Hyphae-mediated bioassembly of carbon fibers derivatives for advanced battery energy storage

Ingenious design and fabrication of advanced carbon-based sulfur cathodes are extremely important to the development of high-energy lithium-sulfur batteries,which hold promise as the next-generation power source.Herein,for the first time,we report a novel versatile hyphae-mediated biological assembly technology to achieve scale production of hyphae carbon fibers(HCFs)derivatives,in which different components including carbon,metal compounds,and semiconductors can be homogeneously assembled with HCFs to form composite networks.The mechanism of biological adsorption assembly is also proposed.As a representative,reduced graphene oxides(rGOs)decorated with hollow carbon spheres(HCSs)successfully co-assemble with HCFs to form HCSs@rGOs/HCFs hosts for sulfur cathodes.In this unique architecture,not only large accommodation space for sulfur but also restrained volume expansion and fast charge transport paths are realized.Meanwhile,multiscale physical barriers plus chemisorption sites are simultaneously established to anchor soluble lithium polysulfides.Accordingly,the designed HCSs@rGOs/HCFs-S cathodes deliver a high capacity(1189 mA h g^(-1)at 0.1 C)and good high-rate capability(686 mA h g^(-1)at 5 C).Our work provides a new approach for the preparation of high-performance carbon-based electrodes for energy storage devices.

Ultra-homogeneous dense Ag nano layer enables long lifespan solid-state lithium metal batteries

The unstable electrolyte/lithium(Li)anode interface has been one of the key challenges in realizing high energy density solid-state lithium metal batteries(LMBs)applications.Herein,a dense and uniform silver(Ag)nano interlayer with a thickness of∼35 nm is designed accurately by magnetron sputtering technology to optimize the electrolyte/Li anode interface.This Ag nano layer reacts with Li metal anode to in-situ form Li-Ag alloy,thus enhancing the physical interfacial contact,and further improving the interfacial wettability and compatibility.In particular,the Li-Ag alloy is inclined to form AgLi phase proved by cryo-TEM and DFT,effectively preventing SN from continuously“attacking”the Li metal anode due to the lower adsorption of succinonitrile(SN)molecules on AgLi than that of pure Li metal,thereby significantly reinforcing the interfacial stability.Hence,the enhanced physical and chemical stability of electrolyte/Li anode interface promotes the homogeneous deposition of Li^(+)and inhibits the dendrite growth.The Li-symmetric cell maintains stable operation for up to 1700 h and the cycling stability of LiFePO_(4)|SPE|Li full cell is remarkably improved at room temperature(capacity retention rate of 91.9%for 200 cycles).This work opens an effective way for accurate and controllable interface design of long lifespan solid-state LMBs.

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.

Revisiting Scientific Issues for Industrial Applications of Lithium–Sulfur Batteries

Inspired by high theoretical energy density(-2600 W h kg^(-1))and cost-effectiveness of sulfur cathode,lithium–sulfur batteries are receiving great attention and considered as one of the most promising next-generation high-energy-density batteries.However,over the past decades,the energy density and reliable safety levels as well as the commercial progress of lithium-sulfur batteries are still far from satisfactory due to the disconnection and huge gap between fundamental research and practical application.

High?Index?Faceted Ni_3S_2 Branch Arrays as Bifunctional Electrocatalysts for Efficient Water Splitting

For efficient electrolysis of water for hydrogen generation or other valueadded chemicals, it is highly relevant to develop low-temperature synthesis of low-cost and high-e ciency metal sulfide electrocatalysts on a large scale. Herein, we construct a new core–branch array and binder-free electrode by growing Ni_3S_2 nanoflake branches on an atomic-layer-deposited(ALD) TiO_2 skeleton. Through induced growth on the ALD-TiO_2 backbone, cross-linked Ni_3S_2 nanoflake branches with exposed { 210} highindex facets are uniformly anchored to the preformed TiO_2 core forming an integrated electrocatalyst. Such a core–branch array structure possesses large active surface area, uniform porous structure, and rich active sites of the exposed { 210 } high-index facet in the Ni_3S_2 nanoflake. Accordingly, the TiO_2@Ni_3S_2 core/branch arrays exhibit remarkable electrocatalytic activities in an alkaline medium, with lower overpotentials for both oxygen evolution reaction(220 mV at 10 mA cm^(-2)) and hydrogen evolution reaction(112 m V at 10 mA cm^(-2)), which are better than those of other Ni_3S_2 counterparts. Stable overall water splitting based on this bifunctional electrolyzer is also demonstrated.

Directional construction of Cu2S branch arrays for advanced oxygen evolution reaction

Metal sulphide electrocatalyst is considered as one of the most promising low-cost candidates for oxygen evolution reaction(OER).In this work,we report a novel free-standing Cu2S branch array via a facile TiO2-induced electrodeposition-sulfurization method.Interestingly,cross-linked Cu2S nanoflake branch is strongly anchored on the TiO2 backbone forming high-quality Cu2S/TiO2/Cu2S core-branch arrays.The branch formation mechanism is also proposed.As compared to the pure Cu2S nanowire arrays,the asprepared Cu2S/TiO2/Cu2S core-branch arrays show much better alkaline OER performance with lower overpotential(284 mV at 10 mA cm^-2)and smaller Tafel slope(72 dec-1)as well as enhanced longterm durability mainly due to larger exposed area and more active electrocatalytic sites.Our work provides a new way for construction of advanced metal sulphide electrocatalysts for electrochemical energy conversion.

Self-supported hierarchical porous Li_(4)Ti_(5)O_(12)/carbon arrays for boosted lithium ion storage

The development of fast rechargeable lithium ion batteries(LIBs)is highly dependent on the innovation of advanced high-power electrode materials.In this work,for the first time,we report a sacrificial NiO arrays template method for controllable synthesis of self-supported hierarchical porous Li_(4)Ti_(5)O_(12)/C(LTO/C)nanoflakes arrays,for use as fast rechargeable anodes for LIBs.The ultrathin(2-3 nm)carbon layer was uniformly coated on the LTO forming arrays architecture.The hierarchical porous LTO/C nanoflakes consisted of primary cross-linked nanoparticles of 50-100 nm and showed large porosity.Because of the enhanced electrical conductivity and accelerated ion transfer channels,the well-designed binderfree porous LTO/C nanoflakes arrays exhibited notable high-rate lithium ion storage performance with smaller polarization,better electrochemical reactivity,higher specific capacity(157 mAh g^(-1) at the current density of 20C)and improved long-term cycling life(96.2% after 6000 cycles at 20C),superior to the unmodified porous LTO arrays counterpart(126 mAh g^(-1) at 20C and 88.0%after 6000 cycles at 20C).Our work provides a new template for the construction of high-performance high-rate electrodes for electrochemical energy storage.

N-doped CoO nanowire arrays as efficient electrocatalysts for oxygen evolution reaction

Rational design of cost-effective high-performance electrocatalysts for oxygen evolution reaction (OER) is of great significance for electrochemical water splitting. Herein, we adopt a nitrogen doping method to fabricate self-supported N-doped CoO nanowire arrays (N-CoO) as active electrocatalysts via a facile hydrothermal combined doping method. The N-CoO nanowires are strongly composited with the carbon cloth substrate forming free-standing electrode with reinforced stability and high electronic conductivity. Owing to the increased accessible and electroactive areas, rich/short pathways for charge transfer and enhanced electronic conductivity, the N-CoO electrode exhibits excellent electrocatalytic performance for OER with a low overpotential (319 mV at 10 mA cm^-2 and 410 mV at 100 mA cm^-2) and a low Tafel slope of 74 mV dec^-1 as well as superior long-term stability with no decay in 24 h continuous test in alkaline solution. Our reported design and optimization strategy provide a promising way to construct interesting well-aligned arrays for application in energy storage and conversion.

Atomic Layer Deposition-Assisted Construction of Binder-Free Ni@N-Doped Carbon Nanospheres Films as Advanced Host for Sulfur Cathode

Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries(LSBs).Herein,novel binder-free Ni@N-doped carbon nanospheres(N-CNSs)films as sulfur host are firstly synthesized via a facile combined hydrothermal-atomic layer deposition method.The cross-linked multilayer N-CNSs films can effectively enhance the electrical conductivity of electrode and provide physical blocking“dams”toward the soluble long-chain polysulfides.Moreover,the doped N heteroatoms and superficial NiO layer on Ni layer can work synergistically to suppress the shuttle of lithium polysulfides by effective chemical interaction/adsorption.In virtue of the unique composite architecture and reinforced dual physical and chemical adsorption to the soluble polysulfides,the obtained Ni@N-CNSs/S electrode is demonstrated with enhanced rate performance(816 mAh g?1 at 2 C)and excellent long cycling life(87%after 200 cycles at 0.1 C),much better than N-CNSs/S electrode and other carbon/S counterparts.Our proposed design strategy offers a promising prospect for construction of advanced sulfur cathodes for applications in LSBs and other energy storage systems.

Rational construction of cross-linked porous nickel arrays for efficient oxygen evolution reaction

It is important but challenging to design and fabricate an efficient and cost-effective electrocatalyst for the oxygen evolution reaction(OER). Herein, we report free-standing 3 D nickel arrays with a cross-linked porous structure as interesting and high-performance electrocatalysts for OER via a facile one-step electrodeposition method. The 3 D nickel arrays are strongly anchored on the substrate, forming self-supported electrocatalysts with reinforced structural stability and high electrical conductivity. Because of their increased active surface area, abundant channels for electron/ion transportation and enhanced electronic conductivity, the designed 3 D nickel arrays exhibit superior electrocatalytic OER performance with a low overpotential(496 mV at 50 mA cm–2) and a small Tafel slope(43 mV dec–1) as well as long-term stability(no decay after 24 h) in alkaline solution. Our proposed rational design strategy may open up a new way to construct other advanced 3 D porous materials for widespread application in electrocatalysis.

Recent progress on MOF-derived carbon materials for energy storage

Metal-organic frameworks(MOFs)are of quite a significance in the field of inorganic-organic hybrid crystals.Especially,MOFs have attracted increasing attention in recent years due to their large specific surface area,desirable electrical conductivity,controllable porosity,tunable geometric structure,and excellent thermal/chemical stability.Some recent studies have shown that carbon materials prepared by MOFs as precursors can retain the privileged structure of MOFs,such as large specific surface area and porous structure and,in contrast,realize in situ doping with heteroatoms(eg,N,S,P,and B).Moreover,by selecting appropriate MOF precursors,the composition and morphology of the carbon products can be easily adjusted.These remarkable structural advantages enable the great potential of MOF-derived carbon as high-performance energy materials,which to date have been applied in the fields of energy storage and conversion systems.In this review,we summarize the latest advances in MOF-derived carbon materials for energy storage applications.We first introduce the compositions,structures,and synthesis methods of MOF-derived carbon materials,and then discuss their applications and potentials in energy storage systems,including rechargeable lithium/sodium-ion batteries,lithium-sulfur batteries,supercapacitors,and so forth,in detail.Finally,we put forward our own perspectives on the future development of MOF-derived carbon materials.

Integrated carbon nanospheres arrays as anode materials for boosted sodium ion storage

Developing cost-effective advanced carbon anode is critical for innovation of sodium ion batteries. Herein, we develop a powerful combined method for rational synthesis of free-standing binder-free carbon nanospheres arrays via chemical bath plus hydrothermal process. Impressively,carbon spheres with diameters of 150-250 nm are randomly interconnected with each other forming highly porous arrays. Positive advantages including large porosity, high surface and strong mechanical stability are combined in the carbon nanospheres arrays. The obtained carbon nanospheres arrays are tested as anode material for sodium ion batteries(SIBs) and deliver a high reversible capacity of 102 mAh g^(-1) and keep a capacity retention of 95% after 100 cycles at a current density of 0.25 A g^(-1) and good rate performance(65 mAh g^(-1) at a high current density of 2 A g^(-1)). The good electrochemical performance is attributed to the stable porous nanosphere structure with fast ion/electron transfer characteristics.

A facile path from fast synthesis of Li-argyrodite conductor to dry forming ultrathin electrolyte membrane for high-energy-density allsolid-state lithium batteries

All-solid-state lithium batteries(ASSLBs),utilizing sulfide solid electrolyte,are considered as the promising design on account of their superior safety and high energy density,whereas the time-consuming preparation process of sulfide electrolyte powders and the thickness of electrolyte layer hinder their practical application.Herein,an innovative ultimate-energy mechanical alloying plus rapid thermal processing approach is employed to rapidly synthesize the crystalline Argyrodite-type conductor Li_(5.3)PS_(4.3)ClBr_(0.7)(LPSCIBr)with superior ionic conductivity(11.7 mS cm^(-1)).Furthermore,to realize the higher energy density of the battery,an ultrathin LPSCIBr sulfide electrolyte membrane with superior ionic conductivity of 6.5 mS cm^(-1)is fabricated with the aid of polytetrafluoroethylene(PTFE)binder and the reinforced cellulose mesh.Moreover,a simple solid electrolyte interphase(SEI)is constructed on the surface of lithium metal to enhance anodic stability.Benefiting from the joint efforts of these merits,the modified ASSLBs with a high cell-level energy density of 311 Wh kg^(-1) show an excellent cyclic stability.The assembled all-solid-state Li_(2) S/Li pouch cell can operate even under the severe conditions of bending and cutting,demonstrating the enormous potential of the sulfide electrolyte membrane for ASSLBs application.

Design of pyrite/carbon nanospheres as high-capacity cathode for lithium-ion batteries

Transition metal sulfides are emerging as promising electrode materials for energy storage and conversion.In this work,hierarchical FeS2/C nanospheres are synthesized through a controllable solvothermal method followed by the annealing process.Spherical FeS2 core is homogeneously coated by thin carbon shell.The hierarchical nanostructure and carbon coating can enhance electron transfer and accommodate the stress originated from the volume change as well as suppress the shuttle effect of polysulfide.Consequently,as the cathode material of lithium ion batteries(LIBs),the FeS2/C nanospheres exhibit high reversible capacity of 676 m Ahg^-1 and excellent cycling life with the capacity retention of 97.1%after100 cycles.In addition,even at the high current density of 1.8 C,a reversible capacity of 437 m Ahg^-1 is obtained for the FeS2/C nanospheres,demonstrating its great prospect for practical applications in highperformance LIBs.

A critical review on composite solid electrolytes for lithium batteries:Design strategies and interface engineering

The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.

Exploring NiCo2S4 nanosheets arrays by hydrothermal conversion for enhanced high-rate batteries

Highly cross-linked porous NiCo2S4 nanosheets arrays are synthesized by a high-efficiency hydrothermal conversion from the preformed electrodeposited NiCo2O4 arrays. By using thioacetamide as the sulfur source, the electrodeposited NiCo2O4 is directly converted into NiCo2O4 nanosheets arrays without hightemperature sulfurization. Higher porosity and better electrical conductivity are obtained for the NiCo2O4 nanosheets arrays. In addition, reduced diffusion paths of electrons/ions and alleviated volume expansion during cycling are achieved due to the unique porous structure of NiCo2S4. Consequently, as the cathode of alkaline batteries, the obtained NiCo2S4 nanosheets arrays show better electrochemical performance with a high specific capacity(83.5 m Ah g-1 at 0.5 A g-1) and better cycling stability(capacity retention of 93% after 5000 cycles) than the NiCo2O4 counterpart arrays(40.3 mAh g-1 at 0.5 A g-1). Our work demonstrates that sulfurization on binary metal oxides can greatly enhance electrochemical performance and shows a new way for construction of advanced electrodes for high-rate batteries.

Correction to:High‑Index‑Faceted Ni3S2 Branch Arrays as Bifunctional Electrocatalysts for Efficient Water Splitting

In the original publication,Figure S4 is an ancillary image to compare the specific surface areas of TiO2/Ni3S2 and Ni3S2 samples and it was incorrectly published.To better serve our readers,the correct figure is provided in this correction.The BET values are correct and unaffected.The corresponding figure caption,data analysis and conclusions are not affected and thus not to be changed.The authors would like to apologize for any inconvenience caused.

Nitrogen-Doped Sponge Ni Fibers as Highly Effcient Electrocatalysts for Oxygen Evolution Reaction

Controllable synthesis of highly active micro/nanostructured metal electrocatalysts for oxygen evolution reaction(OER) is a particularly significant and challenging target.Herein,we report a 3D porous sponge-like Ni material,prepared by a facile hydrothermal method and consisting of cross-linked micro/nanofibers,as an integrated binder-free OER electrocatalyst.To further enhance the electrocatalytic performance,an N-doping strategy is applied to obtain N-doped sponge Ni(N-SN) for the first time,via NH3 annealing.Due to the combination of the unique conductive sponge structure and N doping,the as-obtainedN-SN material shows improved conductivity and a higher number of active sites,resulting in enhanced OER performance and excellent stability.Remarkably,N-SN exhibits a low overpotential of 365 mV at 100 mA cm-2 and an extremely small Tafel slope of 33 mV dec-1,as well as superior long-term stability,outperforming unmodified sponge Ni.Importantly,the combination of X-ray photoelectron spectroscopy and near-edge X-ray adsorption fine structure analyses shows that γ-NiOOH is the surface-active phase for OER.Therefore,the combination of conductive sponge structure and N-doping modification opens a new avenue for fabricating new types of high-performance electrodes with application in electrochemical energy conversion devices.

Assembling Co_9S_8 nanoflakes on Co_3O_4 nanowires as advanced core/shell electrocatalysts for oxygen evolution reaction

Rational design of advanced cost-effective electrocatalysts is vital for the development of water electrolysis. Herein, we report a novel binder-free efficient CoS@CoOcore/shell electrocatalysts for oxygen evolution reaction（OER） via a combined hydrothermal-sulfurization method. The sulfurized net-like CoSnanoflakes are strongly anchored on the CoOnanowire core forming self-supported binder-free core/shell electrocatalysts. Positive advantages including larger active surface area of CoSnanoflakes,and reinforced structural stability are achieved in the CoS@CoOcore/shell arrays. The OER performances of the CoS@CoOcore/shell arrays are thoroughly tested and enhanced electrocatalytic performance with lower over-potential(260 m V at 20 m A cm) and smaller Tafel slopes（56 mV dec-1） as well as long-term durability are demonstrated in alkaline medium. Our proposed core/shell smart design may provide a new way to construct other advanced binder-free electrocatalysts for applications in electrochemical catalysis.

Corrigendum to“Directional construction of Cu2S branch arrays for advanced oxygen evolution reaction”39(2019)61-67

The authors regret that the Fig.S3 in supporting information of this published article needs to be revised.And the BET values are correct and unaffected.All the conclusions in the manuscript are unaffected by this unintentional error.