同槽电解法处理锌—锰废干电池机理研究

针对锌 锰干电池的构成特点 ,结合所采用的研究工艺 ,从试验机理角度对采用同槽电解法处理锌 锰废干电池的工艺方法和工艺条件进行了分析和研究 ,提出了新型的实现废干电池资源化处理技术路线。     

废干电池中锌和汞的分布及其处理

由于民众缺乏环境意识和国家没有相应法规 ,大多数废干电池都随手丢弃 ,回收的废电池处于不同程度的腐蚀状态。介绍了锌、汞在废干电池中的分布状态以及腐蚀对其分布的影响 ,并根据它们的分布特点提出用真空法回收废干电池中的锌、汞。     

Internal short circuit and accelerated rate calorimetry tests of lithium-ion cells: Considerations for methane-air intrinsic safety and explosion proof/flameproof protection methods

Researchers with the National Institute for Occupational Safety and Health (NIOSH) studied the potential for lithium-ion cell thermal runaway from an internal short circuit in equipment for use in underground coal mines. In this third phase of the study, researchers compared plastic wedge crush-induced internal short circuit tests of selected lithium-ion cells within methane (CH₄)-air mixtures with accelerated rate calorimetry tests of similar cells. Plastic wedge crush test results with metal oxide lithium-ion cells extracted from intrinsically safe evaluated equipment were mixed, with one cell model igniting the chamber atmosphere while another cell model did not. The two cells models exhibited different internal short circuit behaviors. A lithium iron phosphate (LiFePO₄) cell model was tolerant to crush-induced internal short circuits within CH₄-air, tested under manufacturer recommended charging conditions. Accelerating rate calorimetry tests with similar cells within a nitrogen purged 353-mL chamber produced ignitions that exceeded explosion proof and flameproof enclosure minimum internal pressure design criteria. Ignition pressures within a 20-L chamber with 6.5% CH₄-air were relatively low, with much larger head space volume and less adiabatic test conditions. The literature indicates that sizeable lithium thionyl chloride (LiSOCl₂) primary (non rechargeable) cell ignitions can be especially violent and toxic. Because ignition of an explosive atmosphere is expected within explosion proof or flameproof enclosures, there is a need to consider the potential for an internal explosive atmosphere ignition in combination with a lithium or lithium-ion battery thermal runaway process, and the resulting effects on the enclosure.     

Cadmium—Towards a rational use of a toxic element

Because of its toxicity, cadmium creates an environmental problem as well as a health hazard for exposed workers. Most cadmium emissions arise from the intentional use of the element. It is therefore mandatory to reduce cadmium consumption to the lowest possible level. Cadmium pigments, mainly used in plastic processing, can be replaced in all applications where the processing temperature does not exceed 300°C. Newly developed polyvinyl chloride stabilizers promise to be an excellent substitute for cadmium stabilizers in even the most demanding applications. Cadmium plating, still extensively used in the United States and the West Germany, has been virtually abandoned in Japan. Improved lead acid batteries are replacing vented nickel cadmium batteries because of their cost effectiveness. While in these applications cadmium use is declining, more and more cadmium is needed for the manufacturing of sealed nickel cadmium batteries. These relatively small electrochemical cells are used mainly by individual consumers. Here cadmium can only be replaced in some marginal applications. The high cadmium content of these batteries (up to 22%) makes them a good candidate for recycling of the heavy metal.     

Do lower electricity storage costs reduce greenhouse gas emissions?

In the electricity sector, innovation in large-scale storage is anticipated to reduce costs and improve performance. The effect on greenhouse gas emissions of lower storage costs depends on the interactions between storage and the entire grid. The literature has disagreed on the role of storage in reducing emissions. In this paper we present a stylized model, which suggests that the effect of storage costs on emissions depends on the supply responsiveness of both fossil and renewable generators. Under common conditions in the United States, lower storage costs are more likely to reduce emissions when wind investment responds to equilibrium electricity prices and when solar investment does not. Simulations of a computational model of grid investment and operation confirm these intuitions. Moreover, because of its effect on coal and natural gas–fired supply responsiveness, introducing a carbon dioxide emissions price may increase the likelihood that lower storage costs reduce emissions.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO₄ solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO_x synthesized in our laboratory.The characterization by XRD, FTIR and XPS reveal the presence of Mn₂O₃ in the EMO and the CMO samples, together with some Mn⁴⁺ cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn₃O₄.The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO₂.The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.     

Further study of the intrinsic safety of internally shorted lithium and lithium-ion cells within methane-air

National Institute for Occupational Safety and Health (NIOSH) researchers continue to study the potential for lithium and lithium-ion battery thermal runaway from an internal short circuit in equipment for use in underground coal mines. Researchers conducted cell crush tests using a plastic wedge within a 20-L explosion-containment chamber filled with 6.5% CH₄-air to simulate the mining hazard. The present work extends earlier findings to include a study of LiFePO₄ cells crushed while under charge, prismatic form factor LiCoO₂ cells, primary spiral-wound constructed LiMnO₂ cells, and crush speed influence on thermal runaway susceptibility. The plastic wedge crush was a more severe test than the flat plate crush with a prismatic format cell. Test results indicate that prismatic Saft MP 174565 LiCoO₂ and primary spiral-wound Saft FRIWO M52EX LiMnO₂ cells pose a CH₄-air ignition hazard from internal short circuit. Under specified test conditions, A123 systems ANR26650M1A LiFePO₄ cylindrical cells produced no chamber ignitions while under a charge of up to 5 A. Common spiral-wound cell separators are too thin to meet intrinsic safety standards provisions for distance through solid insulation, suggesting that a hard internal short circuit within these cells should be considered for intrinsic safety evaluation purposes, even as a non-countable fault. Observed flames from a LiMnO₂ spiral-wound cell after a chamber ignition within an inert atmosphere indicate a sustained exothermic reaction within the cell. The influence of crush speed on ignitions under specified test conditions was not statistically significant.     

Depollution benchmarks for capacitors,batteries and printed wiring boards from waste electrical and electronic equipment (WEEE)

The article compiles and analyses sample data for toxic components removed from waste electronic and electrical equipment (WEEE) from more than 30 recycling companies in Switzerland over the past ten years. According to European and Swiss legislation, toxic components like batteries, capacitors and printed wiring boards have to be removed from WEEE. The control bodies of the Swiss take back schemes have been monitoring the activities of WEEE recyclers in Switzerland for about 15 years. All recyclers have to provide annual mass balance data for every year of operation. From this data, percentage shares of removed batteries and capacitors are calculated in relation to the amount of each respective WEEE category treated. A rationale is developed, why such an indicator should not be calculated for printed wiring boards. The distributions of these de-pollution indicators are analysed and their suitability for defining lower threshold values and benchmarks for the depollution of WEEE is discussed. Recommendations for benchmarks and threshold values for the removal of capacitors and batteries are given.