Corrosion of Li-ion battery cathode materials on mullite insulation materials during calcination

A specially designed experimental device was used in laboratory to investigate the corrosion of mullite during the calcination of Li(Ni_xCo_yMn_z)O₂ (LNCM) materials. The anti-corrosion tests were carried out at 1000, 1100, 1200 and 1300 °C, and characterized with X-ray diffraction and scanning electron microscopy. The influence of temperature on the interactions between mullite insulation materials and LNCM materials was determined. In addition, the high-temperature creep properties of the mullite insulation materials before and after corrosion were tested. The laboratory scale tests, thermodynamic and kinetic calculations allowed a more comprehensive understanding of the evolution of the mullite insulation materials during serving for the roasting process of LNCM materials. Through this research, it is suggested that the upgrading of the kiln lining in the lithium battery industry should select materials with excellent resistance to alkali corrosion, especially excellent resistance to Li⁺ corrosion.     

Interactions of Li2O volatilized from ternary lithium-ion battery cathode materials with mullite saggar materials during calcination

In recent years, the rapid development of Li(Ni_xCo_yMn_1-x-y)O₂ (LNCM) materials for application in ternary lithium-ion batteries has led to an increased demand for refractory kiln saggars in industries. However, saggars used for firing ternary Li-ion battery cathode materials are often subjected to severe corrosion and spalling. To investigate the damage mechanism of the saggar materials, non-contact corrosion experiments were designed to study the effects of the precursor additions, calcination temperature, and number of calcinations during the interaction between mullite saggar and LNCM materials. The phase composition and microstructure of the mullite saggar specimens before and after corrosion were characterized using X-ray diffraction and scanning electron microscopy, respectively, to obtain a comprehensive understanding of the causes of the deterioration of mullite saggar materials during corrosion.     

耐火材料抗冰晶石侵蚀测试方法的发展现状

详细介绍了近年来国内外铝电解槽用耐火材料抗冰晶石侵蚀测试方法的现状,系统分析比较了各种测试方法的优缺点。从耐火材料检测实践出发,提出了根据耐火材料实际应用状况和材料种类来选择适当的检测方法。全部浸入法和半浸入法适用于电解槽侧壁耐火材料,坩埚法主要适用于散状耐火材料。     

Damage mechanism and corrosion resistance improvement of corundum-mullite kiln furniture during calcining of Li-ion cathode materials

In order to improve the cleanliness of cathode materials of Li ion batteries (LIBs), it is necessary to develop and apply advanced kiln furniture. Low-impurities Corundum-mullite materials (CMM) with were prepared, and the damage mechanism in LNCM production was studied. Innovatively amplify the corrosion process in the form of prefabricated cracks and explore their interaction mechanism. Based on the corrosion mechanism, Si-Al sol was selected as a binder to replace PVA. The corrosion resistance of CMM with Si-Al sol was significantly improved. With the improvement of calcination temperature and purity requirements of LIBs, the research and development of this advanced CMM kiln furniture has a good application prospect in the future.     

不同钴含量对三元正极材料性能的影响研究

随着新能源汽车和锂离子电池的普及和推广,钴的需求量逐渐增大,降低动力三元正极材料中钴元素的含量,成为新能源产业链所有公司的当务之急。通过对NCM622三元正极材料中不同钴元素的含量进行实验探索,在最佳实验条件下,分别合成NCM60/20/20、NCM60/15/25、NCM60/10/30、NCM60/05/35 4种正极材料,并对三元正极材料的SEM、XRD、首次放电容量、首次放电效率、倍率性能、循环性能及直流阻抗（DCR）增长等性能指标进行分析,探索钴元素含量对三元正极材料和锂离子电池的影响。实验发现,钴元素物质的量分数由20%降低至5%,材料的首次放电容量由178 mA·h/g降低至165 mA·h/g,50圈循环保持率由96%降低至88%,DCR由10%增长至20%,当钴元素物质的量分数低于10%时,性能衰减更为明显。     

锂离子电池正极材料磷酸铁锂的研究进展

磷酸铁锂（LiFePO₄）具有高温稳定性较好、循环性能良好、环保等特点,已成为锂离子动力电池正极材料之一。但由于磷酸铁锂电导率低及锂离子扩散速率慢等缺点,制约其在动力电池行业的发展。因此主要从包覆碳材料对磷酸铁锂进行表面改性、对磷酸铁锂进行掺杂、制备亚微米或纳米级的磷酸铁锂或制备特殊形貌的磷酸铁锂3方面进行综述,分析改善磷酸铁锂性能最优的方法,对其未来的发展趋势进行了预测。     

高镍三元正极材料表面碱性物质研究进展

高镍三元正极材料表面形成的碱性物质容易导致电池容量衰减加快、寿命缩短,因而调控三元材料表面碱性物质对于提高锂离子二次电池的功能和安全性至关重要。综述了高镍锂离子电池三元正极材料表面碱性物质的形成机理及处理手段,从不同角度阐述了环境中的水、二氧化碳对表面碱性物质形成的影响。探讨了表面碱性物质形成过程中,由于锂离子和过渡金属的迁移与固化引发的表面结构的相变现象,造成了三元正极材料的加工储存性能的恶化。还对降碱工艺中的洗涤、干燥、低温烧结等过程进行了重点说明,阐述了洗涤工艺对三元材料表面碱性物质降低及对材料性质的影响,指出需选择合适的洗涤、干燥条件,减小材料表面发生的变异。最后结合目前降碱工艺对后续研究方向提出了建议。     

锂离子电池正极材料超声强化水洗过程研究

针对高镍三元锂离子电池正极材料的降碱处理方式主要局限于去离子水洗涤且清洗效果不佳的问题,提出了一种超声强化水洗处理高镍三元锂离子电池正极材料的新方法。以LiNi_0.8Co_0.15Al_0.05O₂（NCA）为研究对象,去离子水为溶剂,通过正交试验探讨了超声强化水洗对高镍三元锂离子电池正极材料进行降碱处理的影响因素,并就单一固含量因素影响与简单去离子水洗涤进行对比。采用pH测定、粒度分析、SEM、电化学性能测试等手段进行分析,研究了固含量、搅拌时间、超声时间、超声频率、超声功率等对高镍三元锂离子电池正极材料降碱效果的影响。研究结果表明：在固含量10%、搅拌时间更均匀的情况下,颗粒表面形貌无明显影响,材料电化学性能提高。实际工业生产过程中水洗的固含量为40%更为合适。     

耐火材料损伤蚀变研究的进展

简述了高温、化学腐蚀、热震和多种机械载荷对耐火材料损伤依变的影响；综述了陶瓷耐火材料冲击、磨损、热震、疲劳和慢速裂纹扩展方面研究的进展；讨论了综合破坏作用下材料的行为及模拟性试验。     

Comparison of interactions of MgO-based refractories with Li-ion battery cathode materials during calcination

To select refractory major ingredients of saggers for the calcination of Li-ion battery cathode Li(Ni_xCo_yMn_z)O₂ (LNCM) materials, interactions between MgO-based refractories, ie, magnesium aluminate (MgAl₂O₄) spinel, forsterite (2MgO·SiO₂), and cordierite (2MgO·2Al₂O₃·5SiO₂), and LNCM materials were compared respectively via refractory-LNCM precursor cylinder testing in lab-scale. The phase composition and microstructure evolution of the calcined cylinders were characterized and resulted in comprehensive understanding and comparing of degradation of the MgO-based refractories. The results reveal that cordierite is severely corroded, whereas magnesium-aluminate spinel reacts little with LNCM materials. Refractories contain both SiO₂ and Al₂O₃ with a higher SiO₂ level will suffer a more serious corrosion contacting with LNCM materials.     

计算机分析Al2O3-SiO2系耐火材料的抗FeO侵蚀性能

采用C Builder编制程序绘制了 16 0 0℃下FeO -Al2 O3-SiO2 三元系等温截面图 ,在此基础上 ,判断不同组分的Al2 O3-SiO2 系材料抗FeO侵蚀能力的优劣。该程序具有界面好、使用便捷、准确的特点。     

Enhanced corrosion resistance of magnesia-chrome refractories impregnated with zirconia sol

In order to enhance the corrosion resistance to molten vanadates and silicates of middle and upper checker bricks in glass furnace regenerator with petroleum coke as fuel, the present research improved the microstructure, compactness and corrosion resistance of magnesia-chrome refractories by vacuum impregnation with zirconia sol. The results show that the vacuum impregnation of zirconia sol and the increased impregnation times led to the significant increase in the bulk density and decrease in the apparent porosity of refractories, and the impregnated zirconia particles enhanced the corrosion and penetration resistance. The penetrated zirconia particles in the pores decreased the porosity and pore size of refractories, resulting in the inhibited penetration of vanadate and silicate liquid phases during the corrosion process. In addition, the zirconia particles around periclase particles also prevented the reaction between molten corrosion reagent and periclase, thus enhancing the corrosion resistance of refractories. The present study provides an effective method for improving the corrosion resistance of magnesia-chrome checker bricks in regenerator of glass furnace with petroleum coke as fuel.     

用于锂离子电池负极SnO2MCMB复合材料的研究

以中间相碳微球(MCMB)为核心,用直接沉淀法制备了一种氧化锡颗粒修饰的新型复合碳材料.用X射线衍射和扫描电镜对材料的结构及形貌进行了表征.通过恒流充放电、交流阻抗、循环伏安等测试手段对该材料的嵌脱锂特性进行了研究,循环20周后其比容量仍然保持在360 mAh/g以上.此种复合物可以作为一种锂离子电池新型负极材料.     

Anti-corrosion effect of insulating firebrick coated with CA6 in the calcination of lithium-ion cathode materials

The anti-corrosion properties of calcium hexaluminate (CA6) during the roasting of Li(Ni_xCo_yMn_z)O₂ (LNCM) materials have been investigated by means of specific experimental setups and test methods to verify its feasibility as an adiabatic insulation material for the roasting kiln of LNCM materials. Mullite insulating firebrick currently in industrial use was coated with CA6 (labelled M-CA6) and corrosion tests were carried out. The corrosion tests were carried out at different additions of corrosion sources, roasting temperatures, number of cycles of corrosion experiments. And the materials before and after corrosion characterized by the X-ray diffraction and scanning electron microscopy to determine the influence of different corrosion conditions on the interactions between M-CA6 and LNCM materials. In addition, The corrosion resistance of calcium CA6 and the feasibility of its application in practical industry was identified by characterising and comparing the high-temperature creep properties of the materials. The results of the laboratory scale experiments confirmed that M-CA6 was more resistant to LNCM than mullite insulating firebrick, and confirmed the feasibility and superiority of using CA6 as a lining insulation for LNCN kilns.     

基于显微边界形貌分形特征的耐火材料侵蚀维数研究

通过对侵蚀残砖的显微边界形貌研究发现 :耐火材料的抗侵蚀性能和基于显微边界形貌分形特征的分形维数存在良好的线性关系。根据分形维数的定义和含义 ,作者提出了一种基于分形理论的耐火材料侵蚀维数Rf (Refractoryfractal)的概念和抗侵蚀分类建议。根据耐火材料的使用经验和实绩而定义的Rf =[1.0 ,1.0～ 1.15 ,1.15～ 1.2 0 ,≥ 1.2 ]数值范围 ,可以用于耐火材料抗侵蚀性能的评判、分类 ,并且可用于设计选型和编制相对应的耐火材料的残余安全厚度的日常维护规程等     

含TiO2高炉渣对Sialon结合SiC材料的侵蚀行为

实验考察了含TiO2 高炉渣对Sialon结合SiC耐火材料的侵蚀行为。结果发现 ,渣中TiO2含量仅为 1 .0 5%时 ,耐火材料中将形成Ti(C、N) ,并积聚于工作带 ,阻止熔渣的进一步侵入 ,从而延长了SiC材料的使用寿命     

Research on saggars of lightweight design used to prepare cathode materials for Li-ion batteries

The focus of lightweight refractory is equivalent volume replacement that uses lower-density raw materials to replace the original high-density raw materials. In this study, we employ porous mullite microspheres (PMM) to replace mullite particles to realize the weight-lighting of mullite–cordierite saggars used to prepare cathode materials for Li-ion batteries.To confirm that lightweight saggars satisfy the quality standards of production, we conducted various tests, including mechanical properties, thermal shock stability and corrosion resistance. Compared with samples with mullite particles, samples with PMM have a comparatively stable material structure and excellent performance. Furthermore, PMM reduce mullite consumption and enhance their resistance to prevent stress shedding in the corrosion process.     

SiC结合刚玉材料的抗高炉渣侵蚀性

采用电熔刚玉、Si粉和SiC粉为原料,用酚醛树脂做结合剂,混练成型后于1 450℃埋炭烧成,采用静态坩埚抗渣试验研究了烧后试样对碱度为1.1的高炉渣在1 500℃的抗渣侵蚀性。结果表明:Si与C、CO在高温下原位反应生成纤维状SiC,形成原位SiC结合刚玉材料,该材料具有良好的抗侵蚀性能,渣蚀厚度都在2.6mm以下,其中,加入8%(w)Si粉和5%(w)SiC粉的试样抗渣侵蚀性最好。通过对抗侵蚀后试样的侵蚀层、渗透层和未变层的相组成和显微结构的分析认为:(1)这种复合材料抗渣侵蚀性能良好的主要原因是熔渣难润湿的SiC自身抗渣侵蚀性较好,且原位生成的纤维状SiC穿插在刚玉骨架结构的空隙中,阻挡了熔渣的侵蚀和渗透;(2)熔渣侵蚀材料的过程是SiC先被氧化,然后其氧化产物SiO2与熔渣中的CaO和SiO2以及材料基质中的A l2O3反应生成钙长石低熔相。     

Permeability and corrosion resistance of porous SiOC-bonded SiC ceramics prepared by the preceramic polymer

Porous SiC ceramics have been used in high temperature flue gas filtration fields because of their excellent properties such as high strength, high temperature resistance, corrosion resistance, and long service time. This work reports the porous SiOC-bonded SiC ceramics prepared at low temperature. The properties of porous SiC ceramics were first investigated with silicone resin content from 10 to 25 wt%, and then the effects of different pore-forming agent contents on the behaviors of porous SiC ceramics were discussed by adjusting poly (methyl methacrylate) PMMA microbeads from 5 to 20 wt%. The prepared porous SiC ceramics showed apparent porosity from 17.3% to 57.7%, compressive strength from 6 to 216 MPa, and Darcy permeability k₁ ranging from 7.02 × 10⁻¹⁴ to 1.45 × 10⁻¹² m². The corrosion behavior of porous SiC ceramics was investigated in acidic and alkaline media. The porous SiC ceramics showed better corrosion resistance in acidic solutions.