Tuning fermi level and band gap in Li4Ti5O12 by doping and vacancy for ultrafast Li+ insertion/extraction

Li₄T_i5O₁₂ (LTO) attracts great interest due to the “zero strain” during cycles but the poor electronic and ionic conductivity critically impede the practical application. Herein, we report a synergy strategy of tuning localized electrons to shift Fermi level and band gap by Mg/Zr co-doping and oxygen vacancy incorporation, which significantly improves Li⁺ and electronic transport. More importantly, the intrinsic synergistic mechanism has been revealed by neutron diffraction, X-ray absorption spectra, and first-principles calculations. The “elastic effect” of lattice induced by Mg/Zr co-doping allows LTO to accommodate more oxygen vacancies to a certain degree without a severe lattice distortion, which largely improves the electronic conductivity. Mg/Zr co-doping and oxygen vacancy incorporation effectively enhanced the dynamic characteristics of LTO electrode, achieving the excellent rate performance (90 mAh/g at 20C) and cycle stability (96.9% after 500 cycles at 10C). First-principles calculations confirm Fermi level shifts to the conduction band, and the band gap becomes narrowed due to the synergistic modulation, and the intrinsic mechanism of the enhanced electronic and Li-ion conductivity is clarified. This study offers some insights into achieving the fast Li⁺ insertion/extraction by tuning the crystal and electronic structure with lattice doping and oxygen vacancy engineering.     

复合溶胶–凝胶一锅法制备锂离子电池氧化亚硅/碳复合负极材料

采用复合溶胶–凝胶法结合后续热处理,制备了具有包埋结构的氧化亚硅/碳(SiO_x/C)复合负极材料。扫描电子显微镜分析结果表明:氧化亚硅纳米颗粒嵌入在无定形碳中。电化学性能测试表明:SiO_x/C复合材料具有较高的比容量、优异的循环稳定性和倍率性能。材料在0.1 A/g的电流密度下100次循环后的可逆比容量为710 m A·h/g,容量几乎无衰减;在1.6 A/g的电流密度下,可逆比容量为380 m A·h/g。优异的电化学性能是由于材料的包埋结构能有效地缓冲SiO_x充放电过程中的体积膨胀,保证材料的结构完整性和电化学循环稳定性。     

Si基锂离子电池负极材料研究进展

硅具有高的理论比容量、较低的嵌锂电位、来源广泛且环境友好等优点,被认为是下一代锂离子电池负极材料的有力竞争者。然而,在锂离子脱嵌过程中巨大的体积膨胀引起了活性材料的粉化和破裂,这带来了电极循环性能差、容量衰减快甚至电极失效等一系列问题。迄今为止,有大量关于改性硅基材料的报道。本文将重点介绍硅基材料的纳米结构化设计和硅/碳材料的结合。首先,分析了硅的储锂及失效机制,从机理上理解硅的失效对其电化学性能的影响。其次,从理论上阐述了纳米级硅材料对缓解体积效应的机理,从结构设计、材料合成、形态特征和电化学性能等方面论证了纳米硅材料的优势。随后,从缓解体积膨胀、提高电导率和形成稳定的固体电解质（SEI）膜等方面总结了硅碳复合材料的研究进展。此外,还讨论了将导电聚合物和金属引入硅基材料的电化学性能增强机理。最后,从提高首次库仑效率、SEI膜稳定性和质量负载量等方面对硅基材料的产业化应用提出几点建议。     

预焙阳极铝电解槽阳极降耗技术开发及应用

本文对预焙阳极铝电解槽阳极炭耗问题进行了论述，并介绍了阳极降耗技术的开发应用。     

Electrochemical and microstructural characterization of cyclic redox behaviour of SOFC anodes

The oxidation of Ni to NiO in solid oxide fuel cell (SOFC) anode will result in large bulk volume change, which may change the interfaces of the two phases in the anode cermet and thus may cause significant performance degradation. The reduction and oxidation (redox) of the Ni/YSZ cermet were studied at 800 ℃. Anodic polarization measurements were performed before and after redox cycles. The anode current density at an overpotential of 100 mV kept decreasing during the whole redox treatment. It decreased from 19.11 to 7.95 mA·cm-2 after two redox cycles. Anode supported unit cell was assembled for cell's discharge measurements. Cell performance declined after each redox cycle. The maximum power density decreased from 126.28 to 40.32 mW·cm-2 . The microstructural changes after redox cycling were recorded using scanning electron microscopy (SEM). The results reveal that after re-oxidation, the Ni gets coarse and has a higher porosity; the nickel network structure turns to be desultory.     

氨络合物体系中Ti基IrO2涂层阳极的析氮过程

采用线性扫描技术研究了氯盐氨络合物体系中Ti基IrO2涂层阳极的析氮过程,对3种含有不同氧化物涂层电极的析氮电催化性能进行了比较,并结合扫描电镜(SEM)及能谱(EDX)探讨了不同析氮电催化活性的原因.研究结果表明:当电极电位低于1.1 V(vs SCE)时,Ti基IrO2涂层阳极析气反应主要为析氮反应,氮气的产生主要是由于氨水在电极上发生电化学氧化引起的;Ti基含PdRuTi的IrO2涂层阳极具有最佳的析氮电催化活性,其可能原因是金属元素PdRuTi的存在导致该电极表面特征裂纹最宽且最深,氧化物涂层总析氮面积增多,电催化活性增加.     

热处理对铝合金牺牲阳极电化学性能的影响

针对不同均匀化处理方式会引起合金微观组织和电化学性能变化现象,采用电子探针(EPMA)、动电位极化及恒电流极化等方法研究不同热处理(水淬、空冷、炉冷)方式对Al-Zn-In合金的微观组织和合金在3%NaCl溶液中的开路电位、工作电位、腐蚀形貌和电流效率等电化学性能的影响。结果表明:510℃,10 h的均匀化处理使晶界偏析减少,抑制析氢自腐蚀和晶粒脱落,提高电流效率,但对阳极开路电位、工作电位及溶解行为的影响并不明显,且水淬处理试样的电流效率最高。     

Preparation and properties of Ce0.8Ca0.2O1.8 anode material by glycine-nitrate process

Ce0.8Ca0.2O1.8（CDC82） anode material was prepared by glycine-nitrate process（GNP）. Thermogravimetric（TG） analysis and differential scanning calorimetric（DSC） methods were adopted to characterize the reaction process of CDC82 material. X-ray diffractometry（XRD）, scanning electron microcopy（SEM）, direct current four probe （four-probe DC） and temperature process reduce（TPR） techniques were adopted to characterize the properties of CDC82 material. After the precursor was sintered at 750℃ for 4 h, CDC82 material with pure-fluorite structure and nanometer size was obtained. The total conductivity of CDC82 changes little with temperature in air at 50-850℃, and the maximum value is 0.04 S/cm at 750 ℃. The total conductivity wholly becomes larger when the atmosphere changes from air to hydrogen, which greatly increases with increasing temperature and reaches the maximum value of 1.09 S/cm at 850 ℃. Some impurities such as CeMg and La203 exist after the mixture of CDC82 anode and La1-xSrxGa1-yMgyO3-δ （LSGM） electrolyte material is sintered at 1 200 ℃ for 15 h. The CDC82 material as anode material has excellent catalytic property for hydrogen and methane.     

RuTiSnMn/Ti阳极的电化学性能

热分解制备了RuTiSnMn／Ti阳极，在4mA／cm^2的电流密度下进行了恒电流试验。通过循环伏安法和交流阻抗谱研究了阳极在35g／LNaCl溶液、20g／LNaOH溶液和模拟孔隙液中的电化学行为．利用EsEM对阳极失效前后的微观形貌进行了观察,结果表明：阳极具有优良的耐析氯、氧反应能力；钛基体逐渐形成TiO2的钝化膜使阳极的氧化物膜电阻增大，活性组元的消耗使法拉第电荷传递电阻增加，这两者最终导致阳极失效。     

Prevention of steel corrosion in concrete exposed to seawater with submerged sacrificial anodes

This paper presents the results of a study of the effectiveness of submerged sacrificial anodes in preventing the onset of pitting corrosion in the emerged part of marine piles. Experimental tests were carried out on reinforced concrete columns with steel embedded both in chloride free concrete and chloride contaminated concrete in order to compare the effects of sacrificial anodes on passive steel and on corroding steel. Results have shown, at least under the present testing conditions, that sacrificial anodes may be more effective in preventing corrosion initiation (i.e. in providing cathodic prevention) than in controlling ongoing pitting corrosion (i.e. in guaranteeing cathodic protection). Monitoring criteria for this type of prevention are also discussed.