Surface films formed on SnO<Subscript>2</Subscript> anode in lithium secondary batteries by FTIR spectroscopy

The chemical composition of the passivating layer formed on nano SnO2 anodes in 1 M LiClO4＋ （ethylene carbonate）EC ＋ （dimethyl carbonate）DMC at different charge/discharge states in lithium secondary batteries was studied using extra reflectance FTIR spectra. Results show that solvent decomposition reaction that generally occurs on the surface of carbon and alkali metal electrodes also takes place on nano-SnO2 anode, and the major constituent of the passivating layer is Li2CO3 and ROCO2Li. Formation of the passivating layer would certainly lead to the irreversible capacity loss.     

Investigation on the electrocatalytic characteristics of SnO<Subscript>2</Subscript> electrodes with nanocoating prepared by electrodeposition method

SnO₂ electrodes have many advantages in the degradation of toxic or bio-refractory organic wastewater, and SnO₂ is a kind of anode material which has the potential to be widely used. Electrocatalytic efficiency and service life of TiSnO₂ electrodes are key factors that can influence its applications. In order to enhance the electrocatalytic characteristics of TiSnO₂ electrodes, a type of electrocatalytic electrode with nanocoating was prepared by direct current (DC) electrodeposition method and thermal oxidation technique. With phenol as the model pollutant, the electrochemical degradation efficiencies of electrodes with nanocoating and non-nanocoating were investigated. It was demonstrated that the electrodes with nanocoating have higher efficiency than that of electrodes with non-nanocoating. The degradation time was decreased 33.3% for the same amount of phenol’s degradation. The crystal structure of surface coating, the micrograph of electrode surface and the chemical environment of Sn and Sb in the electrode surface were analyzed with the help of XRD, SEM and XPS. The results showed that the surface of electrode was mainly SnO₂ crystal with rutile structure and that much adsorbed oxygen in nanocoating was the dominant factor for enhancing the electrocatalytic characteristics. Supported by the Excellence Young Teacher Foundation of China Education Ministry and Research Foundation for Outstanding Young Scholars of Heilongjiang Province (Grant No. JC-02-04)     

Cu—Sn合金共还原法制备及电化学性能研究

采用共还原沉淀法制得Cu-Sn合金负极材料Cu6Sn5和Cu6Sn4,并分别进行不同时间的时效处理,对所得样品进行XRD分析、场发射SEM图像观察和恒流充放电性能测试。结果表明,随着时效时间的延长,样品相组成的均质性和电化学活性都得到了提高,300min时效处理的Cu6Sn5和Cu6Sn4试样的第一周比容量分别为267．5mA·h／g和342．0mA·h／g,比20min时效处理试样相应值分别增加了12．7％和17．4％。另外,增加惰性元素Cu的含量,也会改善舍金的电化学性能,增加其循环稳定性。     

过硫酸铵表面处理对富锂锰基正极材料电化学性能的影响

为了提高锂离子电池富锂锰基正极材料的电化学性能,尤其是倍率性能,采用过硫酸铵作为处理剂对富锂锰基正极材料Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2进行表面处理,诱发化学预活化,形成有利于锂离子迁移的表面尖晶石结构。电化学测试结果显示,当过硫酸铵与Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2质量比为1:5时,经过硫酸铵表面处理后的正极表现出优异的电化学性能:0.2 C下放电容量为257.1 mAh/g,首圈库伦效率高达96.8%, 3 C大倍率下放电容量仍达到157.2 mAh/g。交流阻抗测试结果表明,适量过硫酸铵处理之后材料的界面电荷转移阻抗显著降低,导致锂离子界面迁移速率加快,表现出良好的倍率性能。这种简单易行的改性方法为实现富锂锰基正极在动力锂离子电池领域的应用提供了新思路。     

Synthesis and characterization of Li1.05Co0.3Ni0.35Mn0.3M0.05O2 (M=Ge,Sn)cathode materials for lithium ion battery

In order to improve the electrochemical performance and thermal stability of Li_1.05Co_1/3Ni_1/3Mn_1/3O₂ materials,Li_1.05Co_0.3Ni_0.35Mn_0.3M_0.05O₂（M=Ge,Sn）cathode materials were synthesized via co-precipitation method.The structure,electrochemical performance and thermal stability were characterized by X-ray diffraction（XRD）,charge/discharge cycling,cyclic voltammetry（CV）,electrochemical impedance spectroscopy（EIS）and differential scanning calorimetry（DSC）.ESEM showed that Sn-doped and Ge-doped slightly increased the size of grains.XRD and CV showed that Sn-doped and Ge-doped powders were homogeneous and had the better layered structure than the bare one.Sn-doped and Ge-doped improved high rate discharge capacity and cycle-life performance.The reason of the better cycling performance of the doped one was the increasing of lithium-ion diffusion rate and charge transfer rate.Sn-doped and Ge-doped also improved the mateials thermal stability.     

Nano-sized Sn/MWNTs and MWNTs Served as the Anode of Lithium Ion Battery

A chemical deposition was supposed to be an effwient method in preparation of nano-sized Sn/ MWNTs. The nanoconmposites of MWNTs and Sn/ MWNTs were both used as anodes of lithium ion battery. The special capacities and coulomb efficiencies of Snl MWNTs were studied by means of electrochemical methods. The coating of Sn on MWNTs observed by TEM was amorphous and nano-sized. The reversible capacity of Sn/ MWNTs , which was much larger than that of MWNTs , was 824 mAh/ g in the 1 st charge and discharge cycle. The coulomb efficiency of Sn/ MWNTs in the 1 st cycle was increased by 16% compared with that of MWNTs. The additional Sn, which was 37wt% of total Sn/ MWNTs＇ weight, introduced the additional reversible lithiation capacity at least 250 mAh/ g in the 40 charge and discharge cycles. The dispersing degree of Sn on MWNTs was the main reason for the influence of the electrochemical perfomance of the Sn/ MWNTs . Sn/ MWNTs is proved to be a promising candidate as an anode of lithium ion battery.     

Synthesis and properties of Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for Li-ion batteries

Carbon was coated on the surface of Li₂MnSiO₄ to improve the electrochemical performance as cathode materials, which were synthesized by the solution method followed by heat treatment at 700 °C and the solid-state method followed by heat treatment at 950 °C. It is shown that the cycling performance is greatly enhanced by carbon coating, compared with the pristine Li₂MnSiO₄ cathode obtained by the solution method. The initial discharge capacity of Li₂MnSiO₄/C nanocomposite is 280.9 mAh/g at 0.05 C with the carbon content of 33.3 wt%. The reasons for the improved electrochemical performance are smaller grain size and higher electronic conductivity due to the carbon coating. The Li₂MnSiO₄/C cathode material obtained by the solid-state method exhibits poor cycling performance, the initial discharge capacity is less than 25 mAh/g.     

Self-assembled SnO<Subscript>2</Subscript> colloidal particles and their gas sensing performance to H<Subscript>2</Subscript>, C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH and LPG

Using organo-tin Sn(OC4H9)4 as precursor, sodium dodecyl sulfonate (SDS) and SDS-gelatin (SDS-G) complex as template, two tin dioxide colloidal particles were prepared by a self-assembly method. Both SnO2 products were respectively labelled SnO2-B particles with SDS and SnO2-C particles with SDS-G, which are applied in fabricating SnO2 gas sensors corresponding to SnO2-B’ and SnO2-C’ sensors. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermo-gravimetry and different thermal analysis (TG/DTA) were used for characterizations. The experimental results show that SnO2-B colloidal particles are composed of mesoporous piece-like particles, while SnO2-C particles mainly consist of spherical particles. Gas sensing measurements show that SnO2-B’ sensor performs the best sensing response to all target gases, including H2, C2H5OH and liquid petroleum gas (LPG). In particular, the sensing response of SnO2-B’ sensor is achieved at 32 in H2 atmosphere at the concentration of 1000×10-6 M. The gas sensing mechanism was purposely discussed from the electron transfer process and the microstructures of the as-prepared SnO2 products. It is found that serious agglomerations in SnO2-B’ particles facilitate the high gas sensing performance of SnO2-B’ sensor, while mesoporous structures in SnO2-C’ particles decrease the gas sensing response of SnO2-C’ sensor.     

Mechanism of Capacity Fading Caused by Mn(Ⅱ) Deposition on Anodes for Spinel Lithium Manganese Oxide Cell

The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale application.The traditional opinion is that Mn(Ⅱ) ions in the anode are reduced to the metallic manganese that helps for catalyzing electrolyte decomposition.This could poison and damage the solid electrolyte interface(SEI) film,leading to the the capacity fade in Li-ion batteries.We propose a new mechanism that Mn(Ⅱ) deposites at the anode hinders and/or blocks the intercalation/de-intercalation of lithium ions,which leads to the capacity fade in Li-ion batteries.Based on the new mechanism assumption,a kind of new structure with core-shell characteristic is designed to inhabit manganese ion dissolution,thus improving electrochemical cycle performance of the cell.By the way,this mechanism hypothesis is also supported by the results of these experiments.The LiMn_(2-x)Ti_xO_4 shell layer enhances cathode resistance to corrosion attack and effectively suppresses dissolution of Mn,then improves battery cycle performance with LiMn_2O_4 cathode,even at high rate and elevated temperature.     

Synthesis and electrochemical properties of polyradical cathode material for lithium second batteries

A stable polyradical, poly (2 ,2,6,6-tetramethylpiperidinyloxy methacrylate)(PTMA) , was synthesized, and its structure was determined by infrared, ultraviolet-visible, and ESR spectroscopy. Cyclic voltammograms of the PTMA polyradical electrodes were obtained by using a three-electrode cell at a scan rate of 5 mV/s within a potential range of 3. 2-4. 0 V. The results show that the shape of oxidation peak is very similar to that of reduction peak, and oxidation peak current is equal to the corresponding reduction peak current, which suggest that PTMA possesses an excellent reversibility. The difference of the anodic peak potential (Ea,p = 3. 66 V, vs Li/Li+) and ca-thodic peak potential(Ec,p = 3. 58 V, vs Li/Li+ ) is estimated at 80 mV, which is extremely less than that of the other organic positive materials in lithium second batteries such as organosulfide compounds, leading to a capability for high current capability in the charging and discharging process of the battery. The maximum discharge specif     

Mechanical properties of individual core-shell-structured SnO<Subscript>2</Subscript>@C nanofibers investigated by atomic force microscopy and finite element method

Although SnO₂-based nanomaterials used to be considered as being extraordinarily versatile for application to nanosensors, microelectronic devices, lithium-ion batteries, supercapacitors and other devices, the functionalities of SnO₂-based nanomaterials are severely limited by their intrinsic vulnerabilities. Facile electrospinning was used to prepare SnO₂ nanofibers coated with a protective carbon layer. The mechanical properties of individual core-shell-structured SnO₂@C nanofibers were investigated by atomic force microscopy and the finite element method. The elastic moduli of the carbon-coated SnO₂ nanofibers remarkably increased, suggesting that coating SnO₂ nanofibers with carbon could be an effective method of improving their mechanical properties.     

Bilayer carbon-based structure with the promotion of homogenous nucleation for lithium metal anodes

Lithium metal anodes (LMAs) are considered as the promising alternatives for next-generation high energy density batteries, but are still hampered by the severe growth of uncontrollable lithium dendrites. The growth of lithium dendrites induces poor cycling lifespan and serious safety concerns, dragging lithium metal batteries out of practical applications. We designed a bilayer carbon-based structure covered with Co/C nanosheets and vertical graphene sheets (VGS). The enormous specific surface area and uniformly distributed Co nanoparticles of the CC@Co/C-VGS host are derived from its unique design, which can reduce local current density and nucleation overpotential, resulting in a dendrite-free morphology and exceptional cycling stability. Symmetric cells exhibit over 400 cycles (800 h) at a high current density/capacity of 10 mA cm^?2/10 mA h cm^?2. Full cells using LiFePO₄ as the cathode have an enhanced rate capability and a prolonged lifespan, reaching 90 mA h g^?1 after 1000 cycles at 2 C with 73.5% capacity retention. This unique design sheds light on developing high-performance LMAs.

     

Preparation and electrochemical properties of polymer Li-ion battery reinforced by non-woven fabric

A polymer electrolyte based on poly(vinylidene) fluoride-hexafluoropropylene was prepared by evaporating the solvent of dimethyl formamide, and non-woven fabric was used to reinforce the mechanical strength of polymer electrolyte and maintain a good interfacial property between the polymer electrolyte and electrodes. Polymer lithium batteries were assembled by using LiCoO2 as cathode material and lithium foil as anode material. Scanning electron microscopy, alternating current impedance, linear sweep voltammetry and charge-discharge tests were used to study the properties of polymer membrane and polymer Li-ion batteries. The results show that the technics of preparing polymer electrolyte by directly evaporating solvent is simple. The polymer membrane has rich micro-porous structure on both sides and exhibits 280% uptake of electrolyte solution. The electrochemical stability window of this polymer electrolyte is about 5.5 V, and its ionic conductivity at room temperature reaches 0.151 S/m. The polymer lithium battery displays an initial discharge capacity of 138 mA·h/g and discharge plateau of about 3.9 V at 0.2 current rate. After 30 cycles, its loss of discharge capacity is only 2%. When the battery discharges at 0.5 current rate, the voltage plateau is still 3.7 V. The discharge capacities of 0.5 and 1.0 current rates are 96% and 93% of that of 0.1 current rate, respectively.     

Graphene as a high-capacity anode material for lithium ion batteries

Graphene was produced via a soft chemistry synthetic route for lithium ion battery applications. The sample was characterized by X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron microscopy and transmission electron microscopy, respectively. The electrochemical performances of graphene as anode material were measured by cyclic voltammetry and galvanostatic charge/discharge cycling. The experimental results showed that the graphene possessed a thin wrinkled paper-like morphology and large specific surface area (342 m²·g^?1). The first reversible specific capacity of the graphene was as high as 905 mA·h·g^?1 at a current density of 100 mA·g^?1. Even at a high current density of 1000 or 2000 mA·g^?1, the graphene maintained good cycling stability, indicating that it is a promising anode material for high-performance lithium ion batteries.     

In situ growth of NiS2 nanosheet array on Ni foil as cathode to improve the performance of lithium/sodium-sulfur batteries

The NiS₂ nanosheet array on Ni foil (NiS₂/NF) was prepared using an in situ growth strategy and sulfidation method and was used as the cathode of lithium sulfur battery. The unique nanostructure of the NiS₂ nanosheet array can provide abundant active sites for the adsorption and chemical action of polysulfides. Compared with the sulfur powder coated pure NF (pure NF-S) for lithium sulfur battery, the sulfur powder coated NiS₂/NF (NiS₂/NF-S) electrode exhibits superior electrochemical performance. Specifically, the NiS₂/NF-S delivered a high reversible capacity of 1007.5 mAh g⁻¹ at a current density of 0.1 C (1 C= 1675 mA g⁻¹) and kept 74.5% of the initial capacity at 1.0 C after 200 cycles, indicating the great promise of NiS₂/NF-S as the cathode of lithium sulfur battery. In addition, the NiS₂/NF-S electrode also showed satisfactory electrochemical performance when used as the cathode for sodium sulfur battery.

     

一步固相法制备高性能Li_2MnSiO_4/C锂离子电池正极材料

采用一步固相法合成了Li_2MnSiO_4/C正极材料,利用XRD,EIS和循环伏安测试对该材料进行了结构和电化学性能表征.研究了一步固相法中添加不同比例的葡萄糖对Li_2MnSiO_4材料性能的影响.结果表明:葡萄糖作碳源复合可以提高Li_2MnSiO_4正极材料的充放电比容量和循环性能,同时在一步固相合成法中还能细化Li_2MnSiO_4正极材料颗粒.葡萄糖添加量为6%时,制备得到的Li_2MnSiO_4/C正极材料首次可逆放电比容量为213.1 mAh/g.     

报废锂电池高效便捷放电液对比研究

近年来, 随着新能源汽车产业的快速发展, 锂电池的产量不断增长, 市场上现有的锂电池若干年后将要退役。退役锂电池在资源化回收过程中多用NaCl 溶液浸泡放电, 对环境有很大的污染风险。为了探究清洁、高效、经济的放电体系, 通过对比实验, 研究NaCl、NaOH、Na₂SO₄、Na₂CO₃ 溶液浸泡退役锂电池的放电效率、金属元素和氟化物的释放情况, 以及重复利用性能。结果表明, 采用NaOH 溶液可以实现和NaCl 溶液相似的放电效率, 可以有效减少放电过程中污染物的产生和释放, 将电解液泄露产生的HF大部分固定于放电溶液中。而且, 经多次重复放电性能未见衰减, 工业应用前景较大。     

锂离子电池高性能硅基负极材料研究进展

硅基材料因其具有较高的理论比容量被认为是具有广阔前景的锂离子电池负极材料,在近年来得到广泛的研究;但是硅较差的电子导电性和在充放电过程中的巨大的体积膨胀问题,导致其具有较差的循环性能,阻碍了它的商业化应用。本文从介绍硅材料储锂机制及失效原理出发,重点综述了近年来对硅基材料的改性研究,主要包括对硅材料的纳米化及维度设计、硅复合材料的制备及其结构设计、新型粘结剂与电解液/电解液添加剂的研究和预锂化技术的研究。最后文章对硅基负极材料的结构设计、性能改进研究进行了总结,并展望了高容量硅基负极材料在高比能锂电池等领域的应用前景。     

Sn/C纳米复合材料的合成及其电化学嵌放锂性能

用SnCl4和葡萄糖的水热反应合成SnO₂/碳质复合材料,然后在氮气气氛中热处理使SnO₂被碳热还原为Sn纳米粒子,制备得到Sn/C纳米复合材料.用X-射线衍射(XRD), 透射电镜(TEM)和X-射线电子散射能谱(EDX)对样品进行表征.结果显示Sn纳米粒子具有球形的形貌,并均匀地分散在无定形的碳材料中.对于Sn质量分数58.5%和32.3％的Sn/C复合材料,Sn纳米粒子的平均粒径分别为51和20 nm.电化学测试结果显示,Sn/C复合材料具有高的电化学贮锂可逆容量和良好的循环稳定性.讨论了Sn/C纳米复合材料的形成机理及其循环稳定性能改善的原因.     

Preparation and electrochemical performance of MWCNTs@MnO2 nanocomposite for lithium ion batteries

Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-discharge tests were used to characterize the structures and electrochemical performances of the as-prepared nanocomposite.The capacity reaches 1233.6 mA h g-1 at a current density of 100 mA g-1 for the first discharge,and it can still maintain a capacity of 633.1mA h g-1 after 100 charge-discharge cycles.The results show that MWCNTs with good electrical conductivity as anchors of MnO2 can provide fast electron transport channels for MnO2 in the electrochemical reactions,and the as-prepared MWCNTs@MnO2 nanocomposite is a potential anode material for lithium ion batteries.