on the common issues and the recent advances in designing high-performance metal electrodes,solid-state electrolytes,and air electrodes.Bifunctional oxygen electrocatalysts with high activity and long-term stability for constructing efficient air electrodes in flexible metal-air batteries are summarized including metal-free carbon-based materials and nonprecious Co/Fe-based materials(alloys,metal oxides,metal sulfites,metal phosphates,metal nitrates,single-site metal-nitrogen-carbon materials,and composites).Finally,a perspective is provided on the existing challenges and possible future research directions in optimizing the performance and lifetime of the flexible aqueous solid-state metal-air batteries.

Aerophilic Triphase Interface Tuned by Carbon Dots Driving Durable and Flexible Rechargeable Zn‑Air Batteries

Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy.The aerophilic triphase interface of Co@C–O–Cs cathode efficiently boosts oxygen diffusion and transfer.The theoretical calculations and experimental studies revealed that the Co–C–COC active sites can redistribute the local charge density and lower the reaction energy barrier.The Co@C–O–Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm^(−2) for OER.Moreover,it can drive the liquid ZABs with high peak power density(106.4 mW cm^(−2)),specific capacity(720.7 mAh g^(−1)),outstanding long-term cycle stability(over 750 cycles at 10 mA cm^(−2)),and exhibits excellent feasibility in flexible all-solid-state ZABs.These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.

Pushing the Limit of Flexible Batteries

Alongside the rapid development of flexible and wearable electronics,the search for reliable,safe,and high-energy rechargeable flexible batteries(FBs)has become a research hotspot in recent years.Although there are some prototype FBs exhibited by the industry and a rapidly increasing number of publications reported by academia,most demonstrations are shown on a laboratory scale,and it is still difficult to find real implementation of the technology in the market.This perspective aims to discuss and analyze the key metrics,including energy density,flexibility,and safety,that are critical to pushing FBs to a commercially viable level,with a special focus on the lithium batteries and zinc batteries most reported in the literature.We first compare the figure of merit of FBs(fbFOM)of existing lithium-based and zinc-based FBs with the requirement for market applications.We then analyze the most desired cell configurations toward high flexibility,followed by systematic discussions on features and materials selection toward high energy density FBs.Third,we discuss strategies to enhance battery safety.An outlook of the future developments needed to address the gaps between the state-of-the-art demonstrations and real applications is provided at the end of this article.

Affinity-Engineered Flexible Scaffold toward Energy-Dense, Highly Reversible Na Metal Batteries

The practical deployment of metallic anodes in the energy-dense batteries is impeded by the thermodynamically unstable interphase in contact with the aprotic electrolyte,structural collapse of the substrates as well as their insufficient affinity toward the metallic deposits.Herein,the mechanical flexible,lightweight(1.2 mg cm^(−2))carbon nanofiber scaffold with the monodispersed,ultrafine Sn_(4)P_(3) nanoparticles encapsulation(Sn_(4)P_(3)NPs@CNF)is proposed as the deposition substrate toward the high-areal-capacity sodium loadings up to 4 mAh cm^(−2).First-principles calculations manifest that the alloy intermediates,namely the Na_(15)Sn_(4) and Na_(3)P matrix,exhibit the intimate Na affinity as the“sodiophilic”sites.Meanwhile,the porous CNF regulates the heterogeneous alloying process and confines the deposit propagation along the nanofiber orientation.With the precise control of pairing mode with the NaVPO4F cathode(8.7 mg cm^(−2)),the practical feasibility of the Sn_(4)P_(3) NPs@CNF anode(1^(*)Na excess)is demonstrated in 2 mAh single-layer pouch cell prototype,which achieves the 95.7%capacity retention for 150 cycles at various mechanical flexing states as well as balanced energy/power densities.

A Pore-Forming Strategy Toward Porous Carbon-Based Substrates for High Performance Flexible Lithium Metal Full Batteries

Self-standing carbon-based substrates with satisfied structural stability and property adjustability have promising applications in flexible lithium(Li)metal batteries(FLMBs).Current strategies for modifying carbon materials are normally carried out on powder carbon,and very few of them are suitable for self-standing carbon substrates.Herein,a pore-forming strategy based on the redox chemistry of metallic oxide nanodots is developed to prepare two porous carbon substrates for anode and cathode.Starting with cotton cloth,the resulting hollow carbon fibers substrate with nanopores effectively prevents from Li dendrites formation and large volume change in lithium metal anode(LMA).Simulations indicate that the porous structure leads to homogeneous ion flux,Li-ion concentration,and electric field during Li deposition.Li symmetrical cell based on this substrate remains stable for 8300 h with an ultralow voltage hysteresis of 9 mV.Via a similar route,porous carbon cloth substrate is obtained for subsequently seeding V_(2)O_(5)nanowires to prepare the cathode.The assembled FLMBs pouch cell delivers a capacity of 8.2 mAh with a high capacity retention of~100%even under dramatic deformation.The demonstrated strategy has far-reaching potential in preparing free-standing porous carbon-based materials for flexible energy storage devices.

An intrinsically self-healing and anti-freezing molecular chains induced polyacrylamide-based hydrogel electrolytes for zinc manganese dioxide batteries

The anti-freezing strategy of hydrogels and their self-healing structure are often contradictory,it is vital to break through the molecular structure to design and construct hydrogels with intrinsic anti-freezing/self-healing for meeting the rapid development of flexible and wearable devices in diverse service conditions.Herein,we design a new hydrogel electrolyte(AF/SH-Hydrogel)with intrinsic anti-freezing/self-healing capabilities by introducing ethylene glycol molecules,dynamic chemical bonding(disulfide bond),and supramolecular interaction(multi-hydrogen bond)into the polyacrylamide molecular chain.Thanks to the exceptional freeze resistance(84%capacity retention at-20℃)and intrinsic self-healing capabilities(95%capacity retention after 5 cutting/self-healing cycles),the obtained AF/SH-Hydrogel makes the zinc||manganese dioxide cell an economically feasible battery for the state-of-the-art applications.The Zn||AF/SH-Hydrogel||MnO_(2)device offers a near-theoretical specific capacity of 285 m A h g^(-1)at 0.1 A g^(-1)(Coulombic efficiency≈100%),as well as good self-healing capability and mechanical flexibility in an ice bath.This work provides insight that can be utilized to develop multifunctional hydrogel electrolytes for application in next generation of self-healable and freeze-resistance smart aqueous energy storage devices.

Flexible MXene films for batteries and beyond

MXenes add dozens of metallic conductors to the family of two-dimensional(2D)materials.A top-down synthesis approach removing A-layer atoms(e.g.,Al,Si,and Ga)in MAX phases to produce 2D flakes attaches various surface terminations to MXenes.With these terminations,MXenes show tunable properties,promising a range of applications from energy storage devices to electronics,including sensors,transistors,and antennas.MXenes are also excellent building blocks to create flexible films used for flexible and wearable devices.This article summarizes the synthesis of MXene flakes and highlights aspects that need attention for flexible devices.Rather than listing the development of energy storage devices in detail,we focus on the main challenges of and solutions for constructing high-performance devices.Moreover,we show the applications of MXene films in electronics to call on designs to construct a complete system based on MXene with good flexibility,which consists of a power source,sensors,transistors,and wireless communications.

Recent progress in graphene-based electrodes for flexible batteries

The emerging flexible electronic devices have stimulated the development of flexible batteries,in which flexible electrodes are indispensable components.Graphene,known for its excellent electrical conductivity and mechanical stability,can be used as an ideal flexible substrate.Recently,many efforts have been devoted to graphene-based electrodes for flexible batteries.Herein,this review summarizes recent advances in the development of graphene-based electrodes for various flexible batteries,including metal-ion batteries(ions of Li,Na,Zn,Al,etc.),lithiumsulfur batteries,and metal-air batteries(Li-and Zn-air batteries).Besides,major challenges and future developments of flexible batteries are also discussed.

Advanced energy materials for flexible batteries in energy storage:A review

Smart energy storage has revolutionized portable electronics and electrical vehicles.The current smart energy storage devices have penetrated into flexible electronic markets at an unprecedented rate.Flexible batteries are key power sources to enable vast flexible devices,which put forward additional requirements,such as bendable,twistable,stretchable,and ultrathin,to adapt mechanical deformation under the working conditions.This review summarizes the recent advances in construction and configuration of flexible batteries and discusses the general metrics to benchmark various flexible batteries with different materials and chemistries.Moreover,we present advanced prototype flexible batteries developed by some companies to afford general envision of the technological status.Lastly,the critical points are summarized in the development of flexible batteries and remaining challenges are also presented for the future design of flexible batteries in practical perspectives.

Tab engineering-mediated resistance of flexible lithium-ion batteries for high output current

Flexible lithium-ion batteries(LIBs) have received tremendous interest because they can provide essential flexible power for the emerging wearable electronics.However,the realization of the flexibility of LIBs is often related to flexible substrates with high electrical resistance,which results in voltage loss of the battery and is unfavorable for their practical applications.In this work,we demonstrated the use of tab engineering to mediate the resistance of flexible batteries for high current output.The resistance of the obtained pouch cell can be decreased sharply and the output current can be significantly increased by a continuous tab with desirable power and energy density.The surprising performance of the flexible LIBs allows the tab on the current collector providing enough channels for electron transfer,thus enabling electrons to be transferred quickly and enhancing the electrochemical reaction kinetics.Such a flexible battery with sufficient output current could possibly solve some of the most critical problems for their practical applications in wearable electronics.

Natural Cocoons Enabling Flexible and Stable Fabric Lithium–Sulfur Full Batteries

Lithium–sulfur batteries are highly appealing as highenergy power systems and hold great application prospects for flexible and wearable electronics.However,the easy formation of lithium dendrites,shuttle effect of dissolved polysulfides,random deposition of insulating lithium sulfides,and poor mechanical flexibility of both electrodes seriously restrict the utilization of lithium and stabilities of lithium and sulfur for practical applications.Herein,we present a cooperative strategy employing silk fibroin/sericin to stabilize flexible lithium–sulfur full batteries by simultaneously inhibiting lithium dendrites,adsorbing liquid polysulfides,and anchoring solid lithium sulfides.Benefiting from the abundant nitrogen-and oxygen-containing functional groups,the carbonized fibroin fabric serves as a lithiophilic fabric host for stabilizing the lithium anode,while the carbonized fibroin fabric and the extracted sericin are used as sulfiphilic hosts and adhesive binders,respectively,for stabilizing the sulfur cathode.Consequently,the assembled Li–S full battery provided a high areal capacity(5.6 mAh cm−2),limited lithium excess(90%),a high volumetric energy density(457.2 Wh L^(−1)),high-capacity retention(99.8%per cycle),and remarkable bending capability(6000 flexing cycles at a small radius of 5 mm).

Flexible Paper-Based Li-ion Batteries: A Review

Lithium-ion (Li-ion) batteries have been fabricated in various ways to improve flexibility. Flexibility could be enhanced via active materials, separators, electrodes, and electrolytes, which could then be integrated to form flexible electronic devices with promising electrochemical properties compared to traditional non-flexible Li-ion batteries. Recent progress towards flexible Li- ion batteries fabrication, materials, and their electrochemical properties are investigated in this review. Additionally, recent developments in electronic devices utilizing flexible batteries and their future applications are explored. Portable and wearable electronics, as the primary beneficiaries of the flexible, rechargeable, and high-performance Li-ion batteries, are examined. In the end, various applications and challenges of flexible batteries in healthcare and various energy storage systems, considering practical implementation, are argued.

Recent progress of flexible aqueous multivalent ion batteries

Flexible aqueous batteries have been thriving with the growing demand for wearable and portable electrical devices.In particular,flexible aqueous mul tivalent ion batteries(FAMIBs),the charge carriers of which include Zn^(2+),Al^(3+),Mg^(2+),and Ca^(2+),have great potential for development owing to their high safety,high elemental abundance in the Earth's crust,and a multi-electron redox mechanism with a high theoretical specific capacity.Therefore,for a comprehensive understanding of this developing field,it is necessary to summarize the recent research progress of FAMIBs in a timely manner.Herein,the advancements of the state-of-the-art FAMIBs are reviewed,and the prospects toward this field are also proposed.This study focuses on the rational material and configuration design for FAMIBs in recent studies to achieve high battery performances under deformation conditions,which is elaborated on by classification of the anode,cathode,hydrogel electrolyte,and configurations of FAMIBs.Besides,the electrochemical performance of FAMIBs under flexible conditions is also reviewed from the perspective of their working voltage,specific capacity,and cycling stability.Finally,the ap proaches to improve the performance of FAMIBs are comprehensively eval uated,followed by the outlook on the challenges and opportunities in future development of FAMIBs.

Direct growth of ordered N-doped carbon nanotube arrays on carbon fiber cloth as a free-standing and binder-free air electrode for flexible quasi-solid-state rechargeable Zn-Air batteries

The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.

Mechano-electrochemical perspectives on flexible lithium-ion batteries

With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stability,and high energy density are still an enormous challenge.In recent years,many complex and diverse design methods for flexible LIBs have been reported.The design and evaluation of ideal flexible LIBs must take into consideration both mechanical and electrochemical factors.In this review,the recent progress and challenges of flexible LIBs are reviewed from a mechano-electrochemical perspective.The recent progress in flexible LIB design is addressed concerning flexible material and configuration design.The mechanical and electrochemical evaluations of flexible LIBs are also summarized.Furthermore,mechano-electrochemical perspectives for the future direction of flexible LIBs are also discussed.Finally,the relationship between mechanical loading and the electrode process is analyzed from a mechano-electrochemical perspective.The evaluation of flexible LIBs should be based on mechano-electrochemical processes.Reviews and perspectives are of great significance to the design and practicality of flexible LIBs,which is contributed to bridging the gap between laboratory exploration and practical applications.

Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn-Air Batteries

Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability,high efficiency,and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc-air batteries.Here,3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated(referred to as PEMAC@NDCN)by a facile self-templated approach.PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability,which outperforms those of commercial Pt/C and RuO_(2).Theoretical calculations and control experi-ments reveal the boosted electron transfer,electrolyte mass/ion transports,and abundant active surface site preferences.Moreover,the constructed alkaline Zn-air battery with PEMAC@NDCN air-cathode reveals superb power density,capacity,and discharge-charge cycling stability(over 2160 cycles)compared to the reference Pt/C+RuO_(2).Solid-state Zn-air batteries enable a high power density of 211 mW cm^(−2),energy density of 1056 Wh kg^(−1),stable charge-discharge cycling of 2580 cycles for 50 mA cm^(−2),and wide temperature tolerance from−40 to 70℃with retention of 86%capacity compared to room-temperature counterparts,illustrating prospects over harsh operations.