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.

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.

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.

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.

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.

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.

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.

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.

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.

Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn-Air Batteries

Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability,high efficiency,and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc-air batteries.Here,3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated(referred to as PEMAC@NDCN)by a facile self-templated approach.PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability,which outperforms those of commercial Pt/C and RuO_(2).Theoretical calculations and control experi-ments reveal the boosted electron transfer,electrolyte mass/ion transports,and abundant active surface site preferences.Moreover,the constructed alkaline Zn-air battery with PEMAC@NDCN air-cathode reveals superb power density,capacity,and discharge-charge cycling stability(over 2160 cycles)compared to the reference Pt/C+RuO_(2).Solid-state Zn-air batteries enable a high power density of 211 mW cm^(−2),energy density of 1056 Wh kg^(−1),stable charge-discharge cycling of 2580 cycles for 50 mA cm^(−2),and wide temperature tolerance from−40 to 70℃with retention of 86%capacity compared to room-temperature counterparts,illustrating prospects over harsh operations.

LR6,LR03 Alkaline Hige Energy Zinc and Manganese Battery

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Hydrothermal synthesis of Mn-Zn ferrites from spent alkaline Zn-Mn batteries

Nanocrystalline Mn-Zn ferrites （Mno.GZno.4Fe204） with particle size of 12 nm were synthesized hydrotherreally using spent alkaline Zn-Mn batteries, and accompanied by a study of the influencing factors. The nanocrystals were examined by powder X-ray diffraction （XRD） for crystalline phase identification, and scanning electron microscopy （SEM） for grain morphology. The relationship between concentration of Fe（II）, Mn（II）, and Zn（II） and pH value was obtained through thermodynamic analysis of the Fe（II）-Mn（II）-Zn（II）-NaOH-H2O system. The results showed that all ions were precipitated completely at a pH value of 10-11. The optimal preparation conditions are： co-precipitation pH of 10.5, temperature of 200 ℃ and time of 9 h.

Evaluation of Al and Some of Its Alloys as Anode Materials vs γ-MnO_2 as Cathode Material and Ore Produced γ-MnO_2 vs Zn Anode in KOH Solution

In this study electrochemical performance of Al and some of its alloys （Al-Zn, Al-rvlg and Al-rvln） anodes vs MnO2 cathode were carried out in alkaline solution. The results show that the Al-Zn alloy anode has the best cell capacity among the other alloys. Cell capacity values go in the order Al-Zn〉Al-Mg〉Al〉Al-Mn. This result is probably related to the nature of passive films formed on the surface of the alloys which examined by scanning electron microscopy （SEM）. SEM morphologies of Al and its alloys showed coarse grains of passive films formed on the surface of these anode materials while Al-Mn morphology shows a needle-like structure. Electrolytic manganese dioxide （EMD） produced by electrodepositing on platinum anode from liquor resulting from reduction of low grade pyrolusite ore （β-MnO2） by sulfur slag was characterized as cathode in alkaline Zn-MnO2 batteries. Ore produced sample （EMD1） was performed well in comparison with EMD standard （EMD2） （commercial battery grade electrolytic manganese dioxide, TOSOH-Hellas GH-S）. SEM morphology of Zn anode after cell reaction was carried out and showed that Zn anode has fine grains of passive film on its surface.

Effects of temperature and concentration of sulfuric acid on the electrodeposition of grainy electrolytic manganese dioxide

The effects of temperature and the concentration of sulfuric acid on the cell voltage, the anode current efficiency of electrodeposition and the particle size of grainy electrolytic manganese dioxide （EMD） were investigated. The structure, particle size and appearance of grainy EMD were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrograph measurements. As the concentration of sulfuric acid increases, both the cell voltage and the average anode current efficiency decrease. With the increase of electrolysis temperature in the range of 30-60℃, the cell voltage, average anode current efficiency and particle size decrease. The optimum temperature of 30℃ and concentration of sulfuric acid of 2.5 mol/L for electrodeposition of the grainy EMD were obtained. XRD patterns show that the grainy EMD electrodeposited under the optimum conditions consists of γ-MnO2 and has an orthorhombic lattice structure. According to the results of SEM, the grainy EMD has a spherical or sphere-like appearance and a narrow particle size distribution with an average size of about 7μm. The grainy EMD is a promising cathode of rechargeable alkaline batteries for high energy density and a prospective precursor for production of the LiMn2O4 cathode of lithium ion batteries.

Promoting ion adsorption and desolvation kinetics enables high capacity and rate capability of stibium anode for advanced alkaline battery

Stibium(Sb)metal with high theoretic capacity,suitable negative working window and inexpensive nature are promising anode material for advanced aqueous alkaline batteries(AABs).However,the further development of Sb anode is severely hindered by the low capacity and poor rate capability which is originated from deficient adsorption of[Sb(OH)_(4)]^(-)and its sluggish desolvation kinetics.Herein,a nitrogen doped carbon cages(NCCs)substrate is constructed as high capacity and rate capability anode by promoting the adsorption and following desolvation process of[Sb(OH)_(4)]^(-)via the enhanced attraction toward(OH)-in the solvated[Sb(OH)_(4)]^(-).Consequently,the designed Sb/NCCs anode delivers a high capacity of 627 m Ah g^(-1)with an average 95%Sb utilization,an outstanding coulombic efficiency(CE)of 95%and an impressive lifespan(>110 h).Meanwhile,the Ni_(3)Se_(2)//Sb/NCCs batteries show great capacity retention of 86.7%after 2000 cycles with an areal capacity of 0.52 m Ah cm^(-2).Implementation of the designed anode allows for the construction of Sb-based AABs with enhanced rate capability,energy density and cycling performance.

Amorphous Ni-Co-S nanocages assembled with nanosheet arrays as cathode for high-performance zinc ion battery

The selection and development of cathode of alkaline zinc batteries(AZBs)is still hindered and often leads to poor rate capability and short cycle life.Here,amorphous hollow nickel-cobalt-based sulfides nanocages with nanosheet arrays(AM-NCS)are designed and constructed with ZIF-67 as the selftemplate to exchange with Ni^(2+) and S^(2-) by using a two-step ion exchange method.The synthesized AM-NCS possess the high specific capacity(160 m Ah/g at 2 A/g),and the assembled battery has excellent rate performance(146 m Ah/g reversible capacity at 5 A/g).The assembled device has excellent rate performance(155 m Ah/g at 2 A/g)and long cycling stability(7000 cycles,62.5%of initial capacity).The excellent electrochemical properties of the electrode materials are mainly attributed to the unique structure,in particular,polyhedron structure with hollow structure can improve the cyclic stability,and the amorphous structure can expose more reactive sites on the surfaces of nickel,cobalt and sulfur.This work provides a new strategy for the design and fabrication of high performance cathode materials for AZBs.

Electrochemical performances of four lanthanum transition-metal complex oxides

As novel negative electrode materials for alkaline batteries, the electrochemical properties of four lanthanum transition-metal (La-TM) complex oxides LaTiO(3), LaVO(4), LaCrO(3) and LaMnO(3) were investigated. X-ray diffraction (XRD) and scanning electron microscope (SEM) were employed to characterize their microstructures. All the La-TM oxides were made up of single phases. Electrochemical measurements showed that the maximum discharge capacities of LaTiO(3), LaVO(4), LaCrO(3), and LaMnO(3) electrodes at 303 K were 367, 187, 318, and 278 mAh/g, respectively. X-ray photoelectron spectroscopy (XPS) and XRD Rietveld analysis were carried out to discuss the electrochemical reaction mechanism. Electrode kinetics was studied by electrochemical impedance spectrum (EIS). The results showed that the maximum discharge capacity was directly related to the charge-transfer resistance (R(ct)) of La-TM oxide electrode. The cyclic properties of the four oxides should be further improved and the discharge capacity of LaMnO(3) (about 96 mAh/g) was the highest after 10(th) charge/discharge cycles.