Silicon-based nanomaterials for lithium-ion batteries

Silicon-based nanomaterials have been of scientific and commercial interest in lithium-ion batteries due to the low cost,low toxicity,and high specific capacity with an order of magnitude beyond that of conventional graphite.The poor capacity retention,caused by pulverization of Si during cycling,triggers researchers and engineers to explore better battery materials.This review summarizes recent work in improving Si-based anode materials via different approaches from diverse Si nanostructures,Si/metal nanocomposites,to Si/C nanocomposites,and also offers perspectives of the Si-based anode materials.     

Progression of the silicate cathode materials used in lithium ion batteries

Poly anionic silicate materials,which demonstrate a high theoretical capacity,high security,environmental friendliness and low-cost,are considered one of the most promising candidates for use as cathode materials in the next generation of lithium-ion batteries.This paper summarizes the structure and performance characteristics of these materials.The effects of different synthesis methods and calcination temperature on the properties of these materials are reviewed.Materials that demonstrate low conductivity,poor stability,cationic disorder or other drawbacks,and the use of various modification techniques,such as carbon-coating or compositing,elemental doping and combination with mesoporous materials,are evaluated as well.In addition,further research topics and the possibility of using these kinds of cathode materials in lithium-ion batteries are discussed.     

Mechanochemical synthesis and high-capacity performances of transition-metal borides as aqueous anode materials

Transition-metal borides MB0.5(M = Co,Mo,V) were synthesized by high-speed mechanical ball-milling of the corresponding elemental metals and boron,and investigated as aqueous anode materials.The as-synthesized borides can achieve an excellent discharge capacity,about twice that of their parent transition metals.The metal boride electrodes also exhibit polarizations about 100-300 mV lower than those of their parent metals.The galvanostatic discharge curve of CoB0.5 shows a single discharge voltage plateau as a result of simultaneous electro-oxidation of elemental cobalt and/or amorphous cobalt boride.Both MoB0.5 and VB0.5 show two well-defined voltage plateaus,corresponding to the electro-oxidation of the corresponding metal and boride.These results show that the coexisting transition metal and boride in the metal borides co-activate each other in the ball-milling process,thereby significantly enhancing their electrochemical performances.     

Superior corrosion resistance-dependent laser energy density in(CoCrFeNi)95Nb5 high entropy alloy coating fabricated by laser cladding

(CoCrFeNi)95Nb5 high entropy alloy(HEA)coatings were successfully fabricated on a substrate of Q235 steel by laser cladding technology.These(CoCrFeNi)95Nb5 HEA coatings possess excellent properties,particularly corrosion resistance,which is clearly superior to that of some typical bulk HEA and common engineering alloys.In order to obtain appropriate laser cladding preparation process parameters,the effects of laser energy density on the microstructure,microhardness,and corrosion resistance of(CoCrFeNi)95Nb5 HEA coating were closely studied.Results showed that as the laser energy density increases,precipitation of the Laves phase in(CoCrFeNi)95Nb5 HEA coating gradually decreases,and diffusion of the Fe element in the substrate intensifies,affecting the integrity of the(CoCrFeNi)95Nb5 HEA.This decreases the microhardness of(CoCrFeNi)95Nb5 HEA coatings.Moreover,the relative content of Cr2O3,Cr(OH)3,and Nb2O5 in the surface passive film of the coating decreases with increasing energy density,causing corrosion resistance to decrease.This study demonstrates the controllability of a high-performance HEA coating using laser cladding technology,which has significance for the laser cladding preparation of other CoCrFeNi-system HEA coatings.     

Nitrogen-doped graphene nanosheets as high efficient catalysts for oxygen reduction reaction

It is of great significance in exploring alternative catalysts to platinum (Pt)-based materials for oxygen reduction reaction (ORR),because this reaction is invariably involved in various fuel cells and metal-air batteries.We herein reported the nitrogen doped graphene nanosheets (NGNSs) with pore volume of as high as 3.42 m 3 /g and investigated their potential application as ORR catalysts,it was demonstrated the NGNSs featured high activity,improved kinetics and excellent long-term stability for ORR.The NGNSs were successfully used as cathode catalysts of microbial fuel cells (MFCs) and performed even better than the commercial Pt/C (Pt 10%) catalysts at the maximum power output.     

LiNi0.8Co0.2O2的表面修饰及性能

锂离子电池正极材料和电解液之间的恶性相互作用引起正极材料和电池性能的劣化。将LiNi0.8Co0.2O2,LiOH*H2O和H3BO3以摩尔比100∶1∶2均匀混合,500℃热处理10h,在LiNi0.8Co0.2O2表面包覆上一层Li2O-2B2O3玻璃层。用X光电子能谱、扫描电镜和X光衍射分析对包覆前后LiNi0.8Co0.2O2的结构进行了表征。结果表明,表面修饰有效地抑制了LiNi0.8Co0.2O2和电解液之间的恶性相互作用,材料的实际比容量提高,充放电循环稳定性改善,自放电速率减小。表面修饰处理是改善锂离子电池正极材料综合性能的有效途径。     

高密度球形LiNi0.8Co0.2O2的制备及性能

采用控制结晶法合成球形β-Ni0.8Co0.2(OH)2,与LiOH     

Synthesis of spherical Li1.167Ni0.2Co0.1Mn0.533O2 as cathode material for lithium-ion battery via co-precipitation

xLi2MnO3·(1-x)LiNi0.4Co0.2Mn0.4O2(x=0.5) powders were synthesized from co-precipitated spherical metal carbonate,Ni0.2Co0.1Mn0.533(CO3)x.It has been found that the preparation of metal carbonate was si...     

Ca掺杂的对LiNi1/3Co1/3Mn1/3O2正极材料及其电化学性能研究

为探讨Ca的掺杂对LiNi_1/3Co_1/3Mn_1/3O₂材料结构和电性能的影响,以草酸为沉淀剂,以不同含量Ca对LiNi_1/3Co_1/3Mn_1/3O₂进行掺杂改性,并通过X射线衍射（XRD）对产品进行表征,探讨了不同Ca含量样品的电化学性能.结果表明：大量Ca掺杂生成明显CaO杂相,而少量Ca掺杂则能顺利进入材料晶格之中.随着Ca掺入,晶体类型不变,但c轴略收缩,形成更紧密的结构. 充放电显示Ca在低倍率(2.5～4.3 V,0.5 C)时,能一定程度提高材料的循环性能;但在高倍率(2.5～4.3 V,5 C)时,能明显提高容量和循环性能.充放电曲线同时显示未掺杂的材料高倍率下极化严重,放电平台严重降低;而Ca掺杂的材料极化状况则不明显,说明Ca掺杂能抑制极化并提高电化学性能.     

面心立方结构Fe0.1Co0.9/Al2O3纳米复合材料结构和磁性研究

采用溶胶—凝胶法及在氢气中还原的工艺得到面心立方结构的Fe0.1Co0.9/Al2O3纳米复合粉末,利用X射线衍射、透射电子显微镜、振动样品磁强计对样品微观结构和磁性进行了研究.结果表明FeCo合金以面心立方结构存在于纳米复合材料中.由于Co的掺入,FeCo合金的晶粒尺寸下降而晶格常数增大.另外,由于磁矩和晶粒尺寸的变化导致FeCo合金的饱和磁化强度下降而矫顽力增加.     

Synthesis and electrochemical properties of LiNi0.8Al0.2−xTixO2 cathode materials by an ultrasonic-assisted co-precipitation method

A new co-precipitation route was proposed to synthesize LiNi_0.8Al_0.2−xTi_xO₂ (x=0.0-0.20) cathode materials for lithium ion batteries, with Ni(NO₃)₂, Al(NO₃)₃, LiOH·H₂O, and TiO₂ as the starting materials. Ultrasonic vibration was used during preparing the precursors, and the precursors were protected by absolute ethanol before calcination in the air. The influences of doped-Ti content, calcination temperature and time, additional Li content, and ultrasonic vibration on the structure and properties of LiNi_0.8Al_0.2−xTi_xO₂ were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge-discharge tests, respectively. The results show that the optimal molar fraction of Ti, calcination temperature and time, and additional molar fraction of Li for LiNi_0.8Al_0.2−xTi_xO₂ cathode materials are 0.1, 700°C, 20 h, and 0.05, respectively. Ti doping facilitates the formation of the α-NaFeO₂ layered structure, and ultrasonic vibration improves the electrochemical performance of LiNi_0.8Al_0.2−xTi_xO₂.     

Structure and electrochemical properties of LiLaxMn2-xO4 cathode material by the ultrasonic-assisted sol-gel method

Powders of spinel LiLa_xMn_2—xO₄ were successfully synthesized by the ultrasonic-assisted sol-gel (UASG) method. The structure and properties of LiLa_xMn_2—xO₄ were examined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electronic microscopy (SEM), galvanostatic charge-discharge test, and cyclic voltammetry (CV). XRD results show that the La³⁺ can partially replace Mn³⁺ in the spinel and the doped materials with La³⁺ have a larger lattice constant compared with pristine LiMn₂O₄. FT-IR indicates that the absorption peak of Mn³⁺−O and Mn⁴⁺− O bonds has a red and blue shift with the increase of doping lanthanum in LiLa_xMn_2—xO₄, respectively. The charge-discharge test exhibits that the initial discharge capacity of LiLa_xMn_2—xO₄ drops off, and the capacity retention increases gradually at C/5 discharge rate with the increase of doping lanthanum, and LiLa_0.01Mn_1.99O₄ has a higher discharge capacity and a better cycling performance at 1C discharge rate. CV reveals that the doping La³⁺ is beneficial to the reversible extraction and intercalation of Li⁺ ions.     

高容量正极材料Li[Li0.17Mn0.58Ni0.25]O2的倍率性能

采用碳酸盐共沉淀工艺,通过控制结晶合成了显微形貌呈现较大差异的Li[Li0.17Mn0.58Ni0.25]O2样品,并对样品进行了X射线衍射、高分辨透射电镜、场发射扫描电镜分析以及恒电流充放电和交流阻抗测试.合成的Li[Li0.17Mn0.58-Ni0.25]O2材料均具有良好的结晶度,可标定为α-NaFeO2结构(空间群R3m).其中,具有一次颗粒沿六方棱柱长轴方向形成“簇形”团聚的材料比其他样品具有优异的倍率性能,在电压范围为2.5～4.8 V,倍率分别为0.5C、1.0C和3.0C时,Li[Li0.17Mn0.58Ni0.25]O2材料首次放电比容量分别达到205.4、195.5和158.5 mA·h·g-1,100次循环后放电比容量保持在203.5、187.2和151.2 mA·h·g-1,容量保持率分别为99％、96％和95％.Li[Li0.17Mn0.58Ni0.25]O2材料特殊的颗粒团聚状态降低了界面的电荷转移阻抗,材料的倍率性能显著提高.同时,文中对Li[Li0.17Mn0.58Ni0.25]O2材料在不同截止电压下的电化学性能进行了对比分析.     

PdO—CuO／Ce0.8Zr0.2O2催化上CO还原NO反应性能的研究

以Ce0.8Zr0.2O2复合氧化物为载体,采用共浸渍法配制了一系列PdO-CuO/Ce0.8Zr0.2O2双组分催化剂,选择NO－CO反应为模型反应,考察了催化剂的还原活性。结果表明,不同配比的PdO-CuO双组分催化剂的NO还原活性均要优于单组分的PdO和CuO催化剂。     

退火温度对Ti0.975Co0.025O2薄膜样品的结构和磁性的影响

采用溶胶—凝胶法在Si表面通过浸渍提拉制备了Ti0.975Co0.025O2薄膜样品,并在空气氛围下以不同温度对样品进行退火处理.利用差热/热重综合热分析仪(TG-DTA)、X射线衍射仪(XRD)、扫描射电镜(SEM)和振动样品磁场计(VSM)对薄膜样品的结构和磁性进行研究.实验结果表明,薄膜的二维结构提高了TiO2向金红石结构转变的温度,延缓了晶粒的生长.薄膜样品的磁性受超顺磁效应影响较弱,主要受氧空位的影响.随着空气氛围下退火温度的升高,样品的结构就会越完善,从而使得样品中氧空位的浓度减少,饱和磁化强度减弱.