Graphitic Carbon Quantum Dots Modified Nickel Cobalt Sulfide as Cathode Materials for Alkaline Aqueous Batteries

Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.

Manganese Dioxide with High Specific Surface Area for Alkaline Battery

The authors reported a facile method for the synthesis of manganese dioxide without any template and catalyst at a low-temperature. The prepared sample was characterized with X-ray diffraction（XRD）, scanning electron microscopy（SEM）, Brunauer-Emmett-Teller（BET） surface analysis, Fourier transform infrared（FTIR） spectrometry, cyclic voltammetry, alternative current（AC） impedance test and battery discharge test. It is found that the prepared sample belongs to α-MnO2 and has a microsphere morphology and a large BET surface area. The electrochemical characterization indicates that the prepared sample displays a larger electrochemical capacitance than the commercial electrolytic manganese dioxides（EMD） in Na2SO4 solution, and exhibits larger discharge capacity than EMD, especially at a high rate discharge condition when it is used as cathode of alkaline Zn/MnO2 battery.

Synergistic inhibition effect of poly(ethylene glycol) and cetyltrimethylammonium bromide on corrosion of Zn and Zn-Ni alloys for alkaline batteries

The synergistic inhibition effect of poly(ethylene glycol)-400(PEG-400)and cetyltrimethylammonium bromide(CTMAB)on the corrosion of Zn and Zn-Ni alloys in 8 mol/L KOH solution saturated with Zn O was observed by potentiodynamic anodic/cathodic polarization(PDP),and electrochemical impedance spectroscopy(EIS)measurements.The electrochemical studies confirmed that there was a synergism between PEG-400 and CTMAB on corrosion inhibition of Zn and its alloys.Corrosion inhibition efficiency of the mixed inhibitors,250 mg/L CTMAB+250 mg/L PEG-400,was found to be much higher than that of the single inhibitor,500 mg/L PEG-400 or 500 mg/L CTMAB.Scanning electron microscopic(SEM)investigations before and after the corrosion inhibition process emphasize the synergistic effect of the mixed inhibitors.Accordingly,it was found that the addition of the investigated inhibitors to the alkaline solution enhanced the discharge and capacity of the alkaline battery anodes.The obtained electrochemical data exhibited a good correlation with the computational one.

Reductive atmospheric acid leaching of spent alkaline batteries in H_2SO_4/Na_2SO_3 solutions

This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ＇mo1-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely con- verted into zincate （Zn（OH）42-） ions and thus did not co-precipitate with manganese hydroxide during this treatment （2.0 M NaOH, 90 min, 200 r/rain, pH 〉 13）. After the manganese was removed from the solution, the Zn（OH）4^2- was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

Effect of magnesium on the aluminothermic reduction rate of zinc oxide obtained from spent alkaline battery anodes for the preparation of Al–Zn–Mg alloys

The aluminothermic reduction of zinc oxide（ZnO） from alkaline battery anodes using molten Al may be a good option for the elaboration of secondary 7000-series alloys. This process is affected by the initial content of Mg within molten Al, which decreases the surface tension of the molten metal and conversely increases the wettability of ZnO particles. The effect of initial Mg concentration on the aluminothermic reduction rate of ZnO was analyzed at the following values： 0.90wt%, 1.20wt%, 4.00t%, 4.25wt%, and 4.40wt%. The ZnO particles were incorporated by mechanical agitation using a graphite paddle inside a bath of molten Al maintained at a constant temperature of 1123 K and at a constant agitation speed of 250 r/min, the treatment time was 240 min and the ZnO particle size was 450？500 mesh. The results show an increase in Zn concentration in the prepared alloys up to 5.43wt% for the highest initial concentration of Mg. The reaction products obtained were characterized by scanning electron microscopy and X-ray diffraction, and the efficiency of the reaction was measured on the basis of the different concentrations of Mg studied.

Dendritic Nanostructured Waste Copper Wires for High-Energy Alkaline Battery

Rechargeable alkaline batteries(RABs)have received remarkable attention in the past decade for their high energy,low cost,safe operation,facile manufacture,and ecofriendly nature.To date,expensive electrode materials and current collectors were predominantly applied for RABs,which have limited their real-world efficacy.In the present work,we propose a scalable process to utilize electronic waste(e-waste)Cu wires as a cost-effective current collector for high-energy wire-type RABs.Initially,the vertically aligned CuO nanowires were prepared over the waste Cu wires via in situ alkaline corrosion.Then,both atomiclayer-deposited NiO and NiCo-hydroxide were applied to the CuO nanowires to form a uniform dendritic-structured NiCo-hydroxide/NiO/CuO/Cu electrode.When the prepared dendritic-structured electrode was applied to the RAB,it showed excellent electrochemical features,namely high-energy-density(82.42 Wh kg−1),excellent specific capacity(219 mAh g−1),and long-term cycling stability(94%capacity retention over 5000 cycles).The presented approach and material meet the requirements of a cost-effective,abundant,and highly efficient electrode for advanced eco-friendly RABs.More importantly,the present method provides an efficient path to recycle e-waste for value-added energy storage applications.

Recent advances in flexible alkaline zinc-based batteries:Materials,structures,and perspectives

The development of wearable electronic systems has generated increasing demand for flexible power sources.Alkaline zinc(Zn)-based batteries,as one of the most mature energy storage technologies,have been considered as a promising power source owing to their exceptional safety,low costs,and outstanding electrochemical performance.However,the conventional alkaline Zn-based battery systems face many challenges associated with electrodes and electrolytes,causing low capacity,poor cycle life,and inferior mechanical performance.Recent advances in materials and structure design have enabled the revisitation of the alkaline Zn-based battery technology for applications in flexible electronics.Herein,we summarize the up-to-date works in flexible alkaline Zn-based batteries and analyze the strategies employed to improve battery performance.Firstly,we introduce the three most reported cathode materials(including Ag-based,Ni-based,and Co-based materials)for flexible alkaline Zn-based batteries.Then,challenges and modifications in battery anodes are investigated.Thirdly,the recently advanced gel electrolytes are introduced from their properties,functions as well as advanced fabrications.Finally,recent works and the advantages of sandwich-type,fiber-type and thin film-type flexible batteries are summarized and compared.This review provides insights and guidance for the design of high-performance flexible Zn-based batteries for next-generation electronics.

Design strategy and comprehensive performance assessment towards Zn anode for alkaline rechargeable batteries

Alkaline Zn-based primary batteries have been commercialized in the past decades.However,their success has not been extended to secondary batteries due to the poor cycle reversibility of Zn anodes.Although some research has been conducted on alkaline Zn anodes,their performance is still far from commercial requirements.A variety of degradation mechanisms,including passivation,dendrites,morphological changes,and hydrogen precipitation,are claimed responsible for the failure of alkaline Zn metal anodes.What’s worse,these constraints always interact with each other,which leads to a single strategy being unable to suppress all the issues.Therefore,a comprehensive evaluation of the positive and negative effects of various strategies on performance is important to promote the commercialization of alkaline Zn batteries.Herein,the recent progress and performance of improvement strategies for Zn anode in alkaline conditions are reviewed systematically.First,the principles and challenges of alkaline Zn anodes are briefly analyzed.Then,various design strategies for alkaline Zn anodes from the perspectives of ion and electron regulation are highlighted.Last,through a comprehensive summary of various performance parameters,the advantages and disadvantages of different strategies are compared and evaluated.On the basis of this assessment,we aim to provide more insights into the anode design of high-performance alkaline rechargeable Zn batteries.

Self-assembled three-dimensional carbon networks with accessorial Lewis base sites and variational electron characteristics as efficient oxygen reduction reaction catalysts for alkaline metal-air batteries

Heteroatom-doped carbon has been demonstrated to be one of the most promising non-noble metal catalysts with high catalytic activity and stability through the modification of the electronic and geometric structures.In this study,we develop a novel solvent method to prepare interconnected N,S co-doped three-dimensional（3D）carbon networks with tunable nanopores derived from an asso-ciated complex based on melamine and sodium dodecylbenzene sulfonate（SDBS）.After the intro-duction of silica templates and calcination,the catalyst exhibits 3D networks with interconnected 50-nm pores and partial graphitization.With the increase of the number of Lewis base sites caused by the N doping and change of the carbon charge and spin densities caused by the S doping,the designed N,S co-doped catalyst exhibits a similar electrochemical activity to that of the commercial 20-wt%Pt/C as an oxygen reduction reaction catalyst.In addition,in an aluminum-air battery,the proposed catalyst even outperforms the commercial 5-wt%Pt/C catalyst.Both interconnected porous structures and synergistic effects of N and S contribute to the superior catalytic perfor-mance.This study paves the way for the synthesis of various other N-doped and co-doped carbon materials as efficient catalysts in electrochemical energy applications.

Bismuth Oxide Selenium/Graphene Oxide Composites:Toward High-Performance Electrodes for Aqueous Alkaline Battery

Aqueous alkaline battery represents a promising energy storage technology with both high energy density and high power density as rechargeable batteries.However,the low theoretical capacities,kinetics and stability of anode materials have limited their developments and commercializations.In this study,we propose a novel method to produce two-dimensional layered bismuth oxide selenium(Bi_(2)O_(2)Se)and reduced graphene oxide(r GO)composites via a one-step hydrothermal method.The volume change caused by phase change during rapid charging and discharging is significantly reduced and the capacity reaches 263.83 m Ah g^(-1)at a current density of 0.5 A g^(-1).The Bi_(2)O_(2)Se/r GO electrode exhibits excellent cycling stability in which the capacity retention rate is 81.04%after 5000 cycles.More importantly,the Bi_(2)O_(2)Se/r GO nanosheet composite is used as the anode electrode material with MnCo_(2)O_(4.5)@Ni(OH)_(2)as the cathode electrode material in aqueous alkaline battery.When the energy density is 76.16 W h kg^(-1),the power density reaches 308.65 W kg^(-1).At a power density of 10.21 k W kg^(-1),the energy density remains as high as 33.86 W h kg^(-1).The results presented here may advance the understanding of the issues facing the development of aqueous battery anode materials.

Determination of the density of zinc powders for alkaline battery

The density of zinc powder for alkaline battery was determined using a pyknometer.The results showed that powders made before the end of 2003 could reach relative densities above 99% of the theoretical density.Investigating the relative volume swelling of electrolysed gels of zinc powders,no evident relation between swelling and pyknometer density was found.

LR6,LR03 Alkaline Hige Energy Zinc and Manganese Battery

TheNanfuBatteryCo.Ltd.inNanpingFuiian,isChina'sbiggestproducerandexporterofairlinezincandmanganesebatteries.NanfubrandandChaolibrandLR6andLR03alkalinehighenergyzinceandmanganesebatterieshavealargevolume,bigcurrent,longlife,andareleakproofandsafe,andc...

Comparison of Alkaline Treatment of Lead Contaminated Wastewater Using Lime and Sodium Hydroxide

A lead-acid storage battery manufacturing industry in India produces several thousand liters of lead con-taminated acidic wastewater on a daily basis and uses hydrated lime to render the lead-contaminated acidic wastewater alkaline (pH = 8.0). Alkaline treatment of the acidic wastewater with lime though a cost-effective method, generates copious amount of lead-contaminated gypsum sludge. Other alkali agents such as sodium hydroxide, sodium carbonate and dolomite are also used for alkali treatment of the acid wastewaters. The present paper compares the relative efficiency of hydrated lime and 0.05 M to 1 M NaOH solutions with re-spect to 1) amounts of sludge produced, 2) immobilization of the soluble lead in the acidic wastewater (AWW) and 3) increase in TDS (total dissolved solids) levels upon treatment of AWW with NaOH solutions and lime. The study also performs equilibrium speciation upon alkaline treatment of AWW with lime and NaOH (sodium hydroxide) solutions using the Visual MINTEQ program to understand the chemical reac-tions occurring during treatment process.

Perspective of alkaline zinc-based flow batteries

Energy storage technologies have been identified as the key in constructing new electric power systems and achieving carbon neutrality,as they can absorb and smooth the renewables-generated electricity.Alkaline zinc-based flow batteries are well suitable for stationary energy storage applications,since they feature the advantages of high safety,high cell voltage and low cost.Currently,many alkaline zinc-based flow batteries have been proposed and developed,e.g.,the alkaline zinc–iron flow battery and alkaline zinc–nickel flow battery.Their development and application are closely related to advanced materials and battery configurations.In this perspective,we will first provide a brief introduction and discussion of alkaline zinc-based flow batteries.Then we focus on these batteries from the perspective of their current status,challenges and prospects.The bottlenecks for these batteries are briefly analyzed.Combined with the practical requirements and development trends of alkaline zinc-based flow battery technologies,their future development and research direction will be summarized.

NixB/rGO as the cathode for high-performance aqueous alkaline zinc-based battery

Aqueous alkaline zinc batteries(AZBs)exhibit great potential due to their high capacity,high safety and low cost.However,despite these advantages,the lack of high stability and high utilization rate makes the search for high-performance cathode materials a great challenge.Here,an amorphous nickel boride/rGO(NixB/rG O)complex structure was designed.As a result of abundant unsaturated active sites and synergistic electronic effects,amorphous NixB exhibits excellent energy storage properties.As well as having high electrical conductivity,rGO avoids aggregation of NixB nanoparticles,ensuring that NixB/rGO electrodes have a high energy storage capacity.The structure has a strong adhesion between NixB and rGO,which protects its stable structure and extends its life.More importantly,the NixB/rGO//Zn full battery shows remarkable capacity(228.4 m Ah/g at 2 A/g),extraordinary cycle durability(93.7%retained after1000 cycles)and strong energy density 399.7 Wh/kg,when coupled with NixB/rGO cathode.This work will also shed light on other nickel-zinc batteries in order to achieve super durability and capacity.

Long-lifespan aqueous alkaline and acidic batteries enabled by redox conjugated covalent organic polymer anodes

Herein,we introduce a redox conjugated covalent organic polymer(p-HATN,HATN=hexaazatrinaphthylene)anode bearing HATN species for long-lifespan aqueous alkaline and acidic batteries.The p-HATN features intriguing superhydrophilicity and unique wide pH adaptability,while the conjugated network and amorphous cross-linked structure further endow p-HATN with improved electron transport,facile ion diffusion and superior acid-alkali tolerability.As a result,p-HATN exhibits fast surface-controlled redox activity and superior stability for K^(+)and H^(+)ions storage with remarkable capacity retentions in three-electrode cells(88%capacity retention in 13 M KOH over 30000 cycles;nearly 100%capacity retention in 0.5 M H_(2)SO_(4)over 54000 cycles).Moreover,the assembled p-HATN//Ni(OH)_(2)cell with 13 M KOH and p-HATN//PbO_(2)cell with 0.5 M H_(2)SO_(4)also achieve ca-pacity retentions of 83%retention over 55000 cycles and 92%over 15000 cycles,respectively,outperforming most similar systems.This work sheds light on the rational design of advanced polymer anodes for long-lifespan alkaline and acidic batteries.

Alkaline zinc-based flow battery: chemical stability, morphological evolution, and performance of zinc electrode with ionic liquid

Zinc-based flow battery is an energy storage technology with good application prospects because of its advantages of abundant raw materials,low cost,and environmental friendliness.The chemical stability of zinc electrodes exposed to electrolyte is a very important issue for zinc-based batteries.This paper reports on details of chemical stability of the zinc metal exposed to a series of solutions,as well as the relationship between the morphological evolution of zinc electrodes and their properties in an alkaline medium.Chemical corrosion of zinc electrodes by the electrolyte will change their surface morphology.However,we observed that chemical corrosion is not the main contributor to the evolution of zinc electrode surface morphology,but the main contributor is the Zn/Zn^(2+)electrode process.The morphological evolution of zinc electrodes was controlled by using ionic liquids,1-ethyl-3-methylimidazolium acetate(EMIA),and 1-propylsulfonic-3-methylimidazolium tosylate(PSMIT),and the electrode performance was recorded during the morphological evolution process.It was observed that the reversible change of zinc electrode morphology was accompanied by better electrode performance.

High-performance alkaline aqueous zinc battery enabled by nickel-cobalt-tellurium materials

The capacity and cycling performance of cathodes are key factors in aqueous zinc batteries(AZBs).The search for cathode materials with long cycle lives and high specific capacities is of paramount importance.In this study,a bimetallic telluride with a hollow polyhedral structure was synthesized using a hydrothermal method followed by vapor deposition.This composite exhibits high conductivity,facilitates rapid diffusion of electrolyte ions into the interior,and accelerates redox reactions,thereby enhancing electrochemical performance.The CoTe_(2)-NiTe_(2) electrode demonstrates an impressive specific capacity of 188.8 mAh/g at 1 A/g,highlighting its efficiency in storing a significant amount of charge per unit mass during electrochemical reactions.The assembled CoTe_(2)-NiTe_(2)//Zn battery shows favorable capacity retention(76.4%)after 10000 cycles.The energy density is remarkably high,reaching 290.3 Wh/kg,while maintaining a power density of 1.75 kW/kg.This bimetallic telluride strategy holds great promise as an alternative cathode for AZBs.

Iron-incorporated nitrogen-doped carbon materials as oxygen reduction electrocatalysts for zinc-air batteries

The application of electrocatalysts for the oxygen reduction reaction(ORR) is vital in a variety of energy conversion technologies. Exploring low-cost ORR catalysts with high activity and long-term stability is highly desirable, although it still remains challenging. Herein, we report a facile and reliable route to convert ZIF-8 modified by Fe-phenanthroline into Fe-incorporated and N-doped carbon dodecahedron nanoarchitecture(Fe-NCDNA), in which carbon nanosheets are formed in situ as the building blocks with uniform Fe-N-C species decoration. Systematic electrochemical studies demonstrate that the as-synthesized Fe-NCDNA electrocatalyst possesses highly attractive catalytic features toward the ORR in terms of activity and durability in both alkaline and neutral media. The Zn-air battery with the optimal Fe-NCDNA catalyst as the cathode performs impressively, delivering a power density of 184 m W cm^–2 and a specific capacity of 801 m Ah g^–1;thus, it exhibits great competitive advantages over those of the Zn-air devices employing a Pt-based cathode electrocatalyst.

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.