Manganese Batteries Research Articles

Dielectric properties and high temperature thermochemical properties of the pyrolusite-pyrite mixture during reduction roasting

Manganese sulfate is widely used in electrolytic manganese production, catalysts, batteries, and other fields. However, the preparation of manganese sulfate from conventional roasting process of pyrolusite with additive of pyrite has disadvantages including long roasting time and low efficiency. Thus, microwave heating is used as an alternative for the preparation of manganese sulfate instead of traditional heating to destroy the dense structure of minerals and to further improve the heating efficiency which is dominating by dielectric properties of the material. Therefore, to evaluate the mechanism of preparation of manganese sulfate with microwave heating, experiments were carried out to explore the dielectric and thermochemical properties of pyrolusite-pyrite mixture at high temperature. The dielectric properties of pyrolusite-pyrite mixtures with different ratios were measured at high temperature using the resonant cavity perturbation technique, which has been widely used to study the dielectric properties of different metallurgical materials. It was found that with the increase of temperature, the microwave absorption properties of pure pyrolusite decreased from 28.173 F/M to 25.931 F/M. The wave-absorbing property of the soft pyrite/pyrite mixture increased to 41.218 F/M, indicating that pyrite can obviously improve the wave-absorbing property of the mixture. In addition, the characteristics of pyrolysis and reduction were studied systematically, and the pyrolysis and reduction process was divided into four stages according to the difference of temperature: 30 ℃-200 ℃, 200 ℃-400 ℃, 400 ℃-600 ℃, 600 ℃-900 ℃, corresponding to the separation of adsorbed water and bound water, MnO2 decomposition, desulfurization redox reaction of FeS2 and desulfurization redox reaction of Fe(1-x) S, respectively. This work highlights the possibility of reducing manganese ore by microwave heating with an additive of pyrite and finds that pyrite can modify the microwave absorption properties of pyrolusite.

Environmental and economic optima of solar home systems design: A combined LCA and LCC approach

This paper compares the economic and environmental optimal design of Solar Home Systems (SHSs) and explores the role of economic incentives (such as tariffs and technology costs) in approximating the two optima. To achieve that, we present a methodology for the environmental and economic evaluation of grid-connected SHSs: user-scale electric systems involving a photovoltaic (PV) power system and a battery energy storage system. The proposed methodology is based on a mixed integer linear programming (MILP) optimization, life cycle assessment and life cycle costing. This methodological framework is applied to a case study involving a typical SHS installation in Italy. The results of the environmental optimal design brought to the evaluation of a 3.25 kW PV assisted by 8.66 kWh of nickel cobalt manganese batteries, whereas the costs of the SHS are minimized by a small PV system (less than 1 kW). Results underline that the environmental optimal configurations rely on battery technologies, which entails a significant cost compared to the grid connection. In contrast, the economic optimal design solutions is less impactful than the grid mix both from an environmental and economic points of view. Thanks to a reduction of batteries and PV costs, the environmental impact of the economic optimal design is expected to decrease in the future.

Life Cycle Assessment of Classic and Innovative Batteries for Solar Home Systems in Europe

This paper presents an environmental sustainability assessment of residential user-scale energy systems, named solar home systems, encompassing their construction, operation, and end of life. The methodology adopted is composed of three steps, namely a design phase, a simulation of the solar home systems’ performance and a life cycle assessment. The analysis aims to point out the main advantages, features, and challenges of lithium-ion batteries, considered as a benchmark, compared with other innovative devices. As the environmental sustainability of these systems is affected by the solar radiation intensity during the year, a sensitivity analysis is performed varying the latitude of the installation site in Europe. For each site, both isolated and grid-connected solar home systems have been compared considering also the national electricity mix. A general overview of the results shows that, regardless of the installation site, solid state nickel cobalt manganese and nickel cobalt aluminium lithium-ion batteries are the most suitable choices in terms of sustainability. Remarkably, other novel devices, like sodium-ion batteries, are already competitive with them and have great potential. With these batteries, the solar home systems’ eco-profile is generally advantageous compared to the energy mix, especially in on-grid configurations, with some exceptions.

A novel method of preparing ultrafine ZnS particles from waste zinc–manganese batteries by evaporation–separation, sulfurization and inert gas condensation

This paper explores a novel method to produce ultrafine ZnS particles, a high value-added product, from waste zinc–manganese battery through evaporation–separation, sulfurization and inert gas condensation process. The heating temperature, condensation temperature, nitrogen gas pressure and condensation distance were identified as the main factors influencing the morphology of ZnS nanoparticles produced. Ultrafine ZnS particles can be prepared when the heating temperature is 873 K, the condensation temperature is 723 K and the nitrogen gas pressure is 1000–1500 Pa at the condensation distance of 30 cm. Size of ZnS particles was between 10 and 100 nm with average size of about 40 nm. Based on the scientific graphing and statistical analysis, the size of ZnS particles follows the log-normal distribution. This study not only provides the theoretical fundamentals for preparing ultrafine ZnS particles, but also provides a simple and efficient method to recycle the high value-added ZnS products from waste zinc–manganese batteries.

Boundaries of high-power charging for long-range battery electric car from the heat generation perspective

High-power charging (HPC) has been associated with a great potential to shorten the charging time, relative to increasing the all-electric range (AER) of battery electric cars (BECs). Such promise of applicability is however restrained by setbacks attributed to the high-voltage system of BECs, its negative influence on the battery performance, and a higher requirement of charging infrastructures. More importantly, the core issue is the functionality of the battery, as research has found that HPC may cause a high charging rate on the battery cell that consequently promotes its heat generation and eventually results in a significant loss of functionality and safety degradation. Considering these elements, the thermal reaction of a battery under HPC is seemingly the key toward the design of an effective thermal management system. Thus, we conducted the present study with a focal objective of examining the thermal reaction of a traction battery to the HPC, to evaluate the gap between existing battery technologies and HPC to find the suitable condition. We investigated the heat generation characteristics of Nickel–Cobalt–Manganese (NCM) and lithium iron phosphate (LFP) batteries by HPC testing in non-adiabatic and adiabatic conditions, respectively, for different charging rates from 0.5 to 5.0C. We analyzed and incorporated the test results to establish a model of battery heat generation, which could predict temperature rise under specified conditions. Moreover, we proposed an HPC operating boundary by considering the present battery technologies. The findings herein indicate that the increased charging rate leading to higher heat generation and lower charge efficiency can be effectively handled through specific thermal management, which, with the boundary, provides a limit for the optimal operation region to avoid safety risk. More practically, a good thermal management system is required to control the boundary setting and extend the operation region of battery charging.

Recycling Zinc and Preparing High-Value-Added Nanozinc Oxide from Waste Zinc–Manganese Batteries by High-Temperature Evaporation-Separation and Oxygen Control Oxidation

In this work, zinc was recycled and nanozinc oxide with high added values was prepared from waste zinc–manganese batteries by high-temperature evaporation-separation and oxygen control oxidation. Air was used as both the oxidant and the carrier gas. Because of the relatively fast oxidation rate of zinc, this Article attempts to balance the evaporation rate and oxidation rate of zinc by adding foreign materials to contend for the oxygen or covering the zinc with porous materials to isolate the oxygen. The results showed that the oxidation rate was still fast and the effect of contending for the oxygen by adding carbon powder or lead powder was not satisfied. The zinc hull was oxidized fast in the crucible and mixed with other oxides together, while covering the porous material (wire mesh, fiber felt) can accomplish the purpose of oxygen controlling. Zinc can be evaporated and separated from the zinc hull and oxidized during the zinc evaporation process, which is a benefit for producing pure nanozinc oxides. Under the experimental condition of 1123 K heating temperature, 3 kPa air pressure, and blowing air at 723 K, using fiber mat to cover the zinc hull, the recovery efficiency of zinc is ∼98.99%, and the uniform morphology of tetrapod-shaped nanozinc oxide was prepared successfully. This study provides a novel and environmentally friendly method for the resource utilization of zinc from waste zinc–manganese batteries.

Recycling metals from lithium ion battery by mechanical separation and vacuum metallurgy

The large-batch application of lithium ion batteries leads to the mass production of spent batteries. So the enhancement of disposal ability of spent lithium ion batteries is becoming very urgent. This study proposes an integrated process to handle bulk spent lithium manganese (LiMn2O4) batteries to in situ recycle high value-added products without any additives. By mechanical separation, the mixed electrode materials mainly including binder, graphite and LiMn2O4 are firstly obtained from spent batteries. Then, the reaction characteristics for the oxygen-free roasting of mixed electrode materials are analyzed. And the results show that mixed electrode materials can be in situ converted into manganese oxide (MnO) and lithium carbonate (Li2CO3) at 1073K for 45min. In this process, the binder is evaporated and decomposed into gaseous products which can be collected to avoid disposal cost. Finally, 91.30% of Li resource as Li2CO3 is leached from roasted powders by water and then high value-added Li2CO3 crystals are further gained by evaporating the filter liquid. The filter residues are burned in air to remove the graphite and the final residues as manganous-manganic oxide (Mn3O4) is obtained.

废旧锌锰电池的回收利用技术的研究进展

随着电池使用量的增加，越来越多的人开始关注废旧电池的回收利用。锌锰电池中含有多种金属及重金属，其回收利用技术也在不断地发展进步。本文综述了近几年来废旧锌锰电池的回收利用技术方面的技术进展，分析了各种方法之间的联系以及各自的优缺点，并对废旧锌锰电池的回收利用的发展前景作了更深层次的探讨。 More and more attention of the recycling of the waste battery has been attracted with the increase of the battery usage. There are many kinds of metal and heavy metal in zinc manganese battery; its recycling technology is constantly developing. This paper describes the technological progress in the recovery and utilization of Waste Zinc Manganese Batteries in recent years, and analyzes the relation among various processing methods and their advantages and disadvantages. The development prospects of the recovery and utilization of Waste Zinc Manganese Batteries was also discussed.

폐 알칼리망간전지의 산 침출액으로부터 버네사이트(δ-MnO2)의 제조 및 1-naphthol 제거

폐 알칼리망간전지의 산 침출액으로부터 버네사이트(δ-MnO2)의 제조 및 1-naphthol 제거

Recovery of metal values from spent manganese batteries using thermal treatment

This study focused on a newly proposed recycling process to recover electrodic powder enriched with manganese and zinc from spent manganese batteries. In addition, this new process was designed to prevent the explosion of batteries during thermal treatment under inert atmosphere. Spent manganese batteries were heated over a range of 300–600°C for 2 h and each component was completely separated inside the reactor after experimentation. Electrodic powder was successfully recovered from bulk components containing several pieces of metal through a sieving operation. The electrodic powder obtained was examined by X-ray diffraction (XRD) and atomic absorption spectroscopy (AA) and image of the powder was taken by scanning electron microscopy (SEM). It was found that manganese and zinc were recovered at rates of 36 and 23 wt-% respectively in the electrodic powder.

Preparation of zinc nano structured particles from spent zinc manganese batteries by vacuum separation and inert gas condensation

Vacuum separation and inert gas condensation were adopted to recycle zinc and prepare zinc nano-particles from spent zinc manganese batteries in this paper. As a result of the relatively high vapor pressure, zinc can be easily separated from the other metals in zinc manganese batteries by vacuum evaporation with a high separation efficiency. Simultaneously, morphology controlled zinc nano-particles were prepared by inert gas condensation. The results showed that inert gas pressure, heating and condensing temperature, condensation distance away from the evaporation source, and condensation substrate were the significant factors on nano-particles preparation. Higher inert gas pressure was beneficial for preparing inerratic nano-particles because of the diffusing effect. At higher heating temperature and lower condensing temperature, more inerratic nano-particles could be prepared. With more collisions and cementations, the particles became irregular at the places far away from the heater. It was also observed that nano structured particles with different morphologies including hexagonal prisms, fibriform and sheet shapes were prepared on different substrates. Uniform zinc nano hexagonal prisms with the diameter of 100–300nm and the purity of more than 99wt.% were successfully prepared on the quartz substrate under the optimized conditions as follows: 1000Pa inert pressure, 1073K heating temperature, lower than 473K condensing temperature and 10–30cm condensation distance. The zinc separation efficiency can attain to 99.68%. This work provided an efficient and promising way for recycling zinc with high purity and high added values from spent zinc manganese batteries.

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.

The influence of spent household batteries to the organic fraction of municipal solid wastes during composting

The objective of this work was to investigate the potential transfer of 9 heavy metals from spent household batteries (zinc–carbon and alkaline–manganese batteries) to the organic fraction of municipal solid wastes during active composting. Six runs were performed including one control and 2 replications. Eleven types of alkaline and non-alkaline batteries were added at 3 different levels to the organic fraction of municipal solid wastes, namely at percentages equal to 0.98% w/w (low), 5.2% w/w (medium) and 10.6% w/w (high). Experiments were performed in 230 l insulated plastic aerobic bioreactors under a dynamic air flow regime for up to 60 days. Iron, copper and nickel masses contained in the organic fraction of the wastes were found significantly higher in the high level runs compared to the corresponding masses in the control. No metal transfer was obtained in the low and medium level runs. Metal mass balance closures ranged from 51% to 176%. Metals' concentrations in the leachates were below 10 mg l −1 for most metals, except iron, while an increasing concentration trend versus time was measured in the leachates of the high level runs. In all cases, the contents of 5 regulated heavy metals in all end products were below the Hellenic limits.

Electrochemical performance of high specific capacity of lithium-ion cell LiV 3O 8//LiMn 2O 4 with LiNO 3 aqueous solution electrolyte

The electrochemical performance of aqueous rechargeable lithium battery (ARLB) with LiV 3O 8 and LiMn 2O 4 in saturated LiNO 3 electrolyte is studied. The results indicate that these two electrode materials are stable in the aqueous solution and no hydrogen or oxygen produced, moreover, intercalation/de-intercalation of lithium ions occurred within the range of electrochemical stability of water. The electrochemical performance tests show that the specific capacity of LiMn 2O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries.

One-Step Pyrolysis Process for Recover Zinc and Mercury from Spent Zinc-Manganese Batteries

In this paper, One-step pyrolysis process for the recovery of mercury and zinc from spent zinc–manganese batteries is proposed. Laboratory tests were performed to remove mercury and zinc from spent batteries and recover them. Correctitude test were used to analyze the effect of three factors: temperature, weight and time on the removing and recovery efficiency of zinc. In this research, temperature is dominant factor, weight and time are subordinate. After removing mercury, higher temperature could assure the removing efficiency of mercury above 99.9% at the same time of removing zinc. Under 0.02 MPa, efficiency of removing and recycling of zinc were investigated. The removing efficiency is 94.2% at 950 °C and 96.2% at 1000 °C. When the heated time is 1.5 h, the removing efficiency is 95.6%, which reach the aim 95.0%. With the increase of sample weight, the necessary heated time could be kept within 2.5 h without the loss of removing efficiency. The recycling efficiency of zinc could approach 75%. The content of zinc is above 99.0% in condensed zinc product. After being treated, the residue mass is about 40% of sample.

Removal of molybdenum from MnSO 4 solution with freshly precipitated “nascent” Mn 3O 4

The scavenging of molybdenum from MnSO 4 solution with freshly precipitated “nascent” Mn 3O 4 is reported. Firstly, nascent Mn 3O 4 was prepared from MnSO 4 solution by adding NaOH and aerating. The aeration time had a significant influence on the preparation of nascent Mn 3O 4, but other factors such as pH and ageing time had little effect. SEM, XRD, particle size and surface area analysis were used to characterize nascent Mn 3O 4. A study was then carried out on the effects of time, concentration of Mn, initial pH, temperature and dosage of nascent Mn 3O 4 on the adsorption of Mo from MnSO 4 solution. The results showed that the concentration of Mo in 70–200 g L − 1 MnSO 4 at pH 1–3 could be reduced from about 1 mg L − 1 to less than 0.015 mg L − 1 in 30 min at 80 °C by the addition of about 0.3 g L − 1 nascent Mn 3O 4 in suspension. Accordingly, the removal capacity of nascent Mn 3O 4 can reach 4.42 mg Mo/g Mn 3O 4. This Mo removal exceeds the requirement for special electrolytic MnO 2 used in the production of alkaline zinc–manganese batteries.

The proton exchange chemistry of layered Ni(OH) 2 for two types of high-capacity cathode materials in rechargeable batteries

Based on the studies of the first proton exchange/remove of layered Ni(OH) 2, super nickel oxide has been prepared with strongly alkaline concentrated sodium hypochlorite solution. The primary alkaline super nickel battery equipped with the prepared NiOOH cathode provides an energy capacity 2 times as large as that of the existing alkaline manganese batteries under high drain. In addition, according to the second proton exchange of Ni(OH) 2, the layered NiOOLi has also been synthesized by means of the proton/Li-ion exchange of super nickel oxide in LiOH solution, and then in molten lithium hydroxide. It provides higher discharge voltage and capacity than that of the widely adopted LiCoO 2 and LiMn 2O 4.

Nonwovens as Separators for Alkaline Batteries: An Overview

An overview of the manufacturing processes and performance requirements of nonwoven separators used in primary and secondary alkaline battery systems is presented. The systems described are alkaline manganese (Alk-Mn), nickel-cadmium , nickel-metal-hydride , nickel-zinc , and zinc-air batteries. The separators used in these systems consist totally or partially of nonwoven materials. Accordingly, the paper starts with an overview of the typical methods of nonwoven production (web formation, bonding, and post-treatment) and how the products behave within the different battery systems. The paper then discusses the advantages and disadvantages of the different nonwoven products as battery separators in the various electrochemical systems.

Development of Metal Recovery Process from Alkaline Manganese Batteries in Sulfuric Acid Solutions

A process for the recovery of Mn from a waste of spent alkaline batteries using sulfuric acid and hydrogen peroxide has been investigated. The proposed procedure consisted of mechanical separation of metal-containing particles and a leaching process. The effects of leaching agent, reaction temperature, time and pulp density for the leaching were also examined. Crushing and sieving of the spent batteries resulted in satisfactory separation of particle size from the waste. 99% Zn and 97% Mn were successfully extracted from the spent battery powder by the leaching at 60°C for 60 min with the addition of hydrogen peroxide as a reducing agent. The hydrogen peroxide addition led to almost doubling Mn extraction compared to without it.

Studies of corrosion inhibitors for zinc–manganese batteries: quinoline quaternary ammonium phenolates

Three compounds, hydroxyethyl quinoline quaternary ammonium phenolate, hydroxyethyl quinoline quaternary ammonium para-methyl phenolate and hydroxyethyl quinoline quaternary ammonium para-nitro phenolate were synthesized and tested as corrosion inhibitors for zinc–manganese batteries. Such quaternary ammonium salts derived from heterocylic molecule containing N atoms possess a higher density electron cloud around the functional groups and provide a larger projective area. From the analysis of bi-directional polarization curves and the electrochemical impedance spectra of zinc electrode measured in 26% NH 4Cl solutions containing one of these compounds, we demonstrated that the first two compounds exhibit good inhibiting effects toward zinc corrosion as the result of adsorption on zinc surface at open-circuit conditions. These compounds desorb from the surface and will no longer hinder the dissolution of zinc once the zinc electrode is anodically polarized to certain extent. This property is desirable for corrosion inhibitor to be used in chemical batteries.