废旧锂离子电池中有价金属的回收

采用超声波分离电极材料-酸浸-钴锂沉淀新工艺分离并回收了废旧锂离子电池中的有价金属。超声波分离中所研究溶剂的分离效果为：NMP〉DMF〉DMSO〉〉丙酮。超声波处理可降低分离温度与时间。采用该工艺，电极材料用NMP于40℃超声波处理15min可完全剥离；所剥离电极材料中99．4％的钴锂可酸浸出；酸浸液中99．5％的钴离子可以高密度球形CoC2O4回收；钴沉淀分离后，滤液中94．5％的锂离子可以Li2CO3沉淀回收。以所回收钴锂化合物制备的LiCoO2具有良好的电化学性能。     

溶胶-凝胶法合成LiAl0.1Mn1．9O4及其电化学性能

通过溶胶-凝胶法合成LiAl0.1Mn1.9O4，XRD的结果表明掺杂少量的铝后并没有改变晶体的结构。利用恒流充放电测试手段比较研究了尖晶石型的LiAl0.1Mn1.9O4，XRD铝的掺杂后的LiAl0.1Mn1.9O4，XRD比没有掺杂的LiMn2O4更好的可逆性能，更好的循环性能。     

熔盐法合成电化学性能优异的富锂层状正极材料Li_(1.5)Ni_(0.25)Mn_(0.75)O_(2.5)

采用氢氧化物共沉淀和熔盐法相结合的方法制备得到了电化学性能优异的富锂锰基Li_(1.5)Ni_(0.25)Mn_(0.75)O_(2.5)正极材料。借助X射线衍射(XRD)分析、扫描电镜(SEM)、感应耦合等离子体原子发射光谱(ICP-AES)、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)和恒电流充放电测试等表征手段对材料的颗粒形貌、晶体结构和电化学性能进行了系统研究。XRD结果表明该材料具有完善的α-NaFeO2层状结构(空间群为R3m)和较低的Li~+/Ni~(2+)阳离子混排。电化学性能测试表明该材料的首次不可逆容量损失较小,且倍率性能和循环稳定性能十分优异。具体而言,在2.0~4.8V,0.1C时的首次不可逆容量损失为50mAh·g~(-1)(首次库伦效率84%);在10C时的放电比容量还能达到102mAh·g~(-1);在0.5C下循环100次后,放电比容量为205mAh·g~(-1)(容量保持率90%)。     

聚阴离子掺杂LiMnO_(2-y)X_y(X=BF_4~-,SiO_3~(2-),MoO_4~(2-),PO_4~(3-),BO_3~(3-))材料的合成及其电化学性能

采用水热法合成了聚阴离子掺杂LiMnO2-yXy(X=BF4-,SiO32-,MoO42-,PO43-,BO33-,y=0.01、0.03、0.05)锂离子电池正极材料。通过X射线粉末衍射(XRD)、X光电子能谱(XPS)、扫描电镜(SEM)和恒电流充放实验,研究了不同掺杂离子和掺杂量对产物结构和电化学性能的影响。结果表明,少量聚阴离子的掺杂未改变正交LiMnO2的晶体类型,但增大了材料晶胞体积,改善了材料的电化学循环性能。电化学交流阻抗(EIS)测试结果表明,聚阴离子掺杂增大了材料电荷转移阻抗,但明显提高了材料中Li+的扩散能力。     

High power nano-LiMn2Oa cathode materials with high-rate pulse discharge capability for lithium-ion batteries＊

Nano-LiMn2O4 cathode materials with nano-sized particles are synthesized via a citric acid assisted sol-gel route. The structure, the morphology and the electrochemical properties of the nano-LiMn204 are investigated. Compared with the micro-sized LiMn2O4, the nano-LiMn2O4 possesses a high initial capacity （120 mAh/g） at a discharge rate of 0.2 C （29.6 mA/g）. The nano-LiMn2O4 also has a good high-rate discharge capability, retaining 91% of its capacity at a discharge rate of 10 C and 73~ at a discharge rate of 40 C. In particular, the nano-LiMn2O4 shows an excellent high-rate pulse discharge capability. The cut-off voltage at the end of 50-ms pulse discharge with a discharge rate of 80 C is above 3.40 V, and the voltage returns to over 4.10 V after the pulse discharge. These results show that the prepared nano-LiMn2O4 could be a potential cathode material for the power sources with the capability to deliver very high-rate pulse currents.     

Relaxation structure analysis of Li inserted γ-Fe2O3

γ-Fe₂O₃ has a spinel structure with cation vacancy and is expected to perform as a favorable electrode material for secondary lithium-ion battery. When lithium is inserted electrochemically into γ-Fe₂O₃, prolonged potential change is observed after the insertion. In this study, we inserted various amount of Li into γ-Fe₂O₃ (x = 0.66, 1.1, 1.5 in terms of Li_XFe₂O₃), then made the circuit open, measured X-ray diffraction (XRD) patterns at various elapsed time, and analyzed the crystal structure change of γ-Fe₂O₃ with time by the Rietveld method. The X-ray Rietveld analysis revealed that the iron occupancy of 8a site decreased and that of 16c site increased with lithium insertion process and after lithium insertion, the iron occupancy of 8a site increased and that of 16c site decreased gradually with relaxation time. It is indicated that lithium prefer 8a site to occupy kinetically, on the other hand, prefer 16c site thermodynamically.     

Controllable Preparation of Nanosized LiMnPO4/C with Rod-Like Morphology by Hydrothermal Method with Excellent Electrochemical Performance

The nanosized rod-like LiMnPO₄/C cathode materials have successfully in situ synthesized on the surface of flaky structure MnPO₄ · H₂O self-sacrificing template by the hydrothermal method. The crystal microstructure, micro shape, and electrochemical parameters of LiMnPO₄/C are comprehensively studied by XRD, SEM, TEM, and electrochemical measurement methods. The physical and chemical properties analysis confirms that the vinyl acetate solution (VAc-H₂O) with a proper molar ratio is beneficial to generate orthorhombic olivine structure LiMnPO₄ with microporous structure and nanorod-shaped morphology. The electrochemical measurement results indicate that LMP-X1-AA sample delivers an initial discharge capacity of 148.1 mAh g⁻¹ at 0.05 C, the capacity retention rate still maintains at 89.2% after 200 cycles. As the discharge rate increases to 1 C, the discharge capacity still remains at 133.4 mAh g⁻¹. The results indicate that the synergistic effect of nanosized rod-like morphology and conductive carbon coating is beneficial to improving the lithium ions diffusivity and electrochemical properties of LiMnPO₄ materials.     

Synthesis of 2D/2D Structured Mesoporous Co3O4 Nanosheet/N‐Doped Reduced Graphene Oxide Composites as a Highly Stable Negative Electrode for Lithium Battery Applications

Mesoporous Co₃O₄ nanosheets (Co₃O₄‐NS) and nitrogen‐doped reduced graphene oxide (N‐rGO) are synthesized by a facile hydrothermal approach, and the N‐rGO/Co₃O₄‐NS composite is formulated through an infiltration procedure. Eventually, the obtained composites are subjected to various characterization techniques, such as XRD, Raman spectroscopy, surface area analysis, X‐ray photoelectron spectroscopy (XPS), and TEM. The lithium‐storage properties of N‐rGO/Co₃O₄‐NS composites are evaluated in a half‐cell assembly to ascertain their suitability as a negative electrode for lithium‐ion battery applications. The 2D/2D nanostructured mesoporous N‐rGO/Co₃O₄‐NS composite delivered a reversible capacity of about 1305 and 1501 mAh g^?1 at a current density of 80 mA g^?1 for the 1st and 50th cycles, respectively. Furthermore, excellent cyclability, rate capability, and capacity retention characteristics are noted for the N‐rGO/Co₃O₄‐NS composite. This improved performance is mainly related to the existence of mesoporosity and a sheet‐like 2D hierarchical morphology, which translates into extra space for lithium storage and a reduced electron pathway. Also, the presence of N‐rGO and carbon shells in Co₃O₄‐NS should not be excluded from such exceptional performance, which serves as a reliable conductive channel for electrons and act as synergistically to accommodate volume expansion upon redox reactions. Ex‐situ TEM, impedance spectroscopy, and XPS, are also conducted to corroborate the significance of the 2D morphology towards sustained lithium storage.     

锂离子电池LiTi_(0.25)Fe_(0.75)SO_4F正极材料的电子结构

采用密度泛函理论平面波赝势的方法,计算了LiFeSO_4F和LiTi_(0.25)Fe_(0.75)SO_4F正极材料的电子结构。计算结果表明:当锂嵌入材料后,S、O和F的原子布居变化较小,电子主要填充在过渡金属的3d轨道,导致过渡金属被还原,成为电化学反应的活性中心。在嵌锂态中,锂和氧(氟)之间形成了离子键,而过渡金属(Ti和Fe)与氧(氟)之间则形成了共价键,S-O键的共价性最强。态密度的计算结果则表明:Ti和Fe均保持高自旋排列结构;LiFeSO_4F的两个自旋通道的带隙分别为2.88和2.29 e V,其导电性很差;Ti掺杂使体系的带隙消失,显著地提高了正极材料的导电性;LiTi_(0.25)Fe_(0.75)SO_4F系统中Ti-O和Ti-F键均比纯相中的Fe-O和Fe-F键的共价性更强,因此Ti掺杂材料具有更好的结构稳定性。     

Nitrogen‐Doped Mesoporous Carbon‐Encapsulated MoO2 Nanobelts as a High‐Capacity and Stable Host for Lithium‐Ion Storage

N‐doped mesoporous carbon‐capped MoO₂ nanobelts (designated as MoO₂@NC) were synthesized and applied to lithium‐ion storage. Owing to the stable core–shell structural framework and conductive mesoporous carbon matrix, the as‐prepared MoO₂@NC shows a high specific capacity of around 700 mA h g⁻¹ at a current of 0.5 A g⁻¹, excellent cycling stability up to 100 cycles, and superior rate performance. The N‐doped mesoporous carbon can greatly improve the conductivity and provide uninhibited conducting pathways for fast charge transfer and transport. Moreover, the core–shell structure improved the structural integrity, leading to a high stability during the cycling process. All of these merits make the MoO₂@NC to be a suitable and promising material for lithium ion battery.