Effect of the pitch-based carbon anode on the capacity loss of lithium-ion secondary battery

The total capacity loss of lithium-ion secondary cell is reduced by engineering the pitch-based carbon anode through one or more of the following methods: attaining a high degree of graphitization, minimizing the surface oxygen concentration, attaining a large crystal size L_c, degassing, and use of PVDF in place of teflon as the binder.     

MnO2 prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery

Two α-MnO₂ crystals with caddice-clew-like and urchin-like morphologies are prepared by the hydrothermal method, and their structure and electrochemical performance are characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), galvanostatic cell cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The morphology of the MnO₂ prepared under acidic condition is urchin-like, while the one prepared under neutral condition is caddice-clew-like. The identical crystalline phase of MnO₂ crystals is essential to evaluate the relationship between electrochemical performances and morphologies for lithium-ion battery application. In this study, urchin-like α-MnO₂ crystals with compact structure have better electrochemical performance due to the higher specific capacity and lower impedance. We find that the relationship between electrochemical performance and morphology is different when MnO₂ material used as electrochemical supercapacitor or as anode of lithium-ion battery. For lithium-ion battery application, urchin-like MnO₂ material has better electrochemical performance.     

Effect of particle shape on the electrochemical properties of CaSnO3 as an anode material for lithium-ion batteries

Cubic and star-shaped CaSnO₃ particles with a perovskite structure were synthesized successfully using a simple hydrothermal method at a low temperature of 140 °C. The structure and morphology of the CaSnO₃ powders were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties of the CaSnO₃ as anode materials for lithium-ion batteries were tested by constant current discharge/charge and cyclic voltammetry. The large irreversible capacity in the initial cycle was similar to that of tin oxide, due to the decomposition of tin oxide into metallic tin and Li₂O, followed by a reversible Li–Sn formation. The reversible capacity of the cubic CaSnO₃ was 382 mAh g^?1 in the first cycle and was maintained at 365 mAh g^?1 in the following cycles. The cubic CaSnO₃ particles had a higher reversible capacity than the star-shaped CaSnO₃ particles and retained a capacity of about 365 mAh g^?1 after 60 cycles as well as good cycle stability, showing potential as attractive anode materials for lithium-ion batteries. It is found that the particle shape had a marked effect on electrochemical performance.     

热处理对锂离子电池硅/石墨/炭负极电化学性能的影响

将天然石墨、酚醛树脂和微米级硅粉进行球磨处理制备复合材料前驱物,再于N2气氛下700℃炭化得到硅/石墨/炭(Si/G/C)复合电极材料,采用X射线衍射仪、扫描电镜和透射电镜及电化学循环充放电对其形貌、结构及其电化学性能进行表征.结果表明,Si/G/C作为锂离子电池负极材料具有高于900 mA·h/g的可逆比容量,40次循环后保持在550 mA·h/g.对电极进行热处理后,其循环性能显著提高,40次循环后比容量保持在700 mA· h/g.扫描电镜分析结果显示,热处理后集流体上电极材料分布更均匀,因涂抹不均形成的空隙不复存在.热处理后电极结构更致密、内部黏结强度增大使其结构稳定性明显提升,是电极循环性能提高的主要原因.     

锂离子电池负极材料中国专利分析

通过对中国发明专利数据进行挖掘和计量分析,总结了锂离子电池负极材料的专利申请情况、行业发展现状、地域分布及重点创新主体的专利技术布局。结果表明,锂离子电池负极材料经过几年的持续增长后,专利申请趋势放缓。通过对专利进行地域分析,了解到中国本土申请人和日本申请人申请了大量的专利;国内申请人主要集中在广东、上海、北京及浙江。通过分析一些重点企业申请的专利技术布局可以了解目前市场上的负极材料技术热点。     

锂离子电池LiNi_xFe_(1-x)PO_4正极材料的制备及其电化学性能

本文以蔗糖为碳源,采用固相法合成了锂离子电池LiNixFe1-xPO4(x=0、0.05、0.1、0.2和0.3)正极材料,通过XRD和SEM等表征所合成的产物为多孔炭和LiFePO4相以恒电流充放电和电化学阻抗谱研究了材料的电化学性能,结果LiNi0.1Fe0.9PO4的性能最佳,其粒径大小在500～1000nm左右,在2C的充放电条件下,其放电比容量为70.3mAh·g-1,15次循环后容量保持率达90%。     

锂离子电池硅负极材料粉化问题研究进展

硅作为锂离子电池的负极材料由于其很高的理论比容量（4212 mA·h·g^-1）而备受关注。硅材料的研究集中在解决充放电中体积胀缩所引起的粉化问题。通过调研近年来硅负极材料粉化问题研究进展,对比了各种方法的优劣和思路,在此基础上进行了简单的评述。     

Synthesis and electrochemical properties of artificial graphite as an anode for high-performance lithium-ion batteries

Artificial graphite containing abundant in situ grown onion-like carbon hollow nanostructures (OCHNs) was prepared from nickel nanoparticles doped pitch and natural graphite flakes by hot-pressing sintering method. Galvanostatic discharge–charge tests indicate that the synthetic graphite with abundant OCHNs exhibits a high specific capacity of 460 mA h g⁻¹ at 20 mA g⁻¹ as well as an excellent rate capability, with a reversible capacity of 220 mA h g⁻¹ at 1 A g⁻¹. Besides the advantages of common graphite anode materials, these superiorities make synthetic graphite a very promising anode for high-performance lithium-ion batteries.     

Single wall carbon nanotube paper as anode for lithium-ion battery

“Free-standing” single wall carbon nanotube (SWNT) papers have been synthesised by simple filtration method via positive pressure. A conventional SWNT slurry coated electrode was fabricated to compare with the SWNT papers. The results show that the capacity of the “Free-standing” electrode was slightly lower than that of the conventional electrode, but the “Free-standing” electrode was produced without any binder, and metal substrate, so that the weight of electrode was reduced significantly. On the other hand, the procedures for SWNT electrode preparation were simplified, so the cost of the manufacturing could be reduced.     

Electrochemical studies of LiB compound as anode material for lithium-ion battery

Electrochemical studies of LiB compound were carried out for its application as anode for lithium-ion battery. The compound exhibited a reversible discharge-charge behavior between 0 and 0.75 V versus Li/Li⁺ with a first discharge capacity of 293 mA h g⁻¹. Discharging to 1.0 V, the first discharge capacity of LiB compound was 660 mA h g⁻¹, but a part of this capacity was irreversible. Impedance spectra were measured at several potentials corresponding to different discharge plateaus. The impedance spectra obtained below and above 0.8 V presented significantly different features. The solid electrolyte interphase layer (SEI) was formed below 0.8 V and assumed a good performance of LiB electrode in this potential range. The SEI was found to deteriorate above 0.8 V, which might be associated with the irreversible discharge capacity.     

Effect of calcination temperature on the morphology and electrochemical properties of Co3O4 for lithium-ion battery

A simple approach to synthesize Co₃O₄ in mass production by using hexamethylenetetramine (HMT, C₆H₁₂N₄) as a precipitator via hydrothermal treatment has been developed. The samples were calcinated at different temperatures ranging from 300 to 600 °C and characterized by XRD and SEM. The structure became agglomerative and collapsed with an increase in calcination temperature. Evaluation of the electrochemical performance in combination with SEM and BET analysis suggests that there is an optimum calcination temperature for Co₃O₄. It is found that the retention capacity of well crystallized Co₃O₄ hollow microspheres has a higher specific surface area at 300 °C and is almost above 94% after the 5th cycle at different current densities of 40 and 60 mA g⁻¹, which shows good long-life stability and favorable electrochemical behaviors. Using EIS analysis, we demonstrated that lithium-ion conduction inside the SEI layers and charge transfer at the electrode/electrolyte interface became hindered with an increased calcination temperature, which was in good agreement with the electrochemical behaviors of three Co₃O₄ electrodes. It is proposed that drastic capacity fading and the variation of resistive components (SEI layers and charge transfer) can be influenced by morphologies due to the calcination temperature.     

非化学计量比尖晶石型锂离子电池正极材料的合成与表征

采用阴阳离子复合掺杂,以共沉淀法、超声共沉淀法、Pechini法和高温固相法合成掺杂锰酸锂前驱体,使用三段热处理方式,即650℃预烧、780℃烧结、550℃回火制备掺杂非化学计量尖晶石Li _1.05 Co _0.05 Ni _0.05 Mn _1.9 O _3.9 F _0.1 .通过化学容量分析测定Mn含量和平均价态,用粒度分布、电镜扫描（SEM）、X射线衍射（XRD）、电化学性能测试对产物进行表征.结果表明产物的Mn含量和平均价态与理论值吻合.比较各种合成方法,超声共沉淀法产物的粒径分布最窄、比表面积最小（0.96 m²•g^-1）、晶型完整、衍射强度最大、结晶性能最佳、晶格常数a为0.821 nm、晶粒尺寸L为57.78 nm.经装配电池电化学性能测定,超声共沉淀法产物的初始容量更高,循环性能更稳定,经30次循环后容量衰减仅9.3％.     

锂离子电池负极材料钛酸锂的制备与研究

以四氯化钛、氢氧化锂为原料,采用模板法,获得前躯体（Li1.81H0.19）Ti2O5·0.262 5TiO2,再通过煅烧,得到纳米钛酸锂（Li4Ti5O12）。最佳制备工艺条件为：模板∶钛（摩尔比）为4∶1,700℃煅烧1 h。采用TEM电镜观测的粒度达到10~100 nm,XRD拟合粒径5~30 nm,比表面积达100~600 m2/g。     

Effect of magnesium on the electrochemical behavior of lithium anode in LiOH aqueous solution used for lithium-water battery

The effect of adding magnesium to lithium on lithium electrochemical behavior in 4 mol L⁻¹ LiOH is studied using electrochemical techniques. The results show that the hydrogen evolution rate is decreased with increasing Mg content. Through theoretical analysis and X-ray (XRD) investigation, MgH₂ and Mg(OH)₂ are created on the surface film of lithium-magnesium alloys after discharge. The porosity of the lithium surface film is decreased by MgH₂, Mg(OH)₂ combined with LiOH and LiOH·H₂O and the hydrogen evolution rate is decreased effectively. Magnesium addition to lithium reduces the extent of hydrogen evolution by alteration of the hydride-hydroxide layer also reduces the extent of anodic dissolution without a significant change in the system efficiency.     

Synthesis and electrochemical performance of Li4Ti5O12 submicrospheres coated with TiN as anode materials for lithium-ion battery

The TiN coated Li₄Ti₅O₁₂ (LTO) submicrospheres with high electrochemical performance as anode materials for lithium-ion battery were synthesized successfully by solvothermal method and subsequent nitridation process in the presence of ammonia. The XRD results revealed that the crystal structure of LTO did not change after thermal nitridation process. The submicrospheres morphology of LTO and TiN film on the surface of LTO submicrospheres were characterized by FESEM and HRTEM, respectively. XPS result confirmed that a small amount of Ti changed from Ti⁴⁺ to Ti³⁺ after nitridation process, which will increase the electronic conductivity of LTO. Electrochemical results showed that electrochemical performance of TiN coated LTO anode materials compared favorably with that of pure LTO. Also its rate capability and cycling performance were apparently superior to those of pure LTO. The reversible capacity of TiN-LTO is 105.2 mA h g⁻¹ at a current density of 10 C after 100 cycles and maintain 92.9% of its initial discharge capacity, while that of pure LTO is only 83.6 mA h g⁻¹ with a capacity retention of 90.3%. Even at 20 C, the discharge capacity of TiN coated LTO sample is 101.3 mA h g⁻¹, compared with 77.3 mA h g⁻¹ for pristine LTO in the potential range 1.0–2.5 V (vs. Li/Li⁺).     

High rate capability of carbonaceous composites as anode electrodes for lithium-ion secondary battery

Anode materials with high rate capability for Li-ion secondary batteries were investigated by using the mixture of graphite, cokes, and petroleum pitch. Since obvious potential plateaus were obtained at graphite contents above 40 wt.%, which would cause difficulties in perceiving the capacity variations as a function of electrical potential, the graphite content were determined at 20–30 wt.%. The composites with a given content of graphite and remaining content of petroleum pitch/cokes mixtures at 1:4, 1:1, and 4:1 mass ratios were heated at a temperature range of 800–1200 °C. For a given composition of carbonaceous composite, the discharge rate capability improved but the reversible capacity decreased with increasing the heat treatment temperature. Although the reversible capacity increased with increasing content of the petroleum pitch for given graphite content and heat treatment temperature, the discharge rate capability decreased. The carbonaceous composites prepared by the mixture of 30 wt.% graphite and 70 wt.% petroleum pitch/cokes mixture at 1:4 mass ratio with the heat treatment at 800 °C showed relatively high electrochemical properties, of which reversible capacity, initial efficiency, discharge rate capability (retention of discharge capacity in 5 C/0.2 C) and charge capacity at 5 C were 312 mAh/g, 79%, 89% and 78 mAh/g, respectively.     

Modification of petroleum coke by different additives and the impact on anode properties

Anodes, which provide the carbon required for aluminum production, are made from dry aggregates (petroleum coke, rejected anodes, and butts) with coal tar pitch as the binder. Good quality anodes require good interaction between coke and pitch, and this relies on good wetting properties. The objectives of this work are to analyze the wetting properties of four different cokes with and without modification using an additive and to test the effect of the modified coke on anode properties. A FTIR study was done to identify functional groups in non‐modified and modified coke samples since they play an important role on coke‐pitch interactions. The wetting tests were done using the sessile‐drop method to measure the contact angle between coke and pitch. The results showed that the additive improved the wettability of all four cokes by pitch. The least wettable coke was chosen to produce anodes. For anode production, the entire dry aggregate is modified. The additive was mixed with the dry aggregate using two different approaches (one day earlier and 5 min before mixing). The anodes were characterized before and after baking. The early treatment with the additive was found to be better for the modification of dry aggregate.

     

锂离子电池正极材料LiFePO4的电化学性能改进

引言 随着社会的进步,人们对化学电源提出了高能量、长寿命、低成本、低环境污染的要求.虽然锂离子蓄电池目前已经实现了商品化,但正极嵌锂材料结构与性能的研究,以及如何提高容量和降低成本是锂离子蓄电池进一步被开发和应用的关键.