ZnO-Embedded Expanded Graphite Composite Anodes with Controlled Charge Storage Mechanism Enabling Operation of Lithium-Ion Batteries at Ultra-Low Temperatures

As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered by the poor diffusion kinetics of Li ions(Li^(+)).Here,zinc oxide(ZnO) nanoparticles are incorporated into the expanded graphite to improve Li^(+)diffusion kinetics,resulting in a significant improvement in lowtemperature performance.The ZnO-embedded expanded graphite anodes are investigated with different amounts of ZnO to establish the structurecharge storage mechanism-performance relationship with a focus on lowtemperature applications.Electrochemical analysis reveals that the ZnOembedded expanded graphite anode with nano-sized ZnO maintains a large portion of the diffusion-controlled charge storage mechanism at an ultra-low temperature of-50℃ Due to this significantly enhanced Li^(+)diffusion rate,a full cell with the ZnO-embedded expanded graphite anode and a LiNi_(0.88)Co_(0.09)Al_(0.03)O_(2)cathode delivers high capacities of 176 mAh g^(-1)at20℃ and 86 mAh g^(-1)at-50℃ at a high rate of 1 C.The outstanding low-temperature performance of the composite anode by improving the Li^(+)diffusion kinetics provides important scientific insights into the fundamental design principles of anodes for low-temperature Li-ion battery operation.

Properties of a new type Al/Pb-0.3%Ag alloy composite anode for zinc electrowinning

An A1/Pb-0.3%Ag alloy composite anode was produced via composite casting. Its electrocatalytic activity for the oxygen evolution reaction and corrosion resistance was evaluated by anodic polarization curves and accelerated corro- sion test, respectively. The microscopic morphologies of the anode section and anodic oxidation layer during accelerated corrosion test were obtained by scanning electron microscopy. It is found that the composite anode （hard anodizing） dis- plays a more compact interracial combination and a better adhesive strength than plating tin. Compared with industrial Pb-0.3%Ag anodes, the oxygen evolution overpotentials of A1/Pb-0.3%Ag alloy （hard anodizing） and A1/Pb-0.3%Ag alloy （plating tin） at 500 A.m-2 were lower by 57 and 14 mV, respectively. Furthermore, the corrosion rates of Pb-0.3%Ag alloy, A1/Pb-0.3%Ag alloy （hard anodizing）, and A1/Pb-0.3%Ag alloy （plating tin） were 13.977, 9.487, and 11.824 g.m-2.h-1, respectively, in accelerated corrosion test for 8 h at 2000 A-m-2. The anodic oxidation layer of A1/Pb-0.3%Ag alloy （hard anodizing） is more compact than Pb-0.3%Ag alloy and A1/Pb-0.3%Ag alloy （plating tin） after the test.

Polar interaction of polymer host-solvent enables stable solid electrolyte interphase in composite lithium metal anodes

The lithium(Li) metal anode is an integral component in an emerging high-energy-density rechargeable battery.A composite Li anode with a three-dimensional(3 D) host exhibits unique advantages in suppressing Li dendrites and maintaining dimensional stability.However,the fundamental understanding and regulation of solid electrolyte interphase(SEI),which directly dictates the behavior of Li plating/stripping,are rarely researched in composite Li metal anodes.Herein,the interaction between a polar polymer host and solvent molecules was proposed as an emerging but effective strategy to enable a stable SEI and a uniform Li deposition in a working battery.Fluoroethylene carbonate molecules in electrolytes are enriched in the vicinity of a polar polyacrylonitrile(PAN) host due to a strong dipole-dipole interaction,resulting in a LiF-rich SEI on Li metal to improve the uniformity of Li deposition.A composite Li anode with a PAN host delivers 145 cycles compared with 90 cycles when a non-polar host is employed.Moreover,60 cycles are demonstrated in a 1:0 Ah pouch cell without external pressure.This work provides a fresh guidance for designing practical composite Li anodes by unraveling the vital role of the synergy between a 3 D host and solvent molecules for regulating a robust SEI.

An α-Fe_(2)O_(3)/Circulating Fluidized Bed Fly Ash Based Geopolymer Composite Anode for Electrocatalytic Degradation of Indigo Carmine Dye Wastewater

Geopolymers have been developed to various catalysts due to their advantages.However,low conductivity restricts their application in the electrocatalysis field.In this study,anα-Fe_(2)O_(3)/circulating fluidized bed fly ash based geopolymer(CFAG)composite anode was fabricated using a facile dip-coating method by loadingα-Fe_(2)O_(3) in the matrix of CFAG.The effects ofα-Fe_(2)O_(3) content on the composition,surface morphology and electrochemical performance ofα-Fe_(2)O_(3)/CFAG composite anode were investigated.The X-ray diffraction(XRD)and scanning electron microscope(SEM)results demonstrated thatα-Fe_(2)O_(3) was successfully inlaid with the surface of amorphous CFAG matrix.The electrochemical measurements indicated thatα-Fe_(2)O_(3)/CFAG composite anode had higher oxygen evolution potential,greater electrochemical activity area,and smaller electrochemical impedance than CFAG.The as-prepared composite anode was applied for electrocatalytic degradation of indigo carmine dye wastewater.It was discovered that the highest degradation efficiency over 10α-Fe_(2)O_(3)/CFAG reached up 92.6%,and the degradation of indigo carmine followed pseudo-first-order kinetics.Furthermore,10α-Fe_(2)O_(3)/CFAG composite anode presented excellent stability after five cycles.The active hydroxyl radical was generated over theα-Fe_(2)O_(3)/CFAG composite anode,which acted as strong oxidizing agents in the electrocatalytic degradation process.

Single-step Preparation of Nano-homogeneous NiO/YSZ Composite Anode for Solid Oxide Fuel Cells

Homogeneous co-precipitation and hydrothermal treatment were used to prepare nano- and highly dispersed Ni O/YSZ(yttria-stabilized zirconia) composite powders. Composite powders of size less than 100 nm were successfully prepared. This process did not require separate sintering of the YSZ and Ni O to be used as the raw materials for solid oxide fuel cells. The performance of a cell fabricated using the new powders(max.power density ~0.87 W/cm^2) was higher than that of a cell fabricated using conventional powders(max. power density ~0.73 W/cm^2). Co-precipitation and hydrothermal treatment proved to be very effective processes for reducing cell production costs as well as improving cell performance.

Development of High Efficient Composite Anodes

A new type of high efficient Ti composite anodes for electrodeposition of MnO 2 was successfully developed and was widely satisfied with production in many factories in China. The process parameters of electrolysis in using the composite anodes were optimized and discussed.

Properties of Al/Conductive Coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 Composite Anode for Zinc Electrowinning

The properties of Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 composite anode for zinc electrowinning were investigated. The electrochemical performance was studied by Tafel polarization curves（Tafel）, electrochemical impedance spectroscopy（EIS） and corrosion rate obtained in an acidic zinc sulfate electrolyte solution. Scanning electron microscopy（SEM）, X-ray diffraction（XRD）, and energy dispersive X-ray spectroscopy（EDXS） were used to observe the microstructural features of coating. Anodes of Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2, Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC, Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-ZrO2, and Pb-1%Ag anodes were also researched. The results indicated that the Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 showed the best catalytic activity and corrosion resistant performance; the intensity of diffraction peak exhibited the highest value as well as a new PbWO4 phase; the content of WC and ZrO2 in coating showed the highest value as well as the finest grain size.

Rare Earth Application in Sealing Anodized Al-Based Metal Matrix Composites

A new method for corrosion protection of Al-based metal matrix composites (MMC) was developed using two-step process, which involves anodizing in H2SO4 solution and sealing in rare earth solution. Corrosion resistance of the treated surface was evaluated with polarization curves. The results showed that the effect of the protection using rare earth sealing is equivalent to that using chromate sealing for Al6061/SiCp. The rare earth metal salt can be an alternative to the toxic chromate for sealing anodized Al MMC.

Preparation and Properties of Al-Ni Composite Anodic Films on Aluminum Surface

Ni element was introduced to aluminum surface by a simple chemical immersion method, and A1-Ni composite anodic films were obtained by following anodizing. The morphology, structure and composition of the A1-Ni anodic films were examined by scanning electron microscopy （SEM）, energy disperse spectroscopy （EDS） and atomic force microscopy（AFM）. The electrochemical behaviors of the films were studied by means of polarization measurement and electrochemical impedance spectroscopy （EIS）. The experimental results show that the A1-Ni composite anodic film is more compact with smaller pore diameters than that of the A1 anodic film. The introduction of nickel increases the impedances of both the barrier layer and the porous layer of the anodic films. In NaC1 solutions, the A1-Ni composite anodic films show higher impedance values and better corrosion resistance.

Forging Inspired Processing of Sodium-Fluorinated Graphene Composite as Dendrite-Free Anode for Long-Life Na–CO_(2) Cells

Na–CO_(2) batteries recently are emerging as promising energy-storage devices due to the abundance of Na in the earth’s crust and the clean utilization of greenhouse gas CO_(2) .However,similar to metallic Li,metallic Na also suffers from a serious issue of dendrite growth upon repeated cycling,while a facile method to solve this issue is still lacking.In this work,we report an effective,environmentally friendly method to inhibit Na dendrite growth by in situ constructing a stable,NaF-rich solid electrolyte interface(SEI)layer on metallic Na via adding a small amount(~3 wt%)of fluorinated graphene(FG)in bulk Na.Inspired by the forging processing,a uniform Na/FG composite was obtained by melting and repetitive FG-adsorbing/hammering processes.The Na/FG–Na/FG half cell exhibits a low voltage hysteresis of 110–140 mV over 700 h at a current density up to 5 mA cm^(-2) with an areal capacity as high as 5 mAh cm^(-2).Na–CO_(2) full cell with the Na/FG anode is able to sustain a stable cycling of 391 cycles at a limited capacity of 1000 mAh g^(-1).Long cycle life of the cell can be attributed to the protecting effect of the in situ fabricated NaF-rich SEI layer on metallic Na.Both experiments and density functional theory(DFT)calculations confirm the formation of the NaF-rich SEI layer.The inhibition effect of the NaF-rich SEI layer for Na dendrites is verified by in situ optical microscopy observations.

Review on lithium metal anodes towards high energy density batteries

Lithium metal anode(LMA) is a promising candidate for achieving next-generation high-energy-density batteries due to its ultrahigh theoretical capacity and most negative electrochemical potential. However, the practical application of lithium metal battery(LMB) is largely retarded by the instable interfaces, uncontrolled dendrites, and rapid capacity deterioration. Herein, we present a comprehensive overview towards the working principles and inherent challenges of LMAs. Firstly, we diligently summarize the intrinsic mechanism of Li stripping and plating process. The recent advances in atomic and mesoscale simulations which are crucial in guiding mechanism study and material design are also summarized. Furthermore, the advanced engineering strategies which have been proved effective in protecting LMAs are systematically reviewed, including electrolyte optimization, artificial interface, composite/alloy anodes and so on. Finally, we highlight the current limitations and promising research directions of LMAs. This review sheds new lights on deeply understanding the intrinsic mechanism of LMAs, and calls for more endeavors to realize practical Li metal batteries.

Design and application of copper/lithium composite anodes for advanced lithium metal batteries

Lithium(Li)is a promising candidate for nextgeneration battery anode due to its high theoretical specific capacity and low reduction potential.However,safety issues derived from the uncontrolled growth of Li dendrite and huge volume change of Li hinder its practical application.C onstructing dendrite-free composite Li anodes can significantly alleviate the above problems.Copper(Cu)-based materials have bee n widely used as substrates of the composite electrodes due to their chemical stability,excellent conductivity,and good mechanical strength.Copper/lithium(Cu/Li)composite anodes significantly regulate the local current density and decrease Li nucleation overp otential,realizing the uniform and dendrite-free Li deposition.In this review,Cu/Li composite methods including electrodeposition,melting infusion,and mechanical rolling are systematically summarized and discussed.Additionally,design strategies of Cu-based current collectors for high performance Cu/Li composite anodes are illustrated.General challenges and future development for Cu/Li composite anodes are presented and postulated.We hope that this review can provide a comprehensive understanding of Cu/Li composite methods of the latest development of Li metal anode and stimulate more research in the future.

Optimization of two-dimensional solid-state electrolyte-anode interface by integrating zinc into composite anode with dual-conductive phases

Solid-state electrolytes(SSEs)are a solution to safety issues related to flammable organic electrolytes for Li batteries.Insufficient contact between the anode and SSE results in high interface resistance,thus causing the batteries to exhibit high charging and discharging overpotentials.Recently,we reduced the overpotential of Li stripping and plating by introducing a high proportion of dual-conductive phases into a composite anode.The current study investigates the interface resistance and stability of a composite electrode modified with Zn and a lower proportion of dual-conductive phases.Zn-cation-adsorbed Prussian blue is synthesized as an intermediate component for a Zn-modified composite electrode(Li-FeZnNC).The Li-FeZnNC symmetric cell presents a lower interface resistance and overpotential compared with Li-FeNC(without Zn modification)and Li-symmetric cells.The Li-FeZnNC symmetric cell shows high electrochemical stability during Li stripping and plating at different current densities and high stability for 200 h.Full batteries with a Li-FeZnNC composite anode,garnet-type SSE,and LiFePO4 cathode show low charging and discharging overpotentials,a capacity of 152 mAh g^(−1),and high stability for 200 cycles.

Status and challenges facing representative anode materials for rechargeable lithium batteries

Rechargeable lithium batteries have been widely regarded as a revolutionary technology to store renewable energy sources and extensively researched in the recent several decades.As an indispensable part of lithium batteries,the evolution of anode materials has significantly promoted the development of lithium batteries.However,since conventional lithium batteries with graphite anodes cannot meet the ever-increasing demands in different application scenarios(such as electric vehicles and large-scale power supplies)which require high energy/power density and long cycle life,various improvement strategies and alternative anode materials have been exploited for better electrochemical performance.In this review,we detailedly introduced the characteristics and challenges of four representative anode materials for rechargeable lithium batteries,including graphite,Li_(4)Ti_(5)O_(12),silicon,and lithium metal.And some of the latest advances are summarized,which mainly contain the modification strategies of anode materials and partially involve the optimization of electrode/electrolyte interface.Finally,we make the conclusive comments and perspectives,and draw a development timeline on the four anode materials.This review aims to offer a good primer for newcomers in the lithium battery field and benefit the structure and material design of anodes for advanced rechargeable lithium batteries in the future.

Lithiophilic interface guided transient infiltration of molten lithium for stable 3D composite lithium anodes

Fabricating three-dimensional(3D)composite lithium anodes via thermal infusion effectively addresses uncontrollable Li deposition and large volume changes.However,potential risks due to the long wetting time and high melting point remain a critical yet unconsidered issue.Herein,we report a stable 3D composite Li anode by infusing molten Li into a 3D scaffold within 3 s at 220℃.The key-enabling technique is the growth of a lithiophilic Mg-Al double oxide(LDO)nanosheet array layer on the scaffold.The in-situ formed lithiophilic alloy,combined with the capillary forces from the nanosheet arrays,enabled the transient infiltration of molten Li.In addition,the formed high ionic-conductivity Li phase can help construct a robust solid electrolyte interphase(SEI),stabilize the Li anode/electrolyte interface,and guide uniform Li deposition.The 3D composite anode exhibited a long cycling life of 1,000 h under a current density of 1 mA·cm^(−2)and over 1,600 h under a current density of 2 mA·cm^(−2)with a high areal capacity of 4 mAh·cm^(−2)in Li/Li symmetric cells.The 3D composite anodes paired with high areal capacity LiFePO_(4)(LFP)and S cathodes demonstrate its practical application feasibility.

3-Aminopropyltriethoxysilane Complexation with Iron Ion Modified Anode in Marine Sediment Microbial Fuel Cells with Enhanced Electrochemical Performance

Anode modification plays a key role in higher power output in marine sediment microbial fuel cells(MSMFCs).A low-molecular organosilicon compound(3-aminopropyltriethoxysilane)was grafted onto the surface of carbon felt using chemical method and a composite modified anode was prepared through organic ligands coordination Fe^(3+)for better electro-chemical per-formance.Results show that the biofilm resistance of the composite modified anode(2707Ω)is 1.3 times greater than that of the unmodified anode(2100Ω),and its biofilm capacitance also increases by 2.2 times,indicating that the composite modification pro-motes the growth and attachment of electroactive bacteria on the anode.Its specific capacitance(887.8 Fm^(−2))is 3.7 times higher than that of unmodified anode,generating a maximum current density of 1.5Am^(−2).In their Tafel curves,the composite modified anodic exchange current density(5.25×10^(−6)Acm^(−2))is 5.8 times bigger than that of unmodified anode,which suggests that the electro-chemical activity of redox,anti-polarization ability and electron transfer kinetic activity are significantly enhanced.The marine sediment microbial fuel cell with the composite modified anode generates the higher power densities than the blank(203.8mWm^(−2) versus 45.07mWm^(−2)),and its current also increases by 4.4 times.The free amino groups on the anode surface expands a creative idea that the modified anode ligates the natural Fe(Ⅲ)ion in sea water in the MSMFCs for its higher power output.

Solid-state corrosion of lithium for prelithiation of SiO_(x)-C composite anode with carbon-incorporated lithium phosphorus oxynitride

In order to address the issues of low initial Coulombic efficiency of SiO_(x)-C composite anode due to the formation of solid electrolyte interphase,irreversible conversion reaction,and large volume change,the prelithiation method using metal lithium has been employed as one of effective solutions.However,violent side reactions with liquid electrolyte for prelithiation lead to low prelithiation efficiency and induce poor interface between the SiO_(x)-C electrode and liquid electrolyte.Here,a new prelithiation method with so called solid-state corrosion of lithium is developed.By replacing liquid electrolyte with solid-state electrolyte of carbon-incorporated lithium phosphorus oxynitride(LiCPON),not only various side reactions associated with metal lithium are avoided,but also the perfect interface is achieved from the decomposition products of LiCPON.The successful implementation of solid-state corrosion prelithiation can be confirmed by changes in optical image,scanning electron microscopy,and X-ray diffraction.Compared with pristine electrode,the initial Coulombic efficiency of the prelithiated electrode using solid electrolyte can be increased by about 10%,reaching 98.6%in half cell and 88.9%in full cell.Compared with prelithiated electrode using liquid electrolyte,the prelithiation efficiency of the prelithiated anode with solid-state corrosion can be increased from 25.7%to 82.8%.Solid-state corrosion of lithium is expected to become a useful method for prelithiation of SiO_(x)-C composite electrode with high initial Coulombic efficiency and large prelithiation efficiency.

Three-dimensional composite Li metal anode by simple mechanical modification for high-energy batteries

Lithium(Li)metal is believed to be the“Holy Grail”among all anode materials for next-generation Li-based batteries due to its high theoretical specific capacity(3860 mAh/g)and lowest redox potential(−3.04 V).Disappointingly,uncontrolled dendrite formation and“hostless”deposition impede its further development.It is well accepted that the construction of three-dimensional(3D)composite Li metal anode could tackle the above problems to some extent by reducing local current density and maintaining electrode volume during cycling.However,most strategies to build 3D composite Li metal anode require either electrodeposition or melt-infusion process.In spite of their effectiveness,these procedures bring multiple complex processing steps,high temperature,and harsh experimental conditions which cannot meet the actual production demand in consideration of cost and safety.Under this condition,a novel method to construct 3D composite anode via simple mechanical modification has been recently proposed which does not involve harsh conditions,fussy procedures,or fancy equipment.In this mini review,a systematic and in-depth investigation of this mechanical deformation technique to build 3D composite Li metal anode is provided.First,by summarizing a number of recent studies,different mechanical modification approaches are classified clearly according to their specific procedures.Then,the effect of each individual mechanical modification approach and its working mechanisms is reviewed.Afterwards,the merits and limits of different approaches are compared.Finally,a general summary and perspective on construction strategies for next-generation 3D composite Li anode are presented.

MoS2-based anode materials for lithium-ion batteries:Developments and perspectives

In recent years,significant progress has been achieved in the creation of innovative functional materials for energy storage and conversion.Due to their distinct physicochemical characteristics,ultrathin nanosheets composed of common layered transition metal sulfide materials(MoS2)have demonstrated promise as high-capacity anode materials for lithium-ion batteries(LIBs).Nevertheless,their practical application is severely limited by the tendency of monolayer nanosheets to restack due to strong van der Waals forces,dramatic volume changes during successive cycles,and low intrinsic conductivity.Recent research advances have shown that composite structures and nanowire morphologies with specific morphologies effectively overcome these issues.This paper reviews the recent research progress on molybdenum disulfide-based composites as anode materials for LIBs and discusses in detail the struc-tural characteristics of pure molybdenum disulfide and other composite forms of molybdenum disulfide.In addition,the phase engineering,defect engineering,and lithium storage mechanisms of molybdenum disulfide and the synthesis of molybdenum disulfide-based nanocomposites by different preparation methods are focused on.Finally,we review the design(structure),recent developments,and challenges of novel anode materials and consider their electrochemical performance in Li-ion batteries.

Sn nanoparticles embedded into porous hydrogel-derived pyrolytic carbon as composite anode materials for lithium-ion batteries

The composite powders,Sn nanoparticles embedded into the porous hydrogel-derived carbon(Sn@PHDC),were successfully prepared by polymerization and calcination processes,and the characterization results confirmed that Sn nanoparticles were homogeneously dispersed in the porous hydrogel-derived pyrolytic carbon.The coin cell assembled with the Sn@PHDC-50 composite electrode presented good cyclic stability and rate performance when the weight ratio of Sn nanoparticles to hydrogel-derived pyrolytic carbon was maintained at 1:1.Moreover,the Sn@PHDC-50 electrode manifested a lower charge transfer resistance of 58.57 Ω and a higher lithium ions diffusion coefficient of 1.117×10^(-14) cm^(2)·s^(-1) than pure Sn and other Sn@PHDC electrodes.Those improvements can be partly ascribed to the fact that the hydrogelderived pyrolytic c arbon matrix can release the volume strain and enhance the electronic conductivity of the composite electrode,and partly to the fact that the porous hydrogelderived pyrolytic carbon matrix can suppress agglomerations of Sn nanoparticles and shorten Li^(+) diffusion paths.This work may provide a new appro ach for the improvement of Sn-based anode materials for lithium-ion batteries.