Zinc-carbon Batteries Research Articles

ZnO nanoparticles preparation from spent zinc–carbon dry cell batteries: studies on structural, morphological and optical properties

ABSTRACTRecovery and recycling of valuable materials from battery waste is challenging as well as important from economic and environmental point of view. In this work, spent zinc–carbon batteries were processed with HCl and NaOH to synthesize ZnO nanoparticles. ZnO nanopowders were also prepared by using ZnCl2 as precursors with varying amount of NaOH using sol–gel method. In both cases, ZnO nano particles were characterized with XRD, XRF, FESEM, EDAX, particle size analyzer and UV–visible (UV–Vis) spectroscopy. The purity of the synthesized ZnO from spent zinc–carbon batteries was found to be 99.69%. FESEM micrographs showed the reduction in particle size from 50 nm to 20 nm with a decrease in NaOH concentration. UV–Vis study showed significant peak shift with maximum absorption between 365 nm and 359 nm region of the visible spectrum. Because of these remarkable properties, as prepared ZnO nanoparticles can find applications in biomedicine, nanoelectronic devices, sensors, nanomedicine, GATE dielectrics, photovoltaic devices, etc.

Thermal nanosizing: Novel route to synthesize manganese oxide and zinc oxide nanoparticles simultaneously from spent Zn–C battery

Abstract Spent batteries are one of the fast-growing waste streams in electronic waste due to their low cost, maintenance and versatile applications. In this study, a novel thermal route, using spent waste battery is proposed for synthesis of manganese oxide (MnO) and zinc oxide (ZnO) nanoparticles simultaneously instead of metal separation approaches. Thermal transformation of zinc-carbon (Zn C) battery black mixture at 900 °C under argon atmosphere in horizontal quartz tube furnace facilitated the formation of ZnO nanoparticles, after condensation, leaving behind the MnO nanoparticle in the residue. MnO nanoparticles are known to be high capacity anode materials for lithium ion batteries. ZnO has wide band gap and can be used in sensor and electronics applications. Mechanism of MnO and ZnO nanoparticles formation from spent Zn C battery called “Thermal nanosizing”, is established. Characterization of spent Zn C battery was conducted and synthesized nanoparticles are confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and energy dispersive spectroscopy techniques. Morphological analysis was conducted by field emission scanning electron microscopy, transmission electron microscopy and selected area electron diffraction analysis. Both MnO and ZnO nanostructures were spherical shape and within 50 nm in size. “Thermal nanosizing” a novel route, proposed in this study could be a path breaking approach to synthesize MnO and ZnO nanoparticles simultaneously from spent battery and could represent an economic value for industries along with environmental benefits.

Selection of organic acid leaching reagent for recovery of zinc and manganese from zinc-carbon and alkaline spent batteries

Zinc-carbon and alkaline batteries are often used in electronic equipment that requires small quantities of power. The waste from these batteries contains valuable metals, such as zinc and manganese, that are needed in many industries and can pollute the environment if not treated properly. This paper concerns the recovery of zinc and manganese metals from zinc-carbon and alkaline spent batteries with leaching method and using organic acid as the environmental friendly leaching reagent. Three different organic acids, namely citric acid, malic acid and aspartic acid, were used as leaching reagents and compared with sulfuric acid as non-organic acid reagents that often used for leaching. The presence of hydrogen peroxide as manganese reducers was investigated for both organic and non-organic leaching reagents. The result showed that citric acid can recover 64.37% Zinc and 51.32% Manganese, while malic acid and aspartic acid could recover less than these. Hydrogen peroxide gave the significant effect for leaching manganese with non-organic acid, but not with organic acid.

Joint optimisation of arbitrage profits and battery life degradation for grid storage application of battery electric vehicles

To meet European decarbonisation targets by 2050, the electrification of the transport sector is mandatory. Most electric vehicles rely on lithium-ion batteries, because they have a higher energy/power density and longer life span compared to other practical batteries such as zinc-carbon batteries. Electric vehicles can thus provide energy storage to support the system integration of generation from highly variable renewable sources, such as wind and photovoltaics (PV). However, charging/discharging causes batteries to degradate progressively with reduced capacity.In this study, we investigate the impact of the joint optimisation of arbitrage revenue and battery degradation of electric vehicle batteries in a simplified setting, where historical prices allow for market participation of battery electric vehicle owners.It is shown that the joint optimisation of both leads to stronger gains then the sum of both optimisation strategies and that including battery degradation into the model avoids state of charges close to the maximum at times. It can be concluded that degradation is an important aspect to consider in power system models, which incorporate any kind of lithium-ion battery storage.

Production of brown inorganic pigments with spinel structure using spent zinc-carbon batteries

In recent years, there has been an increase in the production of zinc-carbon batteries to fulfil the demand for portable energy. This has led to an increase in the spent batteries disposal, which can cause environmental problems. In this study, inorganic brown pigments were produced using electrode materials from spent zinccarbon batteries with the aim of recycling this residue as it is toxic to the environment and human health when disposed incorrectly. The pigments were produced by the solid state reaction between the oxides mixtures from spent batteries and chromium oxide and heat treated at 1200?C for two hours. The produced pigments were stable and showed good colour and opacity when applied to ceramic pieces at a decorative burning temperature (850?C). At 1050?C, only the ZMC100 sample (with initial composition having ZnMn2O4 : Cr2O3 molar ratio of 1:1) showed stability. A good result was obtained when the produced samples were compared with the standards produced by solid-state reaction of the pure commercial oxides. The compounds produced during battery discharge, favoured the formation of ZnMn2O4 with higher purity at low temperatures. Hence, the pigment produced using dry electrode materials as a precursor was more crystalline than the synthetic sample obtained under the same conditions.

UV-Visible Optical Absorbance of Graphene Oxide Synthesized from Zinc-Carbon Battery Waste via a Custom-Made Ultrasound Generator based on Liquid Sonication Exfoliation Method

The objectives of this study are i) to synthesize graphene oxide (GO) from the waste materials of zinc-carbon (ZnC) batteries via the liquid sonication exfoliation (LSE) method using tweeter piezoelectric probes as speakers, and ii) to study the optical absorbance of the GO produced using a UV-Vis spectrophotometer by varying the mass of the graphite materials obtained from ZnC battery waste. The graphite materials are obtained from the carbon rods of the ZnC batteries , which are ground into powder. The powder is then mixed with distilled water , with powder mass variation s of 0.4, 0.6, 0.8, and 1.0 grams . The solutions obtained are sonicated with a frequency of 30 kHz for six hours using a custom - made ultrasound generator based on piezoelectric probes. The effect of graphite material mass variation is studied by observing the UV-Vis spectrophotometer data before and after sonication. The results of this study show absorbance peaks at wavelengths of 221 nm to 227.5 nm , and shouldering peaks at 260 nm to 270 nm, indicating the presence of GO materials for all graphite mass variations. The best GO performances based on the UV-Vis results are obtained in samples with 0.8 and 1.0 grams of graphite powder, which undergo a red shift from 223.5 nm to 227.5 nm, respectively. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) are conducted upon the sample of 1.0 grams of graphite powder before and after sonication treatment. The SEM results before sonication show graphite materials forming in large chunks, whereas after sonication smaller islands of GO materials consisting of thin, transparent flakes are observed. The EDX results reveal that the sample material after sonication consists of 88% carbon, 11% oxygen, and a remaining 1% of aluminum, silicon, sulphur, ferrum, and zinc

Recycling portable alkaline/ZnC batteries for a circular economy: An assessment of natural resource consumption from a life cycle and criticality perspective

It has been recognized that a proper and sustainable management strategy might help prevent the risks of leaching from waste portable batteries (WPBs), which are an important waste stream, and aid the conservation of raw materials. Unlike existing studies on WPB management, which focus mainly on emissions, this case study uses a resource-oriented approach to thoroughly analyze the performance of a WPB collection and recycling scheme. This study focused on the WPB take-back and recycling system managed by Bebat in Belgium. Life cycle assessment was conducted using three different existing life cycle impact assessment (LCIA) methods representing three different perspectives: Cumulative Exergy Extracted from the Natural Environment; Abiotic Depletion Potential (ADP), split into impact categories called ADPelements and ADPfossilfuels; and damage to Resource Cost. A new LCIA method, the criticality-based impact assessment method, has also been introduced to cover the socioeconomic aspects of natural resource consumption. The performance of the mixed waste (i.e., batteries, flashlights) collection and sorting system was assessed from 2011 to 2013. This analysis showed that in 2012, the use of collection receptacles made of plastic bags with 30% recycled content, instead of non-recycled paper or cardboard with 30% recycled content, was one of the main reasons for the low impact of the whole system from all assessment perspectives. The performance of entire take-back and recycling system for alkaline and zinc-carbon (ZnC) batteries, the two most popular portable batteries, was subsequently analyzed and benchmarked against two incineration scenarios: with and without bottom ash recovery. The comparisons of the four LCIA methods show differing results. The most prominent result is that the ADPelements score of the recycling scenario is 7–9 times lower than that of the incineration scenario, mainly due to metals (i.e., iron and zinc) savings via recycling. The recycling system requires 17–52% less material criticality, but extracts 13–18% more exergy from the natural environment and has a higher ADPfossilfuels score (about 14–16%) than the incineration system. These comparisons indicate that although the alkaline/ZnC battery management system run by Bebat does not reduce consumption of all resources, especially fossil fuels and land, it is beneficial in terms of minerals and metals savings. To further improve the efficiency and environmental performance of the collection system, different measures were implemented. A sensitivity analysis was performed to evaluate the impacts of those measures on the mixed waste collection and sorting system and the alkaline/ZnC battery take-back and recycling system. The results suggested that a combination of different measures, especially reducing the number of receptacles used and enhancing their environmental performance, can considerably reduce the resource footprint.

Investigation of zinc recovery by hydrogen reduction assisted pyrolysis of alkaline and zinc-carbon battery waste

Zinc (Zn) recovery from alkaline and zinc-carbon (Zn-C) battery waste were studied by a laboratory scale pyrolysis process at a reaction temperature of 950°C for 15–60min residence time using 5%H2(g)-N2(g) mixture at 1.0L/min gas flow rate. The effect of different cooling rates on the properties of pyrolysis residue, manganese oxide particles, were also investigated. Morphological and structural characterization of the produced Zn particles were performed. The battery black mass was characterized with respect to the properties and chemical composition of the waste battery particles. The thermodynamics of the pyrolysis process was studied using the HSC Chemistry 5.11 software. A hydrogen reduction reaction of the battery black mass (washed with Milli-Q water) takes place at the chosen temperature and makes it possible to produce fine Zn particles by rapid condensation following the evaporation of Zn from the pyrolysis batch. The amount of Zn that can be separated from the black mass increases by extending the residence time. Recovery of 99.8% of the Zn was achieved at 950°C for 60min residence time using 1.0L/min gas flow rate. The pyrolysis residue contains MnO and Mn2O3 compounds, and the oxidation state of manganese can be controlled by cooling rate and atmosphere. The Zn particles exhibit spherical and hexagonal particle morphology with a particle size varying between 200nm and 3µm. However the particles were formed by aggregation of nanoparticles which are primarily nucleated from the gas phase.

Carbon rod of zinc-carbon primary battery waste as a substrate for CdS and TiO2 photocatalyst layer for visible light driven photocatalytic hydrogen production

In this research, carbon rod as a solid waste of primary Zinc-Carbon batteries was used as a substrate for CdS and TiO2 film. The film was deposited by chemical bath deposition with surfactant molecules as linker agent to promote the connection between the semiconductor film and the substrate. Material characterization was conducted to understand the phases content, its surface morphology, the quantum yield (QY) as measured through isopropanol degradation, and then their activity as a photocatalyst for visible light driven photocatalytic hydrogen production. XRD analysis found that the carbon rod waste is a mechanical mixture of amorphous carbon, represented by width broad peak lying between 22 and 25° and graphitic carbon, represented by a strong (002) peak at 26.3° and also a (001) peak at 42.2°. The result shows that CdS/Carbon (CdS/C) has higher photocatalytic activity than the TiO2/Carbon (TiO2/C) with the quantum yield value at 380nm of a photon is 1.651×10−3. Meanwhile, TiO2/C provide the value of 1.495×10−4. The QY value of CdS/C also higher than TiO2/C at 450nm of the light source. The H2 production which was conducted with CdS/C performs 1.67 times higher than the production with TiO2/C as a photocatalyst, i.e., 0.369μmols−1g−1. Meanwhile, the H2 production rate with TiO2/C is 0.222μmols−1g−1.

High performance MnO2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries

MnO2 nanoflower is prepared by electrochemical conversion of Mn3O4 obtained by heat treatment of spent zinc‒carbon batteries cathode powder. The heat treated and converted powders were characterized by TGA, XRD, FTIR, FESEM and TEM techniques. XRD analyses show formation of Mn3O4 and MnO2 phases for the heat treated and converted powders, respectively. FESEM images indicate the formation of porous nanoflower structure of MnO2, while, condensed aggregated particles are obtained for Mn3O4. The energy band gap of MnO2 is obtained from UV‒Vis spectra to be 2.4 eV. The electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge‒discharge and electrochemical impedance techniques using three-electrode system. The specific capacitance of MnO2 nanoflower (309 F g−1 at 0.1 A g−1) is around six times higher than those obtained from the heat treated one (54 F g−1 at 0.1 A g−1). Moreover, it has high capacitance retention up to 93% over 1650 cycles. Impedance spectra of MnO2 nanoflower show very small resistances and high electrochemical active surface area (340 m2 g−1). The present work demonstrates a novel electrochemical approach to recycle spent zinc-carbon batteries into high value supercapacitor electrode.

Removal of VOCs by catalytic process. A study of MnZnO composites synthesized from waste alkaline and Zn/C batteries

Spent alkaline and zinc-carbon batteries were subjected to a biohydrometallurgy process, in order to recover manganese and mixed manganese zinc oxides. Two solids were synthesized, one of them prepared by reaction of MnSO4 and KMnO4 (MnOx) and the other obtained by chemical precipitation with NaOH (ZnMnO).The characterization by XRD, TPR, FTIR and XPS revealed the presence of Mn3+ and Mn4+ cations in both samples, and the presence of ZnO and Mn-Zn spinels in ZnMnO. The samples were evaluated in the oxidation reaction of ethanol and toluene. The results in the flow reactor showed that ethanol conversion on both catalysts, MnOx and ZnMnO, is rather similar, but toluene conversion is markedly higher on MnOx, due to a greater Mn/Zn ratio and to the absence of a crystallized ZnO phase. The FTIR study demonstrated that ethanol is oxidized to acetaldehyde at low temperature, and to CO2 and CO at 400°C. Traces of CH4 in the gas phase are also detected at high temperature. The formation of ethoxy and acetate groups is observed at the catalyst surface. With respect to toluene oxidation, CO2 is detected at 300°C and when the temperature is increased, CO is also observed in the gas phase. The results showed that: (i) the alkaline and Zn-carbon batteries can be recycled as catalysts and (ii) the solids can be used in the catalytic process for VOCs control.

LEACHING OF ZINC AND MANGANESE FROM SPENT ZINC-CARBON BATTERIES IN ACETIC ACID SOLUTION

ABSTRACT: In this study, extraction of Zn and Mn from spent zinc–carbon batteries in acetic acid solution was studied. Leaching tests were carried out to evaluate the leaching behaviour of Zn and Mn under different conditions. Experimental parameters used were; stirring speed, acetic acid concentration, temperature and particle size. The zinc and manganese extraction were obtained as 83.59% and 52.47%, respectively. The maximum Zn and Mn extraction were obtained in 240 min of leaching time with the following conditions; 600 rpm stirring speed, 2.0 M acetic acid concentration, -53 µm particle size and 60°C leaching temperature.

Processing Zinc from Waste of Used Zinc-Carbon Battery with Natrium Chloride (NaCl) for Biogas Desulfurizer

This research introduces method of processing zinc obtained from waste of used zinc-carbon battery to be used as biogas desulfurizer. The zinc is processed by using Natrium Chloride (NaCl) . The zinc-carbon battery consist of carbon rod as positive terminal and zinc case container as negative terminal. The electrolyte is ammonium chloride mixed with carbon powder. In the Waste of used zinc carbon battery, the zinc case is found still remind and have a potential to be used as desulfurizer. The zinc was taken out from the used battery and chopped to become small piece. About 100 gram of chopped zinc was immersed in various concentration of NaCl (25 gr/l, 50 gr/l, 75 gr/l, and 100 gr/l) at 70°C for 4 hours. The bubble of air introduce in to the solution. The zinc then was taken out from the solution, drying and compacted as a billet with diameter 5 cm and thickness about 2 cm. The billet was installed inside the pipe and 50 liter biogas with flow rate 3 liter/minute is let flown in to the desulfurizer. The Hydrogen sulfide before and after pass the desulfurizer were measured. It is found that the desulfuriser in all variation of concentration of NaCl is working well to elimination H2S to zero level.

Effects of gas flow rate on zinc recovery rate and particle properties by pyrolysis of alkaline and zinc-carbon battery waste

Zinc (Zn) recovery rate and the properties of Zn particles obtained by pyrolysis of alkaline and Zn-C battery waste were studied at a reaction temperature of 950°C for 60min residence time using various N2(g) flow rate (0.5–3.0L/min) without using any additive. The battery black mass was characterized with respect to the properties of waste battery particles, and chemical content. The thermodynamics of the pyrolysis process was studied using the HSC Chemistry 5.11 software. A carbothermic reduction reaction of the washed battery black mass by Milli-Q water takes place at choosen temperature and makes it possible to produce fine Zn particles by a rapid condensation following the evaporation of zinc from the pyrolysis batch. The amount of Zn that can be separated from the black mass slightly increases at higher N2(g) flow rates than 0.5L/min and stabilizes by controlling the gas flow. Zn recovery of 80% was achieved at 950°C and 60min residence time using 1.0L/min and higher flow rates by pyrolysis of the washed battery black mass. The pyrolysis residue was shown to be mainly composes of MnO and Mn2O3 with traces of impurities. The particle size of the produced Zn particle decreased from 874nm to 534nm with increasing flow rate and those particles are formed by the aggregation of primary condensed particles with nano-range sizes. The morphology of the zinc particles also changes from hexagonal shape to spherical morphology by increasing gas flow rate.

Recovery of zinc and manganese, and other metals (Fe, Cu, Ni, Co, Cd, Cr, Na, K) from Zn-MnO2 and Zn-C waste batteries: Hydroxyl and carbonate co-precipitation from solution after reducing acidic leaching with use of oxalic acid

The article discusses the current situation of the spent batteries and portable accumulators management. It reviews recycling technologies of the spent batteries and portable accumulators which are used in the manufacturing installations in the world. Also, it presents the authors’ research results on the reductive acidic leaching of waste material of the zinc-carbon batteries (Zn-C) and zinc-manganese batteries (alkaline Zn-MnO2) delivered by a company dealing with mechanical treatment of this type of waste stream. The research data proved that the reductive acidic leaching (H2SO4 + C2H2O4) of the battery’s black mass allows to recover 85.0% of zinc and 100% of manganese. Moreover, it was found that after the reductive acidic leaching it is possible to recover nearly 100% of manganese, iron, cadmium, and chromium, 98.0% of cobalt, 95.5% of zinc, and 85.0% of copper and nickel from the solution with carbonate method. On the basis of the results, it is possible to assume that the carbonate method can be used for the preparation of manganese-zinc ferrite.

Preparation of polypyrrole nanocomposites for supercapacitor using spent battery powder as raw materials

A strategy has been developed to prepare conductive polymer-based nanocomposites as the electrode materials for supercapacitor with spent battery powder (SBP) as raw materials. Thus the waste resources from power could be sustainably recycled for new energy storage devices. The SBP containing manganese dioxide (MnO2) and graphite powder was obtained from the spent zinc-carbon battery, in which MnO2 was utilized for the oxidative polymerization of pyrrole. The binary graphite/polypyrrole (G/PPy) and ternary MnO2/graphite/polypyrrole (MnO2/G/PPy) nanocomposites were obtained under different reaction conditions, such as hydrochloric acid concentration, MnO2/pyrrole molar ratio, sodium p-toluene sulfonate (p-TSNa)/pyrrole molar ratio, and acid solution volume. The results showed that the electrochemical properties of the G/PPy nanocomposites were better than those of the MnO2/G/PPy. Under the optimized preparation condition (100mL of 1.5mol/L HCl with 0.03mol/L pyrrole, and MnO2/pyrrole/p-TSNa molar ratio of 1:1:1), the G/PPy nanocomposite possessed a relatively high Coulombic efficiency, a high electrical conductivity of 20.0S/cm, and the highest specific capacitance of 212.4F/g at 1mV/s scan rate tested by CV, as well as a retention of 89.5% of its original capacitance after 1000 cycles.

Reuse of Carbon Paste from Used Zinc-Carbon Battery for Biogas Desulfurizer with Clay as a Binder

Reuse of Carbon Paste from Used Zinc-Carbon Battery for Biogas Desulfurizer with Clay as a Binder

Galvanic Leaching of Chalcopyrite Using Manganese Oxides in Spent Zinc-Carbon Batteries

Galvanic Leaching of Chalcopyrite Using Manganese Oxides in Spent Zinc-Carbon Batteries

Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn–C battery waste

Production of zinc and manganese oxide particles from alkaline and zinc–carbon battery black mass was studied by a pyrolysis process at 850–950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature.

Facile electrochemical synthesis of few layered graphene from discharged battery electrode and its application for energy storage

A cost-effective, simple and non-hazardous route for synthesis of few-layered graphene from waste zinc carbon battery (ZCB) electrodes via electrochemical expansion (ECE) has been reported. In this synthesis, we have electrochemically exfoliated the graphene layers, by intercalating sodium dodecyl benzenesulfonate (SDBS) surfactant into graphitic layers at different D.C. voltages with a constant SDBS concentration. The graphene sheets were isolated, purified and characterized by Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD), Raman spectrometry, Ultraviolet absorption (UV), Selected area electron diffraction (SAED) and Cyclic voltammetry. Best result was obtained at 4.5V of D.C. A possible mechanism for the intercalation process has been proposed. A promising application of the produced material for supercapacitor application has also been explored in combination with polyaniline.