Zinc-carbon Batteries Research Articles

Electrical Characteristics According to the Manufacturing Process of the Flexible Li/MnO2 Primary Cell

Manganese dioxide (<TEX>$MnO_2$</TEX>) is one of the most important cathode materials used in both aqueous and non-aqueous batteries. The <TEX>$MnO_2$</TEX> polymorph that is used for lithium primary batteries is synthesized either by electrolytic (EMD-<TEX>$MnO_2$</TEX>) or chemical methods (CMD-<TEX>$MnO_2$</TEX>). Commonly, electrolytic manganese dioxide (EMD) is used as a cathode mixture material for dry-cell batteries, such as a alkaline batteries, zinc-carbon batteries, rechargeable alkaline batteries, etc. The characteristics of lithium/manganese-dioxide primary cells fabricated with EMD-<TEX>$MnO_2$</TEX> powders as cathode were compared as a function of the parameters of a manufacturing process. The flexible primary cells were prepared with EMD-<TEX>$MnO_2$</TEX>, active carbon, and poly vinylidene fluoride (PVDF) binder (10 wt.%) coated on an Al foil substrate. A cathode sheet with micro-porous showed a higher discharge capacity than a cathode sheet compacted by a press process. As the amount of EMD-<TEX>$MnO_2$</TEX> increased, the electrical conductivity decreased and the electrical capacity increased. The cell subjected to heat-treatment at <TEX>$200^{\circ}C$</TEX> for 1 hr showed a high discharge capacity. The flexible primary cell made using the optimum conditions showed a capacity and an average voltage of 220 mAh/g and 2.8 V, respectively, at <TEX>$437.5{\mu}A$</TEX>.

Electrodeposition of Zn and Zn–Mn alloy coatings from an electrolytic bath prepared by recovery of exhausted zinc–carbon batteries

The electrodeposition of galvanic coatings was performed using a chloride-based acidic electrolytic bath containing polyethylene glycol (PEG) as an additive. The electrolytic bath was prepared using Zn and Mn recovered from exhausted zinc–carbon batteries by means of acid leaching with HCl. The coatings were obtained potentiostatically at −1.2V and −1.6V (vs. Ag/AgCl) and galvanostatically with a current density of −10mAcm−2. The results indicated that the presence of PEG in the bath during galvanostatic deposition favored the formation of a coating containing a mixture of Zn and Zn–Mn alloy with an Mn content of around 2wt%.

Microbial Recovery of Manganese using &amp;lt;i&amp;gt;Staphylococcus Epidermidis&amp;lt;/i&amp;gt;

Manganese minerals are widely distributed throughout the globe. The most important industrial uses of Mn are in the manufacture of steel, non-ferrous alloys, carbon-zinc batteries and some chemical reagents. Microbial recovery of manganese from low grade manganese ores using bioleaching was investigated in this paper. A bacterial strain, Staphylococcus epidermidis (MTCC-435) was collected from microbial type culture collection, IMTECH Chandigarh and used for the experiment. The experimental results for bioleaching with S. epidermidis showed that under pH 5.5, particle size –150 μm, pulp density 10%, temperature 35℃ and agitation 200 rpm, about 80% of Mn was recovered within 20 days of incubation.

Characterization of Spent Household Zinc-Carbon Dry Cell Batteries in the Process of Recovery of Value Metals

Spent zinc-carbon dry cell batteries were characterized to assess the environmental impacts and also, to identify the potentials of recovering the metal values from these batteries. Different component parts of both new and spent batteries of all the five types (AAA, AA, C, D and 9V) were examined. The outer steel casings were found to be tin plated. Steel, zinc and manganese constituted 63 percent of the total weight of the battery. Average zinc and manganese contents were about 22 and 24 percent of the total weight of spent batteries. The electrolyte paste of the spent batteries contained 22 wt. percent zinc and 60 wt. percent manganese. The rest was chlorine, carbon and small amounts of iron and other impurity elements. The major phases in the fresh batteries were carbon, MnO2 and NH4Cl, while Zn(NH3)2Cl2, ZnO.Mn2O3, Mn3O2 and Mn2O4 were the prominent phases in the spent batteries. Presence of mercury and cadmium were not detected and a small percentage of lead was found in both the zinc anode and in the electrolyte paste.

신개념 재활용기술을 이용한 폐망간전지 및 폐리튬이온전지의 효율적 처리방안

Annually above 1 billion unit cells (15,000 tons) of spent batteries have been generated as wastes in Korea. Spent Ni-Cd batteries have been recycled but the other spent batteries did not be treated yet. So recycling processes of spent lithium-ion battery and zinc carbon battery should be developed for environmental aspect as well as the effective utility of resources. In case of spent zinc-carbon and alkaline battery, magnetic material and zinc sheet from the battery were regained by physical treatment process. A series of mechanical processing is conducted in the following sequence to yield enriched Zn and Mn particles: crushing, magnetic separation, sieving and classification. The crushed particles including Zn and Mn were dissolved in sulfuric acid solution with hydrogen peroxide as a reducing agent. After removing impurities such as Fe, Cu and Al, Zinc sulfate and Manganese sulfate were precipitated into compounds powders by low pressure vaporization process. These co-precipitated metal-compounds could be used for feedstuff. In case of spent Li-ion battery, physical treatment of waste LIBS is consist of discharge, dehydration, dry, and crushing step; crushing, magnetic separation, and screening. The leaching was carried out on -16 mesh crushed powders of lithium ion batteries by using diluted sulfuric acid solution and reducing agent. After removing impurities such as Fe, Cu and Al, cobalt ion was separated by solvent extraction process. Purified cobalt sulfate solution could be used for source of lithium secondary battery. Therefore the recycling process of spent lithium secondary battery without waste solution could be developed.

HEAVY METAL ACCUMULATION IN Ipomoea reptans AND Helianthus annuus.

Heavy metals contaminations are among the most hazardous environmental pollution due to its ability to resist disintegration in the natural ecosystem. Thus, they pose risk to living organisms as they are persistent in the environment. Reports on the accumulations of heavy metal in edible plants had alarmed many parties that the general public has become more aware on the seriousness of this issue. Bioaccumulation within the food chain poses potential risks of toxicity effects. Thus, it is crucial to conduct appropriate study to analyze the pathway of the heavy metal elements as a measure to understand the behavior of the heavy metal elements. The aim of this paper is to investigate heavy metal accumulation in plant tissue, particularly the leave, stem and root. Ipomoea reptans and Helianthus annuus were selected as the experimental plant species in the study. Spent dry cell or batteries were utilized as the source of heavy metal contamination of which batteries are commonly discarded in the municipal solid waste stream. Results indicated that the accumulation of heavy metals in the two plants were low and below the limit of European Union Standard for edible plants. However, heavy metal in alkaline batteries exposure was found to promote the growth of longer root in both plants as compared to carbon-zinc batteries and the control. Yet, the accumulation of heavy metal in the plants tissues in this study were only monitored for the period based on the maturation of the plants, longer exposure may result with different outcome, that further investigation is deemed necessary. (Keywords: heavy metal, batteries, edible plants, bioaccumulations)

Nanomaterial-Enhanced All-Solid Flexible Zinc−Carbon Batteries

Solid-state and flexible zinc carbon (or Leclanche) batteries are fabricated using a combination of functional nanostructured materials for optimum performance. Flexible carbon nanofiber mats obtained by electrospinning are used as a current collector and cathode support for the batteries. The cathode layer consists of manganese oxide particles combined with single-walled carbon nanotubes for improved conductivity. A polyethylene oxide layer containing titanium oxide nanoparticles forms the electrolyte layer, and a thin zinc foil is used as the anode. The battery is shown to retain its performance under mechanically stressed conditions. The results show that the above configuration can achieve solid-state mechanical flexibility and increased shelf life with little sacrifice in performance.

Acidic leaching and precipitation of zinc and manganese from spent battery powders using various reductants

The main objective of this study was to investigate the effects of reductive acidic leaching and further precipitation on the recovery of manganese and zinc from spent alkaline and zinc-carbon battery powders. Ascorbic acid (AA), citric acid (CA) and oxalic acid (OA) were tested as the reductants. Sodium hydroxide and potassium hydroxide were used as precipitating agents. OA with H(2)SO(4) or HCl was not effective on the leaching of zinc due to the formation of zinc oxalate precipitates. However, the other reducing agents (CA and AA) tested under various experimental conditions were effective in the acidic leaching of both zinc and manganese. Leaching yields of both manganese and zinc were higher at leach temperature of 90 degrees C than those at 30 degrees C. Leach solutions were purified by the selective precipitation of manganese and zinc using KOH or NaOH. Complete precipitation was obtained for Mn at pH 9-10 and for Zn at pH 7-8. The use of ascorbic acid or citric acid as reductants in acidic leaching appears to be effective in the simultaneous leaching and further recovery of zinc and manganese from spent alkaline and zinc-carbon battery powders.

Development of a combined pyro- and hydro-metallurgical route to treat spent zinc–carbon batteries

The potential of solvent extraction using Cynanex ®272 for the recovery of zinc from spent zinc carbon batteries after a prior leaching in hydrochloric acid has been investigated. The elemental analysis of the spent material was carried out by ICP-MS. The major metallic elements are: ZnO (41.30%), Fe 2O 3 (4.38%), MnO 2 (2.69%), Al 2O 3 (1.01%), CaO (0.36%) and PbO (0.11%). The quantitative leaching by hydrochloric acid showed that the dissolution rates are significantly influenced by temperature and concentration of the acid solutions. The experimental data for the dissolution rates have been analyzed and were found to follow the shrinking core model for mixed control reaction with surface chemical reaction as the rate-determining step. About 90.3% dissolution was achieved with 4 M HCl solution at 80 °C with 0.050–0.063 mm particle size within 120 min at 360 rpm. Activation energy value of 22.78 kJ/mol and a reaction order of 0.74 with respect to H + ion concentration were obtained for the dissolution process. An extraction yield of 94.23% zinc by 0.032 M Cyanex ®272 in kerosene was obtained from initial 10 g/L spent battery leach liquor at 25 ± 2 °C and at optimal stirring time of 25 min. Iron has been effectively separated by precipitation prior to extraction using ammoniacal solution at pH 3.5, while lead and other trace elements were firstly separated from Zn and Fe by cementation prior to iron removal and zinc extraction. Finally, the stripping study showed that 0.1 M HCl led to the stripping of about 95% of zinc from the organic phase.

A review of technologies for the recovery of metals from spent alkaline and zinc–carbon batteries

The main aim of this paper is to review and evaluate the recovery studies and associated technologies for metals from spent batteries. More attention was given especially to the recovery of Zn and Mn from spent alkaline and zinc–carbon batteries. Nowadays much research work is concentrated on the recovery of Zn and Mn from alkaline and zinc–carbon batteries. Various different metal recovery processes including physical, pyrometallurgical and hydrometallurgical ones are discussed. Compared to pyrometallurgical methods, hydrometallurgical methods are becoming a well-established and efficient method for recovering metals from raw materials. Although there have been many proposed or currently applied recovery processes majority of them are effective only in recovering certain components of spent batteries. Considering the more stringent regulations and cost, environmental protection, preservation of raw materials issues; thus, effective, economical and practical recovery technologies are required not only for metal recoveries but also for other components of batteries such as plastic, paper, steel, etc. More research work should be conducted to develop such recovery technologies. In addition, process control and plant optimization studies should also be conducted for more feasible full-scale applications.

RVC as new carbon material for batteries

Results of the last 10 years of our investigations on the use of reticulated vitreous carbon (RVC®) in various types of cells show that this kind of porous conductive glassy carbon can be successfully used as a matrix for active mass and as a current collector in many primary and secondary batteries. This paper focuses mainly on the use of RVC® modified with metals like Pt, Rh, Pd, Ni, Pb and their oxides in construction of the following types of cells: (1) zinc-carbon primary and secondary batteries, (2) rechargeable cell systems with NiOOH cathode, (3) electrochemical capacitors with Pd and Pd–Rh alloys, and (4) lead acid battery. The most important improvement in performance has been achieved with lead-acid and zinc-carbon batteries. Especially for the modified zinc-carbon battery, which has been constructed in the popular AA format, manufactured on a small (laboratory) scale, and tested according to the IEC norms as a battery for commercial use, the capacity has been higher by ca. 20% compared with the batteries available on the market. Also, results obtained for thin layers of Pd and their alloys deposited on RVC® are promising in terms of the application of these kinds of electrodes in electrochemical capacitors. The pseudocapacitance of a Pd–Rh/RVC® composition may reach 540 F g−1.

Reductive leaching of manganese and zinc from spent alkaline and zinc–carbon batteries in acidic media

The main purpose of this work was to investigate the effectiveness of oxalic acid as a reductant for the leaching of manganese and zinc from spent alkaline and zinc–carbon batteries in sulfuric acid or hydrochloric acid media. Three different types of battery powders were tested: zinc–carbon, alkaline and mixed (50% zinc–carbon, 50% alkaline). Kinetic tests were initially conducted with the mixed battery powder. Leaching experiments were carried out according to 2 4 full factorial design, and regression equations for the leaching of Mn and Zn were determined. Washing of the powders (neutral leaching) was effective on the removal of potassium and chloride. Increasing solid/liquid ratio from 1/5 to 1/10 in neutral leaching did not significantly change potassium and chloride removal. A leach duration of 3 h was found to be generally sufficient for the equilibrium to be reached for both Zn and Mn. Oxalic acid concentration had strongest negative effect on Zn leaching in both sulfuric and hydrochloric acid media, whereas the concentrations of sulfuric and hydrochloric acids exhibited strongest positive effect for both Mn extraction yield (MnEY) and Zn extraction yield (ZnEY). In the range of tested conditions, pulp density had no important effect on MnEY and ZnEY for both acids. Temperature had negative effect for both MnEY and ZnEY in sulfuric acid solution; however, such effect was less pronounced in hydrochloric acid solution. For the sulfuric acid solution, 91% MnEY and 112% ZnEY were achieved at 45 °C after 3 h of leaching by 10% pulp density, − 30% oxalic acid (30% less than the stoichiometric requirement), + 30% H 2SO 4. For the hydrochloric acid solution, about 86% MnEY and 95% ZnEY were obtained at 20% pulp density, − 30% oxalic acid, + 30% HCl, at 45 °C after 3 h of leaching.

Separation of zinc from spent zinc-carbon batteries by selective leaching with sodium hydroxide

Physical methods such as crushing and sieving followed by magnetic separation steps were applied to separate non-magnetic material (88.4 wt.%) from zinc-carbon spent batteries. The oversize material was processed by eddy current separation to recover zinc sheet, carbon rods, and plastics. The undersize fraction (− 2.36 mm) with a metal composition of 15.5% Zn, 17.5% Mn, and 1.4% Fe was used for the leaching experiments under different conditions such as concentration of sodium hydroxide, temperature, agitation speed, and pulp density. Selective leaching using 4 mol dm − 3 NaOH at 100 g dm − 3 solid/liquid ratio, 80 °C and 200 rpm gave a zinc extraction of 82% and a manganese extraction of less than 0.1%. An overall zinc recovery was about 88.5% by the processes described in this study.

Portable Power: Inventor Samuel Ruben and the Birth of Duracell

This article explores the invention and commercialization of mercury and alkaline batteries by independent inventor Samuel Ruben and his licensee, the P. R. Mallory Company, known today as Duracell. During World War II, the Army Signal Corps turned to the National Inventors Council to help them solve operational problems with zinc-carbon batteries; Ruben invented a more reliable mercury battery, which Mallory manufactured. Ruben and Mallory then adapted the cells for peacetime applications like hearing aids, watches, and pacemakers, placing miniature batteries at the vanguard of the postwar miniaturization movement alongside the more heralded transistor. The company later developed cheaper alkaline batteries and modified its marketing strategy, transforming the battery from a component of other products to a consumer product in its own right. Mallory effectively pursued a “mixed innovation strategy,” relying on long-term consulting relationships with outside inventors like Ruben while simultaneously investing in its own scientific research laboratories.

Preparation of Mn-Zn Ferrite from Spent Zinc-Carbon Batteries by Alkali Leaching, Acid Leaching and Co-Precipitation

The treatment of spent zinc-carbon batteries for the recovery of valuable metals followed by conversion to Mn−Zn ferrite has been conducted employing two-stage alkali and acid leaching and co-precipitation method. In the first stage, leaching process was carried out with 4 M NaOH, which resulted in a recovery of 63.4 %Zn and 0.1% Mn. Electrowinning of alkali leaching solution containing 12.75 g/L Zn at a current density of 0.2 A/cm2 produced Zn metal of 15 nm to 30 nm size and 99.9% purity. The second stage leaching of residue with 3 M H2SO4 and 6 vol.% H2O2 at a solid/liquid ratio of 1∶10 indicated the leaching efficiency of 98.0% Zn, 97.9% Mn and 55.2% Fe. The obtained leaching solution was finally adjusted to suitable mole ratios of Mn∶Zn∶Fe (1∶1∶4) by the addition of Zn and Fe sulfate salts followed by pH control to produce Mn−Zn ferrite powder. The characterization of the ferrite powder showed uniform nano-crystalline particles of about 20 nm size with spinel structure.

Reductive acid leaching of spent zinc–carbon batteries and oxidative precipitation of Mn–Zn ferrite nanoparticles

The non-magnetic 8-mesh undersize material obtained by crushing, magnetic separation and sieving of spent zinc-carbon batteries assayed 23.9% Mn, 14.9% Zn, and 4% Fe. Reductive acid leaching of this material at a solid/liquid ratio of 1:10, and 60 °C with 2 mol dm − 3 H 2SO 4 and 0.39 mol H 2O 2 extracted 97.9% Mn, 98.0% Zn and 55.2% Fe after 60 min. The leach liquor composition was then adjusted to a Mn:Zn:Fe molar ratio of 1:1:4 suitable for producing MnZnFe 4O 8 ferrite powder by adding Mn(II), Zn(II) and Fe(II) sulfates. The effect of pH in the range pH 5–12 on the precipitation of Mn–Zn ferrite powder was investigated over 60 min using O 2 gas flow rate of 1.3 dm 3 min − 1 at 80 °C. The precipitated Mn–Zn ferrite at pH 12 were 20 nm particles that had a spinel structure. The saturation magnetizations of Mn–Zn ferrite powder (Mn 1 − x Zn x Fe 2O 4) were determined to be 39–91 emu/g with various zinc contents ( x = 0.2–0.8).

Process for the recycling of alkaline and zinc–carbon spent batteries

In this paper a recycling process for the recovery of zinc and manganese from spent alkaline and zinc–carbon batteries is proposed. Laboratory tests are performed to obtain a purified pregnant solution from which metallic zinc (purity 99.6%) can be recovered by electrolysis; manganese is recovered as a mixture of oxides by roasting of solid residue coming from the leaching stage. Nearly 99% of zinc and 20% of manganese are extracted after 3 h, at 80 °C with 10% w/v pulp density and 1.5 M sulphuric acid concentration. The leach liquor is purified by a selective precipitation of iron, whereas metallic impurities, such as copper, nickel and cadmium are removed by cementation with zinc powder. The solid residue of leaching is roasted for 30 min at 900 °C, removing graphite completely and obtaining a mixture of Mn 3O 4 and Mn 2O 3 with 70% grade of Mn. After that a technical-economic assessment is carried out for a recycling plant with a feed capacity of 5000 t y −1 of only alkaline and zinc–carbon batteries. This analysis shows the economic feasibility of that plant, supposing a battery price surcharge of 0.5 € kg −1, with a return on investment of 34.5%, gross margin of 35.8% and around 3 years payback time.

Smoke Alarms by Type and Battery Life in Rural Households: A Randomized Controlled Trial

Although the use of smoke alarms is widely recommended, little guidance is available on the types of alarms and batteries that function best. This study examined smoke alarm and battery function 12 months after installation in rural residential households. An RCT, involving the installation of either a photoelectric or ionizing smoke alarm with either a lithium or carbon-zinc battery, was conducted in 643 rural Iowa households in July 2003. The functionality of each installed smoke alarm was tested 12 months later. Generalized estimating equations were used to model the effects of alarm type and battery type on alarm function and false alarms 12 months after installation. Of 643 study homes, 98.8% had at least one functioning alarm, and 81.5% had all alarms functioning 12 months after installation. No difference was observed in alarm function between photoelectric alarms and ionizing alarms 12 months after installation (OR=1.30, 95% CI=0.88, 1.92). However, photoelectric alarms had significantly lower odds of false alarms than ionizing alarms. Alarms with lithium batteries had 91% higher odds of functioning than those with carbon-zinc batteries. The main reasons for nonfunctioning included a missing battery (30.7%); a missing alarm (28%); and a disconnected battery (11.3%). Although lithium batteries and photoelectric alarms are more expensive than their counterparts, the financial investment might be worthwhile in terms of overall performance.

Selective Leaching of Zinc from Spent Zinc-Carbon Battery with Ammoniacal Ammonium Carbonate

This paper describes the ammoniacal ammonium carbonate leaching behavior of zinc and manganese from spent zinc-carbon batteries. For selective extraction of Zn from the spent zinc-carbon battery, leaching tests were carried out as a function of process parameters such as concentration of (NH4)2CO3, ammonia, temperature, time and pulp density. Physical methods of separation such as crushing was applied to reduce the material to 10–20 mm size followed by magnetic separation to separate iron with a recovery about 10 mass% leaving most of Zn and Mn in the non-magnetic fraction. Non-magnetic fraction was further subjected to sieving to separate 2.46 mm over and under size fractions. The oversize material was processed by eddy current separation to recover zinc sheet and carbon rods and plastics. The under size material with chemical composition of Zn 15.5 mass%, Mn 17.5 mass%, and Fe 1.4 mass% was used for leaching studies. Under the optimum leaching conditions (2.0 kmol/m 3 (NH4)2CO3 and 4.0 kmol/m 3 ammonia, 40 � C, 100 g/L pulp density, 30 min and 250 rpm), the leaching efficiency of zinc and manganese was 80.2% and less than 0.1%, respectively, indicating the selective recovery of zinc from the spent zinc-carbon battery. An overall zinc recovery is about 88%. [doi:10.2320/matertrans.MRA2008164]

Comparison of Acid and Alkaline Leaching for Recovery of Valuable Metals from Spent Zinc-carbon Battery

ABSTRACT The spent zinc-carbon batteries are composed of approximately 20% of Mn, 20% of Zn, magnetic materials and small amounts of carbon, plastics and electrolyte. Some of zinc metals in the spent battery reacted into zinc oxides and some of MnO2 reduced into Mn2O3 after discharging reaction. In this study, acid and alkaline processes of spent zinc-carbon battery are proposed and there performances are compared. In case of H2SO4, the results of zinc and manganese dissolution rates obtained by adding H2O2 were 93.3% and 82.2%, respectively at 100g/L solid/liquid ratio, 2.0M H2SO4, 60 °C and 200 rpm. In case of NaOH, the results of zinc and manganese dissolution rates obtained at 100g/L solid/liquid ratio, 4M NaOH, 80 °C and 200 r.p.m. were 82% and below 0.1% respectively. Therefore, the efficiency of selective extraction of Zn was very high.