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.

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.

Self-supporting NiFe LDH-MoS_(x) integrated electrode for highly efficient water splitting at the industrial electrolysis conditions

Developing effective and practical electrocatalyst under industrial electrolysis conditions is critical for renewable hydrogen production.Herein,we report the self-supporting NiFe LDH-MoS_(x) integrated electrode for water oxidation under normal alkaline test condition(1 M KOH at 25℃)and simulated industrial electrolysis conditions(5 M KOH at 65℃).Such optimized electrode exhibits excellent oxygen evolution reaction(OER)performance with overpotential of 195 and 290 mV at current density of 100 and 400 mA·cm^(-2) under normal alkaline test condition.Notably,only over-potential of 156 and 201 mV were required to achieve the current density of 100 and 400mA·cm^(-2) under simulated industrial electrolysis conditions.No significant degradations were observed after long-term durability tests for both conditions.When using in two-electrode system,the operational voltages of 1.44 and 1.72 V were required to achieve a current density of 10 and 100 mA·cm^(-2) for the overall water splitting test(NiFe LDH-MoS_(x)/INF||20%Pt/C).Additionally,the operational voltage of employing NiFe LDH-MoS_(x)/INF as both cathode and anode merely require 1.52 V at 50mA·cm^(-2) at simulated industrial electrolysis conditions.Notably,a membrane electrode assembly(MEA)for anion exchange membrane water electrolysis(AEMWEs)using NiFe LDH-MoS_(x)/INF as an anode catalyst exhibited an energy conversion efficiency of 71.8%at current density of 400 mA·cm^(-2)in 1 M KOH at 60℃.Further experimental results reveal that sulfurized substrate not only improved the conductivity of NiFe LDH,but also regulated its electronic configurations and atomic composition,leading to the excellent activity.The easy-obtained and cost-effective integrated electrodes are expected to meet the large-scale application of industrial water electrolysis.

Deciphering the lithium storage chemistry in flexible carbon fiber-based self-supportive electrodes

Flexible carbon fiber cloth(CFC)is an important scaffold and/or current collector for active materials in the development of flexible self-supportive electrode materials(SSEMs),especially in lithium-ion batteries.However,during the intercalation of Li ions into the matrix of CFC(below 0.5 V vs.Li/Li+),the incompatibility in the capacity of the CFC,when used directly as an anode material or as a current collector for active materials,leads to difficulty in the estimation of its actual contribution.To address this issue,we prepared Ni_(5)P_(4)nanosheets on CFC(denoted CFC@Ni_(5)P_(4))and investigated the contribution of CFC in the CFC@Ni_(5)P_(4)by comparing to the powder Ni_(5)P_(4)nanosheets traditionally coated on a copper foil(CuF)(denoted P-Ni_(5)P_(4)).At a current density of 0.4 mA cm^(−2),the as-prepared CFC@Ni_(5)P_(4)showed an areal capacity of 7.38 mAh cm^(−2),which is significantly higher than that of the PNi_(5)P_(4)electrode.More importantly,theoretical studies revealed that the CFC has a high Li adsorption energy that contributes to the low Li-ion diffusion energy barrier of the Ni_(5)P_(4)due to the strong interaction between the CFC and Ni_(5)P_(4),leading to the superior Li-ion storage performance of the CFC@Ni_(5)P_(4)over the pristine Ni_(5)P_(4)sample.This present work unveils the underlying mechanism leading to the achievement of high performance in SSEMs.

Surface characteristics of rapidly solidified nickel-based superalloy pow-ders prepared by PREP

The surface microstructure and the surface segregation of FGH 95 nickel-basedsuperalloy powders prepared through plasma rotating electrode processing (PREP) have beeninvestigated by using SEM and AES. The results indicate that the surface microstructure of powderschanges from dendrite into cellular stricture as the particle size of powders decrease, and thepredominant precipitates solidified on the particle surfaces were identified as MC' type carbidesenriched with Nb and Ti. It was also indicated that along with the depth of particle surfaces, thesegregation layer of S, C and O elements are thick, and that of Ti, Cr elements are thin for largesire powders while they are in reverse for median size particles.

Coupled cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes supported on nickel foam as a binder-free electrode for overall water splitting

In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N4 as the carbon source on a 3D porous nickel foam substrate.Benefiting from the optimized electronic structure and enhanced mass and charge transport,as well as the 3D conducting pathway,MoxCoy@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in an alkaline medium.The optimal electrocatalyst is Mo2Co1@N-CNSs/CNTs,which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER,respectively,and a relatively low cell voltage(1.63 V)for the overall water electrolysis.The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.

A critical review on nickel-based cathodes in rechargeable batteries

The 3d transition-metal nickel(Ni)-based cathodes have long been widely used in rechargeable batteries for over 100 years,from Ni-based alkaline rechargeable batteries,such as nickel-cadmium(Ni-Cd)and nickel-metal hydride(Ni-MH)batteries,to the Ni-rich cathode featured in lithium-ion batteries(LIBs).Ni-based alkaline batteries were first invented in the 1900s,and the well-developed Ni-MH batteries were used on a large scale in Toyota Prius vehicles in the mid-1990s.Around the same time,however,Sony Corporation commercialized the first LIBs in camcorders.After temporally fading as LiCoO_(2) dominated the cathode in LIBs,nickel oxide-based cathodes eventually found their way back to the mainstreaming battery industry.The uniqueness of Ni in batteries is that it helps to deliver high energy density and great storage capacity at a low cost.This review mainly provides a comprehensive overview of the key role of Ni-based cathodes in rechargeable batteries.After presenting the physical and chemical properties of the 3d transition-metal Ni,which make it an optimal cationic redox center in the cathode of batteries,we introduce the structure,reaction mechanism,and modification of nickel hydroxide electrode in Ni-Cd and Ni-MH rechargeable batteries.We then move on to the Ni-based layered oxide cathode in LIBs,with a focus on the structure,issues,and challenges of layered oxides,LiNiO_(2),and LiNi_(1−x−y)Co_(x)Mn_(y)O_(2).The role of Ni in the electrochemical performance and thermal stability of the Ni-rich cathode is highlighted.By bridging the“old”Ni-based batteries and the“modern”Ni-rich cathode in the LIBs,this review is committed to providing insights into the Ni-based electrochemistry and material design,which have been under research and development for over 100 years.This overview would shed new light on the development of advanced Ni-containing batteries with high energy density and long cycle life.

Effect of tube-electrode inner diameter on electrochemical discharge machining of nickel-based superalloy

Nickel-based superalloys are widely employed in modern aircraft engines because of their excellent material characteristics, particularly in the fabrication of film cooling holes. However, the high machining requirement of a large number of film cooling holes can be extremely challenging. The hybrid machining technique of tube electrode high-speed electrochemical discharge drilling (TEHECDD) has been considered as a promising method for the production of film cooling holes. Compared with any single machining process, this hybrid technique requires the removal of more complex machining by-products, including debris produced in the electrical discharge machining process and hydroxide and bubbles generated in the electrochemical machining process. These by-products significantly affect the machining efficiency and surface quality of the machined products. In this study, tube electrodes in different inner diameters are designed and fabricated, and the effects of inner diameter on the machining efficiency and surface quality of TEHECDD are investigated. The results show that larger inner diameters could effectively improve the flushing condition and facilitate the removal of machining by-products. Therefore, higher material removal efficiency, surface quality, and electrode wear rate could be achieved by increasing the inner diameter of the tube electrode. (C) 2015 The Authors. Production and hosting by Elsevier Ltd. on behalf of Chinese Society of Aeronautics and Astronautics.

Self-supported transition metal phosphide based electrodes as high-efficient water splitting cathodes

Electrolytic water splitting has been considered as a promising technology to produce highly pure H2 by using electrical power produced from wind, solar energy or other fitful renewable energy resources. Combining novel self-supporting structure and high-performance transition metal phosphides （TMP） shows substantial promise for practical application in water splitting. In this review, we try to provide a comprehensive analysis of the design and fabrication of various self-supported TMP electrodes for hydrogen evolution reaction, which are divided into three categories： catalysts growing on carbon-based substrates, catalysts growing on metal-based substrates and free- standing catalyst films. The material structures together with catalytic performances of self-supported electrodes are presented and discussed. We also show the specific strategies to further improve the catalytic performance by elemental doping or incorporation of nanocarbons. The simple and one-step methods to fabricate self-supported TMP electrodes are also highlighted. Finally, the chal- lenges and perspectives for self-supported TMP electrodes in water splitting application are briefly discussed.

Self-supported porous heterostructure WC/WO_(3−x)ceramic electrode for hydrogen evolution reaction in acidic and alkaline media

Tungsten carbide(WC)-based materials are widely considered as the hydrogen evolution reaction(HER)process catalysts due to their“Pt-like”electronic structure.Nonetheless,traditional powder electrodes have a high cost,and display problems related to the process itself and the poor stability over operation time.This paper presented a self-supported asymmetric porous ceramic electrode with WO_(3-x)whiskers formed in situ on the walls of the finger-like holes and membrane surface,which was prepared by combining phase inversion tape-casting,pressureless sintering,and thermal treatment in a CO_(2) atmosphere.The optimized ceramic electrode displayed good catalytic HER activity and outstanding stability at high current densities.More specifically,it demonstrated the lowest overpotentials of 107 and 123 mV and the lowest Tafel slopes of 59.3 and 72.4 mV·dec^(-1)at 10 mA·cm^(-2)in acidic and alkaline media,respectively.This superior performance was ascribed to the structure of the ceramic membrane and the charge transfer efficiency,which was favored by the in situ developed WC/WO_(3-x)heterostructure and the oxygen vacancies.

Self-supported transition metal oxide electrodes for electrochemical energy storage

Electrode materials are of decisive importance in determining the performance of electrochemical energy storage(EES)devices.Typically,the electrode materials are physically mixed with polymer binders and conductive additives,which are then loaded on the current collectors to function in real devices.Such a configuration inevitably reduces the content of active species and introduces quite some undesired interfaces that bring down the energy densities and power capabilities.One viable solution to address this issue is to construct self-supported electrodes where the active species,for example transition metal oxides(TMOs),are directly integrated with conductive substrates without polymer binders and conductive additives.In this review,the recent progress of self-supported TMO-based electrodes for EES devices including lithium-ion batteries(LIBs),sodium-ion batteries(SIBs),aluminum-ion batteries(AIBs),metal-air batteries,and supercapacitors(SCs),is discussed in great detail.The focused attention is firstly concentrated on their structural design and controllable synthesis.Then,the mechanism understanding of the enhanced electrochemical performance is presented.Finally,the challenges and prospects of self-supported TMO-based electrodes are summarized to end this review.

A CuNi/C Nanosheet Array Based on a Metal–Organic Framework Derivate as a Supersensitive Non-Enzymatic Glucose Sensor

Bimetal catalysts are good alternatives for nonenzymatic glucose sensors owing to their low cost, high activity, good conductivity, and ease of fabrication. In the present study, a self-supported CuNi/C electrode prepared by electrodepositing Cu nanoparticles on a Ni-based metal–organic framework(MOF) derivate was used as a non-enzymatic glucose sensor. The porous construction and carbon scaffold inherited from the Ni-MOF guarantee good kinetics of the electrode process in electrochemical glucose detection. Furthermore, Cu nanoparticles disturb the array structure of MOF derived films and evidently enhance their electrochemical performances in glucose detection. Electrochemical measurements indicate that the CuNi/C electrode possesses a high sensitivity of17.12 mA mM^(-1) cm^(-2), a low detection limit of 66.67 nM,and a wider linearity range from 0.20 to 2.72 mM. Additionally, the electrode exhibits good reusability, reproducibility, and stability, thereby catering to the practical use of glucose sensors. Similar values of glucose concentrations in human blood serum samples are detected with our electrode and with the method involving glucose-6-phosphate dehydrogenase; the results further demonstrate the practical feasibility of our electrode.

Modulating proton binding energy on the tungsten carbide nanowires surfaces for boosting hydrogen evolution in acid

ungsten carbides have attracted wide attentions as Pt substitute electrocatalysts for hydrogen evolution reaction (HER), due to their good stability in an acid environment and Pt-like behaviour in hydrolysis. However, quantum chemistry calculations predict that the strong tungsten-hydrogen bonding hinders hydrogen desorption and restricts the overall catalytic activity. Synergistic modulation of host and guest electronic interaction can change the local work function of a compound, and therefore, improve its electrocatalytic activity over either of the elements individually. Herein, we develop a creative and facile solid-state approach to synthesize self-supported carbon-encapsulated single-phase WC hybrid nanowires arrays (nanoarrays) as HER catalyst. The theoretical calculations reveal that carbon encapsulation modifies the Gibbs free energy of H* values for the WC adsorption sites, endowing a more favorable C@WC active site for HER. The experimental results exhibit that the hybrid WC nanoarrays possess remarkable Pt-like catalytic behavior, with superior activity and stability in an acidic media, which can be compared to the best non-noble metal catalysts reported to date for hydrogen evolution reaction. The present results and the facile synthesis method open up an exciting avenue for developing cost-effective catalysts with controllable morphology and functionality for scalable hydrogen generation and other carbide nanomaterials applicable to a range of electrocatalytic reactions.

Multi-layer hierarchical cellulose nanofibers/carbon nanotubes/vinasse activated carbon composite materials for supercapacitors and electromagnetic interference shielding

Developing porous self-supporting electrodes with excellent conductivity,good mechanical properties,and high electrochemical activity is crucial for constructing electrode materials with lightweight,ultra-thin,flexible,and high capacitance performance.In this work,we prepared a cellulose nanofibers(CNFs)/carbon nanotubes(CNTs)/vinasse activated carbon(VAC)(CCV)composite material with a multi-layer hierarchical conductive structure through simple vacuum filtration and freeze-drying.In this composite material,the self-assembly of CNF provides the main skeleton structure of a multi-layer hierarchical structure.CNT provides a fast path for the rapid transfer of electrons and is beneficial for the loss of electromagnetic waves.VAC provides sufficient double layer performance.The synergistic effect of the above three endows CCV composite materials with excellent energy storage performance and electromagnetic interference(EMI)shielding performance.In addition,we endowed the CCV composite with a certain shape and performance by introducing a vitrimer polymer with a dynamic cross-linked network structure.In summary,thanks to the synergistic effect of various components in the multi-layer hierarchical structure,CCV composite materials exhibit excellent integration performance,especially stable energy storage performance and EMI shielding performance.These significant properties make CCV composite materials have great application prospects in the fields of energy storage and intelligent EMI shielding.

Self-supported ternary Co0.5Mn0.5P/carbon cloth （CC） as a high-performance hydrogen evolution electrocatalyst

Scalable production of earth-abundant, easy-to-prepare, and cost-effective electrocatalysts for the hydrogen evolution reaction （HER） is essential for sustainable energy-based systems. Herein, we systematically studied the electrocatalytic HER performance of a self-supported ternary Co0.5Mn0.5P/carbon cloth （CC） nanomaterial prepared using a hydrothermal reaction and phosphorizafion process. Electrochemical tests demonstrated that the ternary Co0.5Mn0.5P/CC nanomaterial could be a highly active electrocatalyst in acidic media, with overpotentials of only 41 and 89 mV, affording current densities of 10 and 100 mA.cm-2, respectively, and a Tafel slope of 41.7 mV.dec-1. Furthermore, the electrocatalyst exhibited superior stability, with 3,000 cycles of cyclic voltammetry from -0.2 to 0.2 V at a scan rate of 100 mV.s-1 and 40 h of static polarization at a fixed overpotential of large-scale hydrogen production. 83 mV, indicating its potential for

Cracked bark-inspired ternary metallic sulfide(NiCoMnS_(4)) nanostructure on carbon cloth for high-performance aqueous asymmetric supercapacitors

In this paper,we report a high-performance selfsupported supercapacitor electrode composed of a cracked bark-shaped Ni-Co-Mn ternary metallic sulfide(NiCoMnS4)nanostructure on carbon cloth prepared by a simple one-step hydrothermal process and subsequent electrochemical treatment.The electrode delivers a high specific discharge capacity of up to 2470.4 F g^(-1) at 1 A g^(-1) and high rate performances of1635.6 F g^(-1) at 10 A g^(-1) and 910.2 F g^(-1) even at 32 A g^(-1).Cycling tests indicate that NiCoMnS_(4) could maintain >91.1% of its initial capacity and nearly 100% Coulombic efficiency over10,000 cycles at 8 A g^(-1).An aqueous asymmetric supercapacitor assembled with NiCoMnS_(4) as the cathode,activated carbon as the anode,and 1 mol L^(-1) KOH as the electrolyte delivers an energy density of 68.2 W h kg^(-1)at 850.1 W kg^(-1) and capacity retention of 92.5% after 10,000 cycles at 4 A g^(-1).Given the excellent performance and simple material preparation of our proposed device,this study provides a valuable foundation for the development of self-supported metallic sulfide-based electrodes with high electrochemical properties for potential application in aqueous asymmetric supercapacitors.

N-doped carbon-coated Co_3O_4 nanosheet array/carbon cloth for stable rechargeable Zn-air batteries

Although the application of various nonprecious compounds as the air cathodes of Zn-air batteries has been explored, the construction of highly efficient selfsupported Co-based electrodes remains challenging and highly desired given their outstanding electrocatalytic activity and cost-effectiveness. Herein, we fabricated a three-dimensional(3D) self-supported electrode based on N-doped,carbon-coated Co3O4 nanosheets grown on a carbon cloth(i.e., NC-Co3O4/CC) through the electrochemical deposition and carbonization. When used as a binder-free electrode for oxygen evolution reaction(OER), the NC–Co3O4/CC electrode demonstrated excellent electrocatalytic activity with an overpotential of 210 mV at 10 mA cm^-2 and a Tafel slope of79.6 mV dec^-1. In the Zn-air battery test, the electrode delivered a small charge/discharge voltage gap(0.87 V at 10 mA cm^-2) and exhibited high durability without degradation after 93 cycles at the large current density of 25 mA cm^-2.The durability of our electrode was superior to that of a commercial Pt/C+RuO2 catalyst. The excellent performance of NC–Co3O4/CC could be attributed to the presence of 3D structures that promoted electron/ion transfer. By the absence of a binder, the carbon coating improved electron conductivity and promoted electrochemical stability. Moreover, N doping could be used to adjust the C electron structure and accelerate electron transfer. The present study provides a facile and effective route for the synthesis of various self-supported electrodes that fulfill the requirements of different energy storage and conversion devices.