尖晶石LiMn2O4掺杂改性研究进展

尖晶石型LiMn2O4是一种极有前途的锂离子电池正极材料，具有原材料资源丰富、价格低、环境污染小、合成工艺简单等优点，但在循环及存放的过程中，存在容量衰减，在高温情况下尤为严重．对尖晶石型LiMn2O4材料的容量衰减机理进行了探讨，并对该正极材料的金属离子掺杂改性研究进行了综述．     

Nanostructure designing and hybridizing of high-capacity silicon-based anode for lithium-ion batteries

Lithium-ion batteries have long been used in electronic products and electric vehicles, but their energy density is slowly failing to keep up with demand. Because of its extraordinarily high theoretical specific capacity, silicon is regarded as the most potential next-generation anode material for practical lithium-ion batteries. However, its unavoidable volume expansion issue can cause electrode deformation and loss of electrical contact during cycling,resulting in significant performance reduc...     

Double carbon decorated lithium titanate as anode material with high rate performance for lithium-ion batteries

Spinel lithium titanate(Li_4Ti_5O_(12)) has the advantages of structural stability, however it suffers the disadvantages of low lithium-ion diffusion coefficient as well as low conductivity. In order to solve issues,we reported a simple method to prepare carbon-coated Li_4Ti_5O_(12)/CNTs(C@Li_4Ti_5O_(12)/CNTs) using stearic acid as surfactant and carbon source to prepare carbon coated nanosized particles. The obtained Li_4Ti_5O_(12) particles of 100 nm in size are coated with the carbon layers pyrolyzed from stearic acid and dispersed in CNTs matrix homogeneously. These results show that the synthesized C@Li_4Ti_5O_(12)/CNTs material used as anode materials for lithium ion batteries, presenting a better high-rate performance(147 m Ahg~(-1)at20 C). The key factors affecting the high-rate properties of the C@Li_4Ti_5O_(12)/CNTs composite may be related to the synergistic effects of the CNTs matrix and the carbon- coating layers with conductivity enhancement. Additionally, the amorphous carbon coating is an effective route to ameliorate the rate capability of Li_4Ti_5O_(12)/CNTs.     

尖晶石型LiMn2O4的溶胶凝胶法制备

采用溶胶 凝胶法合成了锂离子电池正极材料LiMn2O4·研究了干凝胶制备锰酸锂的机理·由于干凝胶燃烧时生成的产物颗粒很细,燃烧过程中就有大量的锰酸锂生成,剩下的Mn3O4和Li2O2在300℃左右已完全转化为锰酸锂,大大降低了合成温度·通过对700℃合成的锰酸锂XRD分析表明,样品的衍射峰峰形尖锐,晶型发育良好·考察了pH值对合成样品粒度及电化学性能的影响,SEM分析表明,随pH值增加,所得溶胶制备的锰酸锂电化学容量增加,当pH=6 0时合成样品颗粒分布均匀,达到亚微米级·以0 1C的电流、电压范围3 30～4 35V充放电测试表明,该条件下合成的样品初始放电容量为121.0mAh·g-1,显...     

Al,Zr dual-doped cobalt-free nickel-rich cathode materials for lithium-ion batteries

Nickel-rich and cobalt-free cathode materials have obvious advantages in the aspects of energy density and economic efficiency. However, these materials are restricted from being used in commercial lithium-ion batteries due to the problems of poor structural stability and rate capability. In this study, the aluminum and zirconium dual-doped Co-free Ni-rich LiNi_0.96Mn_0.04O₂cathode material(NMAZ) is prepared by a facile high-temperature solid-phase method. The obta...     

Comparative study of LiNiO2, LiNi0.8Co0.2O2 and LiNi0.75Al0.25O2 for lithium-ion batteries

The comparative study of LiNi0.8Co0.2O2 and LiNi0.75Al0.25O2 was carried out by X-ray diffraction (XRD) and electrochemical methods. The results show that Co and Al doping suppress the phase transition during charge-discharge. The experiments indicate that LiNi0.75Al0.25O2 has the better cycle-ability and over-charge resistance comparing with LiNi0.8Co0.2O2. The interfacial behavior was studied by use of electrochemical impedance spectroscopy (EIS). The results show that LiNi0.75Al0.25O2 has a slightly larger polarization character than LiNi0.8Co0.2O2.     

A review on SnFe2O4 and their composites: Synthesis,properties, and emerging applications

Tin ferrite (SnFe₂O₄) and their composites have been extensively studied due to their unique functional properties including appealing electronic band structure, good chemical stability, high magnetization, excellent biocompatible and earth-abundant nature. Over the past few years, SnFe₂O₄ and their composites have been well designed and investigated for various kind of applications. In this review, the most important methods for SnFe₂O₄ and their composites synthesis, such as co-precipitation, hydrothermal, solvothermal and sol-gel techniques are summarized. It is important to emphasize that this review mainly focuses on the application of SnFe₂O₄ and their composites for environmental remediation, lithium-ion batteries and hydrogen peroxide sensors, which are discussed in detail for the first time. Apart from that, the key factors and essential means to improve their performance and functionality are systematically reported. Finally, the development prospect and challenge of SnFe₂O₄ and their composites are introduced. It is anticipated that this review will be helpful in development of SnFe₂O₄ and their composites with ameliorated performances for practical application in various fields.     

锂离子电池正极材料Li2FeSiO4的改性

采用高温固相反应法在氩气气氛下合成锂离子电池正极材料Li2FeSiO4、Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C,并采用X线衍射、扫描电镜和电化学方法研究材料的结构与性能.研究结果表明:改性后的Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C材料与Li2FeSiO4具有相同的晶体结构,锰离子掺杂和表面碳包覆有效地提高了材料的比容量和循环性能.以C/16倍率充放电,Li2FeSiO4/C的首次放电容量为112mA·h/g,Li2Fe0.9Mn0.1SiO4/C材料首次放电容量达122 mA·h/g,充放电循环30次后容量衰减仅为9％.     

纳米LiMn2O4的溶胶-凝胶合成及表征

LiMn2O4是一种优良的锂离子电池正极材料。本文利用溶胶一凝胶法制备了LiMn2O4纳米粉体，使用XRD、TEM和IR进行表征。结果表明纳米样品的平均粒度为32nm。     

PLD制备LiMn2O4薄膜及参数对薄膜微观结构的影响

用脉冲激光沉积（PLD）,分别在不锈钢和单晶硅（111）衬底上生长了LiMn2O4薄膜,并对所生长LiMn2O4薄膜的结构进行了研究。结果发现,生长在不锈钢衬底上的薄膜具有粗糙的表面和随机的结晶取向,生长在单晶硅衬底上的薄膜具有相对光滑的表面,并具有明显的（111）方向上的择优取向。还研究了脉冲频率和总脉冲数对薄膜生长的影响,结果显示,在相同的沉积条件下,对于不同衬底,LiMn2O4薄膜的生长率不同;脉冲频率对薄膜生长的影响明显,在相同总脉冲数情况下,脉冲频率大,薄膜生长率明显增大。     

Nanostructured TiO2（B）:the effect of size and shape on anode properties for Li-ion batteries

Reducing the dimensions of electrode materials from the micron to the nanoscale can have a profound influence on their properties and hence on the performance of electrochemical devices,e.g.Li-ion batteries,that employ such electrodes.TiO2(B) has received growing interest as a possible anode for Li-ion batteries in recent years.It offers the possibility of higher energy storage compared with the commercialized Li4Ti5O12.Bulk,nanowire,nanotube,and nanoparticle morphologies have been prepared and studied.However,to date these materials have not be compared in one article.In the current review we first summarize the different synthesis methods for the preparation of nanostructured TiO2(B);then present the effects of size and shape on the electrochemical properties.Finally TiO2(B) with nanometer dimensions exhibit a higher capacity to store Li,regardless of rate,due to structural distortions inherent at the nanoscale.     

尖晶石型LiMn2O4电池材料的研究现状

对尖晶石型LiMn2O4电池正极材料的制备和性能,以及掺杂、表面修饰等的研究现状做了简要评述,分析了对LiMn2O4容量衰减的改善及循环性能提高的影响因素.     

Promotive effect of multi-walled carbon nanotubes on Co3O4 nanosheets and their application in lithium-ion battery

Co3O4/MWCNTs composites have been synthesized by a simple hydrothermal method using a surfactant(CTAB) and a precipitation agent(urea). The samples were characterized by XRD, SEM and BET methods. The electrochemical properties of the samples as anode materials for lithium batteries were studied by EIS and Galvanostatic measurements. The Co3O4/MWCNTs composites displayed higher capacity and better cycle performance in comparison with the Co3O4 nanosheets. The remarkable improvement of electrochemical performance within the hybrid composites is probably related to the addition of MWCNTs that possesses improved properties such as excellent electric conductivity and large surface area, which helps to alleviate the effect of volume change, shorten the distance of lithium ion diffusion, facilitate the transmission of electron and keep the structure stable.     

尖晶石型LiMn2O4的研究进展

尖晶石型LiMn2O4作为锂离子电池的正极材料之一是近年来的研究热点。尖晶石型LiMn2O4的合成方法有许多种，主要有固相法、水热合成法、共沉淀法、溶胶一凝胶法等。对各种合成方法的优缺点进行比较。同时就近年来科技工作者对LiMn2O4的性能优化作综合论述，主要包括掺杂和表面包覆，并对今后LiMn2O4的发展方向做了阐述。     

Rational design of MnS nanoparticles anchored on N,S-codoped carbon matrix as anode for lithium-ion batteries

The manganese sulfide (MnS) has attracted more attention as anode material on energy storage and conversion field, owing to its high theoretical capacity (616 ​mA ​h ​g⁻¹) and good electrochemical activity. However, low electronic conductivity and large volume expansion during charge-discharge processes have limited its further application. In order to address above mentioned problems, the composites, MnS nanoparticles embedded in N,S-codoped porous carbon skeleton (named as MnS/N,S–C composites), herein have been prepared successfully using metal organic framework (Mn-NTA) as template. The porous carbon skeleton not only can enhance electrode conductivity, but also relieve volume expansion during charge-discharge processes. Thus, the rational design towards electrode architectures has endowed MnS/N,S–C nanocomposites with superior electrochemical performance, which delivers the specific capacities of 676.7 ​mA ​h ​g⁻¹ at the current density of 100 ​mA ​g⁻¹.     

Embedding Co3O4 nanoparticles into graphene nanoscrolls as anode for lithium ion batteries with superior capacity and outstanding cycling stability

Co_3O_4 is a promising high-performance anode for lithium ion batteries(LIBs), but suffers from unsatisfied cyclability originating duo to low electrical conductivity and large volume expansion during charge and discharge process. Herein, we successfully constructed the Co_3O_4 nanoparticles embedded into graphene nanoscrolls(GNSs) as advanced anode for high-performance LIBs with large capacity and exceptional cyclability. The onedimensional(1 D) Co_3O_4/GNSs were synthesized via liquid nitrogen cold quenching of large-size graphene oxide nanosheets and sodium citrate(SC) modified Co_3O_4 nanoparticles, followed by freeze drying and annealing at400 °C for 2 h in nitrogen atmosphere. Benefiting from the interconnected porous network constructed by 1 D Co_3O_4/GNSs for fast electron transfer and rapid ion diffusion, and wrinkled graphene shell for significantly alleviating the huge volume expansion of Co_3O_4 during lithiation and delithiation. The resultant Co_3O_4/GNSs exhibited ultrahigh reversible capacity of 1200 mAh g~(-1) at 0.1 C, outperforming most reported Co_3O_4 anodes.Moreover, they showed high rate capability of 600 m Ah g-1 at 5 C, and outstanding cycling stability with a high capacity retention of 90% after 500 cycles. Therefore, this developed strategy could be extended as an universal and scalable approach for intergrating various metal oxide materials into GNSs for energy storage and conversion applications.     

Preparation and electrochemical properties of re-synthesized LiCoO2 from spent lithium-ion batteries

A new idea for reuse of the cathode materials of lithium-ion batteries(LIBs) is investigated to develop an environmentally friend-ly process for recycling spent batteries.LiCoO2 is re-synthesized from spent LIBs by leaching and a sol-gel method calcined at high temperature.Thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC) are employed to study the re-actions occurring calcination that are responsible for the weight losses.X-ray diffraction(XRD) and scanning electron microscopy(SEM) are used to determine the structures of the LiCoO2 powders.It was found that a pure phase of LiCoO2 can be obtained by the re-synthesis process.Cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) are used to evaluate the electrochemical properties of the LiCoO2 powders.The discharge capacity of re-synthesized LiCoO2 is 137 mAh g-1 at the 0.1 C rate,and the capacity retention of the re-synthesized LiCoO2 is 97.98% after 20 cycles at the 0.1 C rate,and 88.14% after 40 cy-cles.The results indicate that the re-synthesized LiCoO2 displays good charge/discharge performance and cycling behavior.     

高性能锂离子电池负极材料一氧化锰/石墨烯复合材料的合成

通过冻干-煅烧合成了一氧化锰/石墨烯(MnO/rGO)复合材料,并将其用作锂离子电池负极材料.在500 mA·g-1的电流密度下,MnO/rGO复合材料表现出高达830 mAh·g-1的可逆容量,且在充放电循环160圈后,其可逆容量依然高达805 mAh·g-1.倍率测试结果显示,循环225圈后,在2.0 A·g-1的电流密度下,其可逆容量高达412 mAh·g-1.复合材料中的石墨烯在提高材料导电性的同时有效地缓解了一氧化锰充放电过程中的体积膨胀.通过对比容量-电压的微分分析,发现复合材料超出一氧化锰理论容量的部分是由形成了更高价态的锰引起的.MnO/rGO复合材料比纯一氧化锰(p-MnO)更容易出现高价态的锰,可能是因为rGO上残留的氧为电极反应提供了额外所需的氧源.该一氧化锰/石墨烯复合材料因其简单绿色的合成过程及优异的电化学性质,有望在未来的锂电负极中得到广泛的实际应用.     

锂离子电池正极材料LiMn2O4的Al2O3包覆研究

文章采用高温固相法合成尖晶石LiMn2O4,并采用液相包覆的方法对其进行改性处理。采用XRD、SEM、XPS以及电池测试系统等,研究了所制备材料的结构、组成、性能和包覆机理。实验结果表明:表面处理后的LiMn2O4循环性能显著提高,以A12O3对尖晶石LiMn2O4进行表面包覆,使LiMn2O4颗粒不与电解液直接接触,可以防止锰离子溶解在电解液中,获得结构稳定、循环性能优异的锂离子电池正极材料;同时Al2O3会和电解液中微量的HF反应,减小了HF对锰离子溶解的加速作用。