Insights into Nano-and Micro-Structured Scaffolds for Advanced Electrochemical Energy Storage

Adopting a nano-and micro-structuring approach to fully unleashing the genuine potential of electrode active material benefits in-depth understandings and research progress toward higher energy density electrochemical energy stor-age devices at all technology readiness levels.Due to various challenging issues,especially limited stability,nano-and micro-structured(NMS)electrodes undergo fast electrochemical performance degradation.The emerging NMS scaffold design is a pivotal aspect of many electrodes as it endows them with both robustness and electrochemical performance enhancement,even though it only occupies comple-mentary and facilitating components for the main mechanism.However,extensive efforts are urgently needed toward optimizing the stereoscopic geometrical design of NMS scaffolds to minimize the volume ratio and maximize their functionality to fulfill the ever-increasing dependency and desire for energy power source supplies.This review will aim at highlighting these NMS scaffold design strategies,summariz-ing their corresponding strengths and challenges,and thereby outlining the potential solutions to resolve these challenges,design principles,and key perspectives for future research in this field.Therefore,this review will be one of the earliest reviews from this viewpoint.

Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices

The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity.However,conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients,limiting reaction kinetics.We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity.This free-standing device structure also avoids short-circuiting without needing a separator.The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion.Starting with a 3D-printed interpenetrated polymer substrate,we metallize it to make it conductive.This substrate has two individually addressable electrodes,allowing selective electrodeposition of energy storage materials.Using a Zn//MnO_(2) battery as a model system,the interpenetrated device outperforms conventional separate electrode configurations,improving volumetric energy density by 221%and exhibiting a higher capacity retention rate of 49%compared to 35%at temperatures from 20 to 0℃.Our study introduces a new EESD architecture applicable to Li-ion,Na-ion batteries,supercapacitors,etc.

Preparation and electrochemical lithium storage performance of porous silicon microsphere composite with metal modification and carbon coating

This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.

Recent advances in electrochemical performance of Mg-based electrochemical energy storage materials in supercapacitors:Enhancement and mechanism

The application of Mg-based electrochemical energy storage materials in high performance supercapacitors is an essential step to promote the exploitation and utilization of magnesium resources in the field of energy storage.Unfortunately,the inherent chemical properties of magnesium lead to poor cycling stability and electrochemical reactivity,which seriously limit the application of Mg-based materials in supercapacitors.Herein,in this review,more than 70 research papers published in recent 10 years were collected and analyzed.Some representative research works were selected,and the results of various regulative strategies to improve the electrochemical performance of Mg-based materials were discussed.The effects of various regulative strategies(such as constructing nanostructures,synthesizing composites,defect engineering,and binder-free synthesis,etc.)on the electrochemical performance and their mechanism are demonstrated using spinelstructured MgX_(2)O_(4) and layered structured Mg-X-LDHs as examples.In addition,the application of magnesium oxide and magnesium hydroxide in electrode materials,MXene's solid spacers and hard templates are introduced.Finally,the challenges and outlooks of Mg-based electrochemical energy storage materials in high performance supercapacitors are also discussed.

Electrochemical hydrogen storage characteristics of nanocrystalline and amorphous Mg_2Ni-type alloys prepared by melt-spinning

The nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg2Ni1-xMnx （x=0, 0.1, 0.2, 0.3, 0.4） were synthesized by melt-spinning technique. The spun alloy ribbons with a continuous length, a thickness of about 30 μm and a width of about 25 mm are obtained. The structures of the as-spun alloy ribbons were characterized by XRD and HRTEM. The electrochemical hydrogen storage characteristics of the as-spun alloy ribbons were measured by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation. The hydrogen diffusion coefficients （D） in the alloys were calculated by virtue of potential-step measurement. The results show that all the as-spun （x=0） alloys hold a typical nanocrystalline structure, whereas the as-spun （x=0.4） alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. The substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn substitution from 0 to 0.4, the discharge capacity of the as-spun （20 m/s） alloy increases from 96.5 to 265.3 mA·h/g, and its capacity retaining rate （S20） at the 20th cycle increases from 31.3% to 70.2%. Furthermore, the high rate dischargeability （HRD）, electrochemical impedance spectrum and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases then decreases with raising the amount of Mn substitution.

Mathematical modeling of electrochemical storage for incorporation in methods to optimize the operational planning of an interconnected micro grid

We extract a mathematical model to simulate the steady-state charging and discharging behaviors of an electrochemical storage over a 24-hour time interval.Moreover,we develop a model for optimizing the daily operational planning of an interconnected micro grid considering electrochemical storage.The optimization model is formulated to maximize the total benefit of the micro grid via selling power to its end consumers and also exchanging power with the wholesale energy market so that the constraints of distributed energy resources(DERs) and low-voltage grid are met.The optimization problem is solved by a genetic algorithm,and applied on two micro grids operating under different scenarios containing the absence or presence of electrochemical storages.Comparison of the results of the optimization model for this micro grid,with and without electrochemical storage,shows that the electrochemical storage can improve the economical efficiency of the interconnected micro grids by up to 10.16%.

Interest of molecular functionalization for electrochemical storage

Despite great interests in electrochemical energy storage systems for numerous applications, considerable challenges remain to be overcome. Among the various approaches to improving the stability, safety, performance, and cost of these systems, molecular functionalization has recently been proved an attractive method that allows the tuning of material surface reactivity while retaining the properties of the bulk material. For this purpose, the reduction of aryldiazonium salt, which is a versatile method, is considered suitable; it forms robust covalent bonds with the material surface, however, with the formation of multilayer structures and sp3 defects （for carbon substrate） that can be detrimental to the electronic conductivity. Alternatively, non-covalent molecular functionalization based on π-π interactions using aromatic ring units has been proposed. In this review, the various advances in molecular functionalization concerning the current limitations in lithium-ion batteries and electrochemical capacitors are discussed. According to the targeted applications and required properties, both covalent and non-covalent functionalizafion methods have proved to be very efficient and versatile. Fundamental aspects to achieve a better understanding of the funcfionalization reactions as well as molecular layer properties and their effects on the electrochemical performance are also discussed. Finally, perspectives are proposed for future implementation of molecular functionalization in the field of electrochemical storage.

Lignin-based materials for electrochemical energy storage devices

Lignin is the most abundant aromatic polymer in nature,which is rich in a large number of benzene ring structures and active functional groups.The molecular structure of lignin has unique designability and controllability,and is a class of functional materials with great application prospects in energy storage and conversion.Here,this review firstly focuses on the concept,classification,and physicochemical property of lignin.Then,the application research of lignin in the field of electrochemical storage materials and devices are summarized,such as lignin-carbon materials and lignin-carbon composites in supercapacitors and secondary batteries.Finally,this review points out the bottlenecks that need to be solved urgently and the prospects for future research priorities.

Electrochemical lithium storage performance of three-dimensional foam-like biocarbon/MoS2 composites

Molybdenum disulfide(MoS2)was loaded on biocarbon using waste camellia dregs(CDs)as the carbon source,which was further coated with dopamine hydrochloride to construct biocarbon/MoS2 electrode composites.The electrochemical lithium storage performance of the composites with different MoS2 contents was investigated.SEM results demonstrated that the composite had a three-dimensional foam-like structure with MoS2 as the interlayer.XRD and HRTEM tests revealed that MoS2 interlayer spacing in the composite was expanded.XPS analysis showed that new Mo—N bonds were formed in the active material.The electrochemical tests showed that the composite with a MoS2 content of 63%had a high initial specific capacity of 1434 mA·h/g at a current density of 100 mA/g.After a long cycle at a high current,it also showed good cycling stability and the capacity retention was nearly 100%.In addition,it had good lithium ion deintercalation ability in the electrochemical kinetics test.

Effect of Ni,Fe and Fe-Ni alloy catalysts on the synthesis of metal contained carbon nano-onions and studies of their electrochemical hydrogen storage properties

Three types of carbon nano-onions（CNOs） including Ni@CNOs.Fe3C@CNOs and Fe0.64Ni0.36@CNOs nanoparticles have been synthesized by catalytic decomposition of methane at 850 ℃ using nickel,iron and iron-nickel alloy catalysts.Comparative and systematic studies have been carried out on the morphology,structural characteristics and graphitic crystallinity of these CNOs products.Furthermore,the electrochemical hydrogen storage properties of three types of CNOs have been investigated.Measurements show that the Ni@CNOs have the highest discharge capacity of 387.2 mAh/g,coiTesponding to a hydrogen storage of 1.42%.This comparison study shows the advantages of each catalyst in the growth of CNOs.enabling the controllable synthesis and tuning the properties of CNOs by mediating different metals and their alloy for using in the fuel cell system.

Electrochemical Proton Storage:From Fundamental Understanding to Materials to Devices

Simultaneously improving the energy density and power density of electrochemical energy storage systems is the ultimate goal of electrochemical energy storage technology.An effective strategy to achieve this goal is to take advantage of the high capacity and rapid kinetics of electrochemical proton storage to break through the power limit of batteries and the energy limit of capacitors.This article aims to review the research progress on the physicochemical properties,electrochemical performance,and reaction mechanisms of electrode materials for electrochemical proton storage.According to the different charge storage mechanisms,the surface redox,intercalation,and conversion materials are classified and introduced in detail,where the influence of crystal water and other nanostructures on the migration kinetics of protons is clarified.Several reported advanced full cell devices are summarized to promote the commercialization of electrochemical proton storage.Finally,this review provides a framework for research directions of charge storage mechanism,basic principles of material structure design,construction strategies of full cell device,and goals of practical application for electrochemical proton storage.

MXene-based materials for electrochemical energy storage

Rechargeable batteries and supercapacitors are widely investigated as the most important electrochemical energy storage devices nowadays due to the booming energy demand for electric vehicles and hand-held electronics. The large surface-area-to-volume ratio and internal surface areas endow two-dimensional（2D） materials with high mobility and high energy density; therefore, 2D materials are very promising candidates for Li ion batteries and supercapacitors with comprehensive investigations. In 2011, a new kind of 2D transition metal carbides, nitrides and carbonitrides, MXene, were successfully obtained from MAX phases. Since then about 20 different kinds of MXene have been prepared. Other precursors besides MAX phases and even other methods such as chemical vapor deposition（CVD） were also applied to prepare MXene, opening new doors for the preparation of new MXene. Their 2D nature and good electronic properties ensure the inherent advantages as electrode materials for electrochemical energy storage. In this review, we summarize the recent progress in the development of MXene with emphasis on the applications to electrochemical energy storage. Also, future perspective and challenges of MXene-based materials are briefly discussed regrading electrochemical energy storage.

Recent advances in 3D printed electrode materials for electrochemical energy storage devices

Electrochemical energy storage(EES)systems like batteries and supercapacitors are becoming the key power sources for attempts to change the energy dependency from inadequate fossil fuels to sustainable and renewable resources.Electrochemical energy storage devices(EESDs)operate efficiently as a result of the construction and assemblage of electrodes and electrolytes with appropriate structures and effective materials.Conventional manufacturing procedures have restrictions on regulating the morphology and architecture of the electrodes,which would influence the performance of the devices.3D printing(3DP)is an advanced manufacturing technology combining computer-aided design and has been recognised as an artistic method of fabricating different fragments of energy storage devices with its ability to precisely control the geometry,porosity,and morphology with improved specific energy and power densities.The capacity to create mathematically challenging shape or configuration designs and high-aspect-ratio 3D architectures makes 3D printing technology unique in its benefits.Nevertheless,the control settings,interactive manufacturing processes,and protracted post-treatments will affect the reproducibility of the printed components.More intelligent software,sophisticated control systems,high-grade industrial equipment,and post-treatment-free methods are necessary to develop.3D printed(3DPd)EESDs necessitate dynamic printable materials and composites that are influenced by performance criteria and fundamental electrochemistry.Herein,we review the recent advances in 3DPd electrodes for EES applications.The emphasis is on printable material synthesis,3DP techniques,and the electrochemical performance of printed electrodes.For the fabrication of electrodes,we concentrate on major 3DP technologies such as direct ink writing(DIW),inkjet printing(IJP),fused deposition modelling(FDM),and stereolithography3DP(SLA).The benefits and drawbacks of each 3DP technology are extensively discussed.We provide an outlook on the integration of synthesis of emerging nanomaterials and fabrication of complex structures from micro to macroscale to construct highly effective electrodes for the EESDs.

3D Printing of Next-generation Electrochemical Energy Storage Devices: from Multiscale to Multimaterial

The increasing energy requirements to power the modern world has driven active research into more advanced electrochemical energy storage devices(EESD)with both high energy densities and power densities.Wide range of newly discovered materials with promising electrochemical properties has shown great potential for next-generation devices,but their performance is normally associated with contradicting demands of thin electrodes and high mass loading that can be hardly achieved for practical applications.Design of three-dimensional(3D)porous electrodes can increase the mass loading while maintaining the effective charge transport even with thick electrodes,which has proven to be efficient to overcome the limitations.3D structures have also been demonstrated excellent structural stability to withstand strong strains and stresses generated during charge/discharge cycle.3D printing,which can fabricate various delicate and complex structural designs,thus offering brand-new opportunities for the rational design and facile construction of next-generation EESDs.The recent developments in 3D printing of next-generation EESDs with high performance are reviewed.Advanced/multiscale electrode structures,such as hierarchically porous structure that can be constructed via high-resolution 3D printing or with post-treatment,are further emphasized.The ability of current 3D printing techniques to fulfill multimaterial printing to fulfill simple packaging will be covered.

Application and Progress of Confinement Synthesis Strategy in Electrochemical Energy Storage

Designing high-performance nanostructured electrode materials is the current core of electrochemical energy storage devices.Multi-scaled nanomaterials have triggered considerable interest because they effectively combine a library of advantages of each component on different scales for energy storage.However,serious aggregation,structural degradation,and even poor stability of nanomaterials are well-known issues during electrochemically driven volume expansion/contraction processes.The confinement strategy provides a new route to construct controllable internal void spaces to avoid the intrinsic volume effects of nanomaterials during the reaction or charge/discharge process.Herein,we discuss the confinement strategies and methods for energy storage-related electrode materials with a one-dimensional channel,two-dimensional interlayer,and three-dimensional space as reaction environments.For each confinement environment,the correlation between the confinement condition/structure and the behavioral characteristics of energy storage devices in the scope of metal-ion batteries(e.g.,Li-ion,Na-ion,K-ion,and Mg-ion batteries),Li-S batteries(LSBs),Zn-air batteries(ZIBs),and supercapacitors.Finally,we discussed the challenges and perspectives on future nanomaterial confinement strategies for electrochemical energy storage devices.

Opportunities and challenges of organic flow battery for electrochemical energy storage technology

For flow batteries(FBs), the current technologies are still expensive and have relatively low energy density, which limits their large-scale applications. Organic FBs(OFBs) which employ organic molecules as redox-active materials have been considered as one of the promising technologies for achieving lowcost and high-performance. Herein, we present a critical overview of the progress on the OFBs, including the design principles of key components(redox-active molecules, membranes, and electrodes) and the latest achievement in both aqueous and nonaqueous systems. Finally, future directions in explorations of the high-performance OFB for electrochemical energy storage are also highlighted.

Towards electrochemical hydrogen storage in liquid organic hydrogen carriers via proton-coupled electron transfers

Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO_(2).A possible solution for the transport of H_(2)in a safe and low-cost way is in the form of liquid organic hydrogen carriers(LOHCs).As an alternative to loading LOHC with H_(2)via a two-step procedure involving preliminary electrolytic production of H_(2)and subsequent chemical hydrogenation of the LOHC,we explore here the possibility of electrochemical hydrogen storage(EHS)via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC(R)via a protoncoupled electron transfer(PCET)reaction:2nH^(+)+2ne^(-)+Rox■n H_(2)^(0)Rred.We chose 9-fluorenone/fluorenol(Fnone/Fnol)conversion as such a model PCET reaction.The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity,which enabled us to both quantify and get the mechanistic insight on PCET.The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.

Improved electrochemical hydrogen storage properties of Mg-Y thin films as a function of substrate temperature

Pd-capped Mg78Y22 thin films have been prepared by direct current magnetron co-sputtering system at different substrate temperatures and their electrochemical hydrogen storage properties have been investigated.It is found that rising substrate temperature to 60 ℃ can coarsen the surface of thin film,thus facilitating the diffusion of hydrogen atoms and then enhancing its discharge capacity to 1725 mAh·g-1.Simultaneously,the cyclic stability is effectively improved due to the increased adhesion force between film and substrate as a function of temperature.In addition,the specimen exhibits a very long and flat discharge plateau at about —0.67 V,at which nearly 60%of capacity is maintained.The property is favorable for the application in metal hydride/nickel secondary batteries.The results indicate that rising optimal substrate temperature has a beneficial effect on the electrochemical hydrogen storage of Mg-Y thin films.

Two-dimensional polymer-based nanosheets for electrochemical energy storage and conversion

Over the past decades, two-dimensional（2D） nanomaterials possessing planar layered architecture and unique electronic structures have been being quickly developed, due to their wide potential application in the fields of chemistry, physics, and materials science. As a new family of 2D nanomaterials, 2D polymerbased nanosheets, featuring excellent characters, such as tunable framework structures, light weight, flexibility, high specific surface, and good semiconducting properties, have been emerging as one kind of promising functional materials for optoelectronics, gas separation, catalysis and sensing, etc. In this review, the recent progress in synthetic approach and characterization of 2D polymer-based nanosheets were summarized, and their current advances in electrochemical energy storage and conversion including second batteries, supercapacitors, oxygen reduction and hydrogen evolution were discussed systematically.

Organic fast ion-conductor with ordered Li-ion conductive nano-pathways and high ionic conductivity for electrochemical energy storage

Solid electrolyte(SE)is the most crucial factor to fabricate safe and high-performance all-solid-state lithium-ion batteries.However,the most commonly reported SE,including solid polymer electrolyte(SPE)and inorganic oxides and sulfides,suffer problems of low ionic conductivity at room temperature for SPE and large interfacial impedance with electrodes for inorganic electrolytes.Here we for the first time demonstrate a novel ionic plastic crystal lithium salt solid electrolyte(OLiSSE)fast ion-conductor dilithium(1,3-diethyl-4,5-dicarboxylate)imidazole bromide with ordered Li-ion conductive nanopathways and an exceptional ionic conductivity of 4.4×10^(−3)Scm^(−1)at 30℃.The prepared OLiSSE exhibits apparent characters of typical ionic plastic crystals in the temperature range of−20 to 70℃,and shows remarkable thermal stability and electrochemical stability below 150℃ and 4.7 V,respectively.No lithium dendrite or short circuit behavior is detected for the Li|OLiSSE|Li cell after the galvanostatic charge-discharge test for 500 h.The fabricated Li|OLiSSE|LiFePO_(4) all-solid-state cell without using any separator and liquid plasticizer directly delivers an initial discharge capacity of 151.4 mAh g^(−1) at the discharge rate of 0.1 C,and shows excellent charge-discharge cycle stability,implying large potential application in the next generation of safe and flexible all-solid-state lithium batteries.