废旧电池中有价金属回收利用探讨

随着中国经济的稳步发展和投资环境的不断优化,中国已成为电池的制造和消费大国,每年产生数亿只废旧电池。对废旧电池的回收利用已成为全社会关注的问题。介绍了废旧电池中有价金属的回收利用方法,着重介绍了锂离子二次电池正极材料有价金属的回收利用方法。指出,中国商品化的正极材料只有钴酸锂（LiCoO2）,这种正极材料钴含量高,且钴价值高,并且回收工艺可行,因此,从钴酸锂正极材料中回收钴等有价金属,对发展中国的循环经济具有重要意义。同时介绍了锂离子二次电池正极材料的研究现状。     

Cooperative effect of crystallization temperature and NaF addition in the formation process and hydrothermal stability of MCM-48 mesoporous molecular sieve

The hydrothermal stability of MCM-48 was conveniently and effectively improved by increasing the crystallization temperature and directly adding NaF to the synthesis gel. The crystallization temperature varied from 373 K to 403 K. The influences of NaF addition, crystallization temperature and crystallization time on the formation process and hydrothermal stability of MCM-48 were systematically studied here to solve the problem of poor reproducibility. Results from XRD patterns indicated that the crystallization temperature and crystallization time were very critical factors for the improvement of the hydrothermal stability besides NaF addition. The formation process of MCM-48 was significantly accelerated and the pore structure ordering was also greatly improved by increasing the crystallization temperature and F⁻/Si ratio. A high hydrothermally stable MCM-48 mesoporous molecular sieve was obtained after being crystallized at 393 K for 36 h in the presence of NaF, which endured the hydrothermal treatment in boiling water at least for 4 days. However, only an amorphous product was obtained when the crystallization temperature was further increased to 403 K. Results from Si MAS NMR, N₂ adsorption isotherms, TEM, Raman spectra and XRD patterns manifested that the improved stability of MCM-48 was attributed to the high silicates condensation degree and the excellent pore structure ordering. The possible reason for the successful formation of hydrothermally stable MCM-48 sample by controlling the crystallization temperature, time and F⁻/Si ratio was explained here.     

Investigation of transport phenomena in a hybrid ion exchange-electrodialysis system for the removal of copper ions

Hybrid ion exchange electrodialysis processes allow the removal of metal ions from dilute waste liquids and the recovery of more concentrated solutions. The work reported here was aimed at investigating the two steps in the treatment process, namely, adsorption of metal ions onto the packed bed of resin and electromigration (i.e., the transport of these ions in the complex system under the applied electrical field). The case of copper sulfate was investigated. Dowex resins with a cross-linking degree of 2 and 8% were used. The flux of copper through the resin bed and the current efficiency for ion transfer to the cathode compartment were determined as a function of potential gradient and copper ionic fraction in the bed. Apparent diffusion coefficients of Cu²⁺ in the overall system were deduced from the experimental data.     

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br₂ cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application.     

Improvement of structural stability and electrochemical activity of a cathode material LiNi0.7Co0.3O2 by chlorine doping

In the process of Li⁺ intercalation-deintercalation, electron removal is accompanied simultaneously. Oxygen was found to compensate electron removal both in theoretical calculations and practical experiments. Chlorine addition to LiNi_0.7Co_0.3O₂ was expected to exchange electrons in that Cl⁻ was easier to lose electrons than O²⁻. LiNi_0.7Co_0.3O_2−xCl_x was identified as a pure hexagonal lattice of α-NaFeO₂ type by X-ray diffraction. X-ray photoelectron spectroscopy was used to analyze the influence of chlorine substitution on the oxidation state of transition-metal ions. Charge-discharge experiments and cyclic voltammetry confirmed that chlorine addition was an effective way to improve reversible capacity and structural stability in cycles.     

溶剂对全氟磺酸再铸膜性能的影响

将氯碱工业用过的废离子交换膜放入乙醇水溶液中，在250℃和10MPa条件下溶解4h，固液分离后，得到，浓度为7．2％的全氟磺酸离子交换树脂（PFSI）溶液。并分别利用高沸点溶剂（HBPS）——二甲基亚砜（DMSO）、乙二醇（EO）、吡硌烷酮（NMP）和二甲基甲酰胺（DMF）置换其中的低沸点溶剂，采用浇铸法制备了再铸全氟磺酸质子交换膜。通过测定再铸膜（RCM）的交换容量、电导率、抗拉强度和X射线衍射谱图等研究了浇铸温度、浇铸时间和HBPS种类等条件对RCM性能的影响。结果显示：RCM的最佳成膜温度和时间分别为140℃和2h，温度高于180℃，部分PFSI开始分解，电导率和离子交换容量有所下降，时间低于2h，HBPS不能完全从RCM中挥发，RCM的机械强度和稳定性低。HBPS的种类和加入比例影响RCM的结晶程度和晶粒大小，HBPS加入量过少，在HBPS挥发完之前，PFSI没有足够的时间结晶，稳定性差，最好的HBPS是二甲基亚砜和吡硌烷酮，RCM与Nafion112具有相近的燃料电池性能。     

负离子乳胶漆的研究及应用进展

介绍了空气中负离子的作用、负离子乳胶漆释放负离子的原理和国内外负离子乳胶漆产品的研发进展。     

聚丙烯酸锂的合成与性能

研制了一种新型阳离子导电聚合物—聚丙烯酸锂 (PAALi) ,分子量在 2 0 ,0 0 0～4 0 0 ,0 0 0范围内 ,室温离子电导率为 10 - 8～ 10 - 9S·cm- 1;研究了聚合条件对产率的影响 ;探讨了分子量、锂离子含量、温度对其离子导电率的影响。     

离子交换增强玻璃表面化学稳定性的研究

系统研究了化学钢化及盐溶液后处理对Na2O-CaO-SiO2玻璃表面化学稳定性的影响。详细考察了用熔融KNO3化学钢化的玻璃以及用适当盐溶液后处理的化学钢化玻璃,在受水侵蚀后R2O的沥滤量和失重以及受碱侵蚀后SiO2的溶出量和失重。结果表明,用熔融KNO3对玻璃进行钢化处理后,玻璃的耐水性和耐碱性均有明显下降。而将化学钢化的玻璃利用适当盐溶液处理后,可以改善钢化玻璃的化学稳定性,因而可以进一步提高化学钢化玻璃的使用性能和拓展其使用范围。     

Co-LsX催化苯乙烯生成环氧苯乙烷绿色合成工艺研究

采用离子交换法制备Co-LsX催化剂,分子筛经Co2+离子交换后,其骨架结构没有发生变化。考察了反应温度、反应时间、催化剂用量、溶剂加入量及氧气通入速率等因素对苯乙烯环氧化反应的影响。得出最佳工艺条件:反应温度100℃,反应时间6 h,Co-LsX与苯乙烯质量比为0.16,混合溶剂与苯乙烯体积比为5;V(O2)∶V(苯乙烯)=1.3 min-1。在此条件下苯乙烯转化率达到62.5%,环氧苯乙烷的选择性达到57.1%。催化剂经6次循环使用后活性和稳定性都比较好。