碳纳米管的电化学贮锂性能研究

以纳米镍粉为催化剂,热分解法制备了碳纳米管.应用X射线衍射对碳纳米管的结构进行了研究,透射电子显微镜观察了碳纳米管的形貌.碳纳米管的直径在15nm左右,长>100nm,d₀₀₂为0.338nm.在结构上,纳米碳管具有与石墨类似的良好规整性,具有较高的可石墨化度,又具有纳米级的孔径,因此具有良好的贮锂性能.对碳纳米管的充放电性能研究结果表明,碳纳米管初始放电比容量为654mAh/g,高于纯石墨的理论容量372mAh/g,循环性能较好.     

锂离子电池负极材料钼掺杂钛酸锂的制备及电化学表征

采用固相合成法制备了钽掺杂材料Li₄Ti_4.95Mo_0.05O₁₂. 通过XRD和SEM来表征Li₄Ti_4.95Mo_0.05O₁₂的结构和形貌. 结果表明: 钼掺杂并没有改变本体材料的结构和形貌, 而且显著提高了材料的循环性能和倍率性能. Li₄Ti_4.95Mo_0.05O₁₂在10C和30C倍率的放电容量分别为117.03和94.24mAh/g.Mo掺杂取代了Li₄Ti₅O₁₂中的Ti位置, 产生了Ti⁴⁺/Ti³⁺混合价态, 从而提高了钛酸锂的电导率. 所以Li₄Ti_4.95Mo_0.05O₁₂是一种高倍率性能优异的锂离子电池负极材料.     

高性能Si@SiO_x@C负极材料的制备及其电化学性能

本文通过对粉体Si进行球磨,结合在球磨产物中引入柠檬酸并对其进行碳热分解处理,制备了一种低碳高SiO_x含量的Si@SiO_x@C复合材料。采用现代材料分析测试技术和电化学测试技术,研究了500~700℃的碳热分解处理温度对复合材料的结构和其作为锂离子电池负极材料的电化学性能的影响。研究结果表明,不同温度获得的复合材料均为微米/亚微米尺寸的Si核外包覆有不同厚度的SiO_x及碳的Si@SiO_x@C颗粒,其中650℃条件下制得的复合材料中SiO_x和碳的含量分别约为55wt%和10wt%。该复合材料作为负极材料,表现出优于其它温度下获得的复合材料的结构和电化学性能,其在不再额外添加碳导电剂的条件下,在300 mA/g充放电时的首次库伦效率为74%,经200次循环后的容量为776mAh/g,容量保持率达75%。该低碳含量的微米/亚微米尺寸的Si基负极材料振实密度高,对于获得高体积比容量的电池极具使用潜力。     

锂离子电池Li3-xMx N(M:Co,Ni,Cu)系列负极材料研究进展

Li3-xMxN(M:Co,Ni,Cu)具有首次脱锂容量大,良好的充放电可逆性等优点,是制备锂离子电池负极的优良材料.本文介绍了此系列材料的制备方法、结构、特性及其性能.     

石墨烯/锂金属复合材料的制备和电化学性能

对于高能量密度锂金属电池体系,安全、稳定的锂负极材料是关键。采用微波还原、热还原和机械剥离方法制备了3种具有不同形貌结构的石墨烯,并通过压制和叠层工艺,制备出石墨烯/锂金属复合材料。通过扫描电子显微镜(SEM)、拉曼(Raman)、X射线光电子能谱(XPS)和N₂吸脱附曲线分析了不同石墨烯材料的形貌、组成、结构以及石墨烯/锂金属复合材料的形貌。同时采用Li||Li对称电池和LiFeO₄全电池,评价了石墨烯/锂金属复合材料作为负极的电化学性能。结果表明,石墨烯/锂金属复合材料具有层状结构,在微波还原石墨烯(MRGO)、热还原石墨烯(RGO)和机械剥离石墨烯(EG)中,MRGO最适用于改性金属锂,叠层3次得到的4MRGO/3Li复合材料具有最优的电化学性能。基于4MRGO/3Li的Li||Li对称电池在9.9 mV左右的极化电压下稳定循环1200圈,相对于纯锂金属,极化电压降低10.6 mV,安全性和稳定性大大提升。以4MRGO/3Li复合材料为负极的LiFeO₄全电池稳定循环800圈后,放电容量保持为156 mAh/g。     

锂离子电池负极材料球形钛酸锂的合成及性能

以3.98mol/L的四氯化钛为前驱体溶液,采用内凝胶法制备了具有尖晶石结构的球形钛酸锂(Li4Ti5O12)粉末。通过XRD、SEM及电化学性能测试等分析手段表明,合成的Li4Ti5O12材料均为纳米一次粒子(晶粒)组成的球形二次粒子(颗粒),且具有较大的比表面积。以这种流动性好、粒径分布均匀、结晶度好的球形钛酸锂为正极材料和Li片为负极材料组成的锂离子电池具有平稳的充放电电压平台和优异的循环性能。在1.0~2.5V充放电,其首次放电容量为173.8mAh/g,经30次充放电循环后,其放电比容量仍有170.2mAh/g。     

石墨烯/富锂三元正极复合材料的制备及电化学性能研究

通过水热法制备了石墨烯包覆量不同的石墨烯/富锂三元正极复合材料。采用X射线衍射仪、扫描电子显微镜和电化学交流阻抗等对包覆后富锂三元正极复合材料的物相结构、形貌及电化学性能进行了研究。结果表明:石墨烯包覆量为2%(质量分数)时,包覆效果较好,石墨烯/富锂三元正极复合材料首次库仑效率为89.6%,比富锂三元正极材料提高了17.16%,放电比容量为226.41mAh/g,比原材料提高了21.38mAh/g;以0.5C循环100次后石墨烯/富锂三元正极复合材料放电比容量可保持在154mAh/g,容量保持率为88%,比富锂三元正极材料提高了5.3%;石墨烯/富锂三元正极复合材料阻抗为75Ω,比富锂三元正极材料阻抗低50Ω。     

Si-Al-Si复合薄膜的制备及电化学性能研究

采用磁控溅射法,通过控制其中Si薄膜的溅射时间,在铜箔集流体上沉积了4种不同Si厚度的Si-Al-Si夹层结构复合薄膜。采用原子力显微镜(AFM)和扫描电子显微镜(SEM)以及能谱仪(EDS)分析样品表面形貌和结构。采用恒电流充放电和慢循环伏安等方法研究了复合薄膜作为锂二次电池负极材料的电化学性能。结果表明,随着Si溅射时间的延长,复合薄膜首周放电容量增加,不可逆容量损失也增加;Si-Al-Si复合薄膜作为锂离子电池负极材料的循环性能随着Si溅射时间的延长而变差,但与纯Si薄膜相比,Al的加入明显降低了首周不可逆容量损失,改善了Si薄膜的循环性能。     

新型高比能量磷酸铁锂的制备及电化学性能

采用沉淀法制备了高比能量的LiFePO4/C及纯相LiFePO4正极材料,并用XRD、SEM、傅立叶红外光谱仪、程控充放电仪等对样品的结构和电化学性能进行了测试分析.结果表明,样品具有单一的橄榄石结构和良好的充放电平台,掺碳的LiFePO4具有更优良的性能,粒度较小,粒径分布均匀,振实密度达1.46g/cm3,0.1C首次放电比容量为144.6mAh/g,循环20次后容量保持率为93.2%.     

射频磁控溅射制备Sn薄膜及其电化学性能研究

采用射频磁控溅射方法在铜基片上制备了锡薄膜,把在两种溅射功率(200和350W)下制备的Sn薄膜制成锂离子电池电极。用X射线衍射、电子探针、扫描电镜及充放电实验研究比较了二电极的性能。结果表明,在350W的溅射功率下制备的Sn薄膜,与基底生成了锡铜合金;锡铜合金的生成提高了Sn薄膜与铜基片的结合力,因而具有更高的循环性能,其首次嵌锂比容量为707mAh/g,30次循环后,仍保持有643mAh/g的嵌锂比容量。     

Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

Key Aspects of Lithium Metal Anodes for Lithium Metal Batteries

Rechargeable batteries are considered promising replacements for environmentally hazardous fossil fuel‐based energy technologies. High‐energy lithium‐metal batteries have received tremendous attention for use in portable electronic devices and electric vehicles. However, the low Coulombic efficiency, short life cycle, huge volume expansion, uncontrolled dendrite growth, and endless interfacial reactions of the metallic lithium anode are major obstacles in their commercialization. Extensive research efforts have been devoted to address these issues and significant progress has been made by tuning electrolyte chemistry, designing electrode frameworks, discovering nanotechnology‐based solutions, etc. This Review aims to provide a conceptual understanding of the current issues involved in using a lithium metal anode and to unveil its electrochemistry. The most recent advancements in lithium metal battery technology are outlined and suggestions for future research to develop a safe and stable lithium anode are presented.     

Exploiting Zirconium-Based Metallic Glass Thin Films for Anode-Free Lithium-Ion Batteries and Lithium Metal Batteries With Ultra-Long Cycling Life

Coating Zr-based metallic glass, Zr₅₃Cu₃₁Ni₁₁Al₅ (Zr-MG), on a Cu current collector (CC) and Li metal anode (LMA) significantly improves the cycle performance of both types of Li-ion batteries, namely, anode-free Li-ion batteries (AFLBs) and Li metal batteries (LMB). The inherent isotropy and homogeneity of the Zr-MG significantly improve the surface uniformity of the CC and LMA. A 12 nm-thick Zr-MG thin film coating on the CC reduces the overpotential in the AFLB, leading to a more uniform Li plating morphology. The Li film covers almost the entire surface of the Zr-CC, whereas it only covers ≈75% of the bare CC during charging. An LFP||Zr-CC full-cell exhibits a capacity retention of 63.6% after the 100th cycle, with an average CE of 99.55% at a 0.2 C rate. In the case of the LMB, a 12 nm-thick Zr-MG thin film-coated LMA (Zr-LMA) exhibits a stable capacity of up to 1500 cycles. An LFP||Zr-LMA full-cell exhibits capacity retention and CE after 1500 cycles of 66.6% and 99.97%, respectively, at a 1 C rate. Zirconium-MG thin films with atomic-level uniformity, outstanding corrosion resistance, lithiophilic characteristics, and high diffusivity result in superior AFLB and LMB performances.     

钒酸锂化合物的制备和性能

采用一种新的方法合成LiV₃O₈化合物,以LiOH、V₂O₅和NH₃H₂O为反应物质,先合成出含有Li和V的反应前驱物质,再用焙烧的方法生成最终产物.X射线试验结果发现,产物在(100)方向上的衍射峰强度与用传统方法得到的产物相比明显降低.充放电结果显示,当电流为0.3mA/cm²时,在1.8～4.0V区间内,产物的首次放电比容量达到264mAh/g,循环15次后仍能达到249mAh/g.     

High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm⁻². Li anodes paired with lithium cobalt oxide (LiCoO₂) and lithium nickel cobalt manganese oxide (LiNi_0.8Co_0.1Mn_0.1O₂, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g⁻¹ and ≈765 Wh kg⁻¹ respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.     

锂离子电池电解质锂盐双乙二酸硼酸锂的制备与性能

综述了近年来锂离子电池的新型锂盐--双乙二酸硼酸锂(LiBOB)研究成果.介绍了双乙二酸硼酸锂的合成方法、组成与结构、化学和电化学性能及其与结构的关系,重点综述了对LiBOB电解液导电性的研究,对负极材料、正极材料稳定性的研究,以及与其他锂盐在锂离子电池中混合使用时的性能的研究等.总结了LiBOB的优缺点,指出了其进一步研究的方向.