Zn Mn Batteries Research Articles

Synthesis of and Characterization of Polyhedron of Mn<sub>2</sub>O<sub>3</sub> Nanoparticles Using Spent Zn-Mn Batteries

Polyhedron composed of Mn2O3nanoparticles with an average diameter of 0.5-1.0 μm have been prepared using spent Zn-Mn batteries. The product was characterized by X-ray powder diffraction and scanning electron microscope. The adsorption performance of polyhedron composed of Mn2O3 for 2-(5-Bromo-2-pyridylazo)-5-(diethylamino) phenol was investigated. The adsorbent showed high efficiency for the removal of 2-(5-Bromo-2-pyridylazo)-5-(diethylamino) phenol in water. The equilibrium of adsorption was achieved within 40 min. The isotherm adsorption data obeyed the Langmuir model, with a maximum adsorption capacity of 62 mg g-1.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10%

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu2+ improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu2+ content increased from 0 to 0.8g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu2+ catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe3+ based on a cycle of Fe3+/Fe2+. However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe3+/Fe2+, stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu2+ catalytic bioleaching of spent ZMBs.

The Properties of LiMn2O4 Synthesized by Molten Salt Method Using MnO2 as Manganese Source Recycled from Spent Zn-Mn Batteries

The Properties of LiMn2O4 Synthesized by Molten Salt Method Using MnO2 as Manganese Source Recycled from Spent Zn-Mn Batteries

Preparation of Zn–Mn ferrite from spent Zn–Mn batteries using a novel multi-step process of bioleaching and co-precipitation and boiling reflux

Synthesis of wide-application Zn–Mn ferrite soft magnetic materials using spent Zn–Mn batteries as starting raw materials has attained growing attentions in recent years. The multi-step series processes of reductive acid leaching and oxidative co-precipitation and high temperature calcination or hydrothermal reaction were generally utilized to carry out the conversion. In this work, a novel multi-step process of bioleaching and co-precipitation at 30°C and boiling reflux at 100°C, which was characteristic of low cost, environmental friendliness and energy saving, was attempted to accomplish the conversion for the first time. The results showed that synthesis of Zn–Mn ferrite using bioleaching liquor as a precursor was feasible. NaOH was the best coprecipitator for manufacturing the soft magnetic material from bioleaching liquor compared with NaHCO3 and NH4HCO3. Higher pH value of the second co-precipitation at 13.0, higher total concentration of Mn2++Zn2++Fe2+ at 2.0mol/l and longer reflux time at 5h were essential for greater magnetization and better crystallinity. Under optimum conditions, this novel multi-step process harvested soft magnetic material with highest saturation magnetization of 102emu·g−1, offering an alternative to convert spent Zn–Mn batteries into Zn–Mn ferrite.

Optimization of bioleaching conditions for metal removal from spent zinc‐manganese batteries using response surface methodology

AbstractBACKGROUNDAs a special residue containing zinc and manganese, spent Zn–Mn batteries cause a serious concern due to their toxicity, abundance and permanence in the environment, and biotechnological recovery of Zn and Mn is one method of recycling this waste. In this study identification of the optimum values of the effective parameters in biotechnological processes was investigated using response surface methodology.RESULTSThe released dose of Zn and Mn was highly dependent on many parameters. Non‐linear equations were formulated to describe the relationship between bioleaching efficiency of Zn and Mn and four important parameters. The optimum parameter values were determined as follows: dose of mixed energy substrates, exogenous‐acid pH adjustment, incubating temperature and pulp density of 28 g L−1, 1.9, 33 °C, 9.7%, respectively, for Zn release and 29 g L−1, 1.8, 36.7 °C, 8%, respectively, for Mn mobilization. The maximum predictive extraction efficiency of Zn and Mn was 52.5% and 52.4%, respectively.CONCLUSIONThe maximum efficiency of extraction of both Zn and Mn reached 50% under optimum conditions after 9 days of bioleaching. Additionally, XRD analyses suggested that Zn and Mn existed mainly as Hetaerolite (ZnMn2O4) in the spent Zn–Mn batteries, which gradually disappeared and released Zn2+ and Mn2+ into solution during bioleaching process. © 2014 Society of Chemical Industry

Electrochemical evaluation of manganese reducers – Recovery of Mn from Zn–Mn and Zn–C battery waste

Extraction of manganese from ores or battery waste involves the use of reductive reagents for transformation of MnO2 to Mn2+ ions. There are many reducers, both organic and inorganic, described in the literature. A series of 18 reducers has been discussed in the paper and they were classified according to standard redox potential (pE = −log ae− where pE is used to express formal electron activity and ae- is formal electron activity). The experiments of manganese extraction from paramagnetic fraction of Zn–C and Zn–Mn battery waste in the laboratory scale have been described for 3 reducers of different origin. The best result was achieved with oxalic acid (75%, with the lowest redox potential) and urea (with typical redox potential) appeared inactive. Extraction supported by hydrogen peroxide resulted in moderate yield (50%). It shows that formal thermodynamic scale is only preliminary information useful for selection of possible reducers for manganese extraction resources.

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H2SO4 (2molL−1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37–40°C and 300Am−2. The most of MnO2 and a small quantity of electrolytic MnO2 are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi0.5Mn1.5O4 material of lithium-ion battery. The as-synthesized LiNi0.5Mn1.5O4 discharges 118.3mAhg−1 capacity and 4.7V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO2. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.

Study on the performance of LiCoxMn2−xO4−yFy using spent alkaline Zn–Mn batteries as manganese source

Abstract We have successfully synthesized the spinel LiCo x Mn 2 − x O 4 − y F y cathode materials by simple sol-gel method using the manganese source that is recovered from spent alkaline Zn–Mn batteries through hydrometallurgy recycling technology. The charge–discharge curves demonstrate that the LiCo 0.1 Mn 1.9 O 4 exhibited good cycling performance with 94.0% capacity retention after 100 cycles. The LiMn 2 O 3.9 F 0.1 possesses the maximum initial discharge capacity of 124.54 mAh · g − 1 . The LiCo 0.1 Mn 1.9 O 3.9 F 0.1 has the best comprehensive performance. The initial discharge capacity of LiCo 0.1 Mn 1.9 O 3.9 F 0.1 is 120.7 mAh · g − 1 , the capacity retention is 91.7% after 100 cycles.

Study on the performance of LiMn2O4 using spent Zn–Mn batteries as manganese source

Recycling spent Zn–Mn batteries by synthesizing the products with high added value is very active internationally. In this work, we have successfully synthesized the spinel LiMn2O4 cathode materials for rechargeable lithium-ion batteries by simple sol–gel method using the manganese source that is recovered from spent Zn–Mn batteries through hydrometallurgy recycling technology. The influence of sintering temperature on the structure, the morphological properties, and the electrochemical properties of the product is investigated. The results show that spinel LiMn2O4 prepared at 700 °C has the best comprehensive performance. Moreover, the electrochemical performance of spinel LiMn2O4 has been further optimized by Co-ion doping.

Rapid analysis on the heavy metal content of spent zinc–manganese batteries by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) technique was used to investigate the applicability for the rapid analysis on the heavy metals in spent Zn–Mn batteries. Besides the major elements carbon and zinc, a number of minor and trace elements, such as iron, manganese, vanadium, chromium, aluminum, silicon, calcium, copper, magnesium and lead were identified in the positive and negative electrode materials, and their concentrations were determined. It was found that the concentrations of heavy metals of vanadium, vanadium, manganese, zinc, iron and copper were high in the mixture of positive electrode material, while zinc and lead had high concentration in the negative electrode material. These heavy metals are of a great harm to the environment and human health.

Synthesis of Spherical Assembly Composed of MnO<sub>2</sub> Nanoparticles Using Spent Zn-Mn Batteries

Spherical assembly composed of MnO2 nanoparticles with an average diameter of 0.8-2.0 μm have been prepared using spent Zn-Mn batteries. The product was characterized by X-ray powder diffraction and scanning electron microscope. The adsorption performance of spherical assembly composed of MnO2 for methyl red was investigated. The adsorbent showed high efficiency for the removal of methyl red in water. The equilibrium of adsorption was achieved within 30 min. The isotherm adsorption data obeyed the Langmuir model, with a maximum adsorption capacity of 92.6 mg g-1.

Analysis of reasons for decline of bioleaching efficiency of spent Zn–Mn batteries at high pulp densities and exploration measure for improving performance

The reasons for decline of bioleaching efficiency of Zn and Mn from spent batteries at high pulp densities were analyzed; the measures for improving bioleaching efficiency were investigated. The results showed that extraction efficiency of Zn dropped from 100% at 1% of pulp density to 29.9% at 8% of pulp density, with Mn from 94% to only 2.5%. It was almost the linear reduction of the activity of the sulfur-oxidizing bacteria with increase of pulp density that witnessed declined bioleaching efficiency of Zn; it was the complete inactivation of the iron-oxidizing bacteria at 2% of pulp density or higher that witnessed declined bioleaching dose of Mn. By means of reducing initial pH value of leaching media, increasing concentration of energy matters and exogenous acid adjustment of media during bioleaching, the maximum extraction efficiency of almost 100% for Zn and 89% for Mn at 4% of pulp density was attained, respectively.

Bioleaching of zinc and manganese from spent Zn–Mn batteries and mechanism exploration

In this work, bioleaching was used to extract valuable Zn and Mn from spent Zn–Mn batteries. The results showed that 96% of Zn extraction was achieved within 24 h regardless of energy source types and bioleaching bacteria species. However, initial pH had a remarkable influence on Zn release, extraction dose sharply decreased from 2200 to 500 mg/l when the initial pH value increased from 1.5 to 3.0 or higher. In contrast to Zn, all the tested factors evidently affected Mn extraction; the maximum released dose of 3020 mg/l was obtained under the optimum conditions. The acidic dissolution by biogenic H 2SO 4 by the non-contact mechanism was responsible for Zn extraction, while Mn extraction was owed to both contact/biological and non-contact mechanisms. The combined action of acidic dissolution of soluble Mn 2+ by biogenic H 2SO 4 and reductive dissolution of insoluble Mn 4+ by Fe 2+ resulted in 60% of Mn extraction, while contact of microbial cells with the spent battery material and incubation for more than 7 days was required to achieve the maximum extraction of Mn.

ChemInform Abstract: Mn—Zn Soft Magnetic Ferrite Nanoparticles Synthesized from Spent Alkaline Zn—Mn Batteries.

AbstractMn0.5Zn0.5Fe2O4 nanoparticles are prepared using spent alkaline batteries as raw materials by a multi‐step process including acid leaching, chemical treatment of iron shells, and citrate—nitrate precursor auto‐combustion.

Mn–Zn soft magnetic ferrite nanoparticles synthesized from spent alkaline Zn–Mn batteries

Using spent alkaline Zn–Mn batteries as raw material, Mn–Zn soft magnetic ferrite nanoparticles are prepared by multi-step processes including acid leaching, chemical treatment of battery iron shells and citrate-nitrate precursor auto-combustion. Acid leaching and chemical treatment mechanisms are investigated. Dried gels thermal decomposition process, auto-combustion, phase composition, morphological and magnetic properties of as-prepared Mn–Zn ferrite nanoparticles are characterized by thermogravimetric and differential thermal analysis, X-ray powder diffraction, transmission electron microscopy and vibrating sample magnetometer. Synthesized Mn–Zn ferrite nanoparticles (Mn0.5Zn0.5Fe2O4) have pure ferrite phase, larger saturation magnetization (Ms=60.62emug−1) and lower coercivity (Hc=30Oe) compared with the same composition ferrites prepared by other techniques due to better crystallinity. Mn–Zn ferrite nanoparticles synthesis method presents a viable alternative for alkaline Zn–Mn batteries recycling.

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

Nanocrystalline Mn–Zn ferrites (Mn 0.6Zn 0.4Fe 2O 4) with particle size of 12 nm were synthesized hydrothermally 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–H 2O 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 °C and time of 9 h.

Study on preparation of nanocrystalline ferrites using spent alkaline Zn–Mn batteries

The nanocrystalline ferrites were synthesized by sol–gel and self-propagating combustion methods using spent alkaline Zn–Mn batteries dissolved in nitric acid. The thermal decomposition process of dried gels, the essence of auto-combustion and the morphological structure of nanocrystalline ferrites were investigated by using DTA, TG, IR, XRD and SEM. The precise metal ion stoichiometry of the nanocrystalline ferrites was analyzed by ICP. The results demonstrated that the essence of auto-combustion of the dried gels was oxidation–reduction reaction induced by heat and the nanocrystalline Mn–Zn ferrites with a diameter of 20 nm could be prepared directly by auto-combustion reaction.

The dissolution mechanism of cathodic active materials of spent Zn–Mn batteries in HCl

The cathodic active materials of spent Zn–Mn batteries are complicated. The majority materials that they contain are Mn(OH) 2, Mn 2O 4, λ-Mn 2O 2, ZnMn 2O 4, Zn(NH 3) 2Cl 2, [Zn(OH) 2] 4·ZnCl 2, etc. Dissolving these kinds of materials is important to the environmental pollution control and materials recycle. In present paper we investigated the dissolution mechanism of the cathodic active materials in HCl by testing the factors that can influence the dissolution procedure, including temperature, time, and the concentration of HCl and H 2O 2. Our results showed that both neutralization and oxidation–reduction reactions occurred in the dissolution process, and that H 2O 2 had a great effect on the dissolution efficiency.

Study on preparation of manganese–zinc ferrites using spent Zn–Mn batteries

Studies on preparing manganese–zinc ferrites by coprecipitation method using spent Zn–Mn batteries have been carried out to determine the influential factors on preparing process, including coprecipitation pH value, coprecipitation temperature and calcining temperature, etc. Results show that the suitable preparing conditions are: coprecipitation pH value, 7–7.5; copecipitation temperature, 50 °C and calcining temperature, 1100–1150 °C. It also finds that Fe powder is the suitable material to remove Hg existing in spent Zn–Mn batteries completely.

Polishing apparatus

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H2SO4 (2 mol L−1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37–40 °C and 300 A m−2. The most of MnO2 and a small quantity of electrolytic MnO2 are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi0.5Mn1.5O4 material of lithium-ion battery. The as-synthesized LiNi0.5Mn1.5O4 discharges 118.3 mAh g−1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO2. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.