复合金属氧化物正极材料 Li(CoxNiyMn1-x-y)O2高功率锂离子动力电池的试制及电化学性能的研究

用化学方法合成用于锂离子动力电池正极的新型高电压高容量复合金属氧化物材料Li(Co_xNi_yMn_1-x-y)O₂试制了具有良好热稳定性的高功率 8 Ah 锂离子动力 电池。在研究了该电池的电化学性能后, 研制了用于混合动力电动车辆的电池系统并进行了车载实验。结果表明该 电池系统在深度放电条件下不仅显现出十分优越的循环性能和一致性, 经过模拟工况测试后的数据还表明单体电池升温最高仅为 5℃, 即电池系统还具有良好的热稳定性, 因此该电池系统是适合用于混合动力电动汽车的。     

High-performance lithium–sulfur battery based on porous N-rich g-C3N4 nan-otubes via a self-template method

The commercial development of lithium–sulfur batteries (Li–S) is severely limited by the shuttle effect of lithium polysulfides (LPSs) and the non-conductivity of sulfur. Herein, porous g-C3N4 nanotubes (PCNNTs) are synthesized via a self-template method and util-ized as an efficient sulfur host material. The one-dimensional PCNNTs have a high specific surface area (143.47 m2·g?1) and an abundance of macro-/mesopores, which could achieve a high sulfur loading rate of 74.7wt%. A Li–S battery bearing the PCNNTs/S composite as a cathode displays a low capacity decay of 0.021% per cycle over 800 cycles at 0.5 C with an initial capacity of 704.8 mAh·g?1. PCNNTs with a tubular structure could alleviate the volume expansion caused by sulfur and lithium sulfide during charge/discharge cycling. High N contents could greatly enhance the adsorption capacity of the carbon nitride for LPSs. These synergistic effects contribute to the excellent cycling stability and rate performance of the PCNNTs/S composite electrode.     

氮化硼复合石墨毡及其氧还原电极的电化学性能研究

为了提升石墨毡作为氧还原电极的电化学性能,将五硼酸铵热解生成氮化硼原位复合至石墨毡碳纤维上,具体探究了不同比例氮化硼/石墨毡复合材料用作锂—空气电池的氧还原电极时的电化学性能,其中10%比例下氮化硼/石墨毡的电化学性能最佳,主要表现在首次深度放电容量较原始石墨毡提升了20%,首次放电充电的氧还原反应和氧析出反应极化降低了约0.3 V.该方案操作简便,成本低廉且绿色无污染,对锂空电池性能的提升有较好效果.     

锂离子电池正极材料安全性能——热稳定性

锂离子电池由于安全性问题，使大容量电池的应用受到限制，比如用作电动汽车（EV）、混合动力汽车（HEV）的动力电源。以不同正极材料组装成AA型锂离子电池，研究其热稳定性。试验结果表明尖晶石型LiMn2O4作为锂离子电池正极材料，热稳定性最好；新型包埋镍酸锂梯度正极材料有高的比能量和优良的循环性。     

锂离子电池正极材料安全性能——过充性能

锂离子电池由于安全性问题,使大容量电池的应用受到限制,比如用作电动汽车（EV）、混合动力汽车（HEV）的动力电源.以不同正极材料组装成AA型锂离子电池,研究其过充性能.试验结果表明尖晶石型LiMn2O4作为锂离子电池正极材料,耐过充性较好;新型包埋镍酸锂梯度正极材料有很好的耐过充性能.     

One Step Bali-Milling Synthesis of LiFePO4 Nanoparticles as the Cathode Material of Li-lon Batteries

A one-step synthetic method was used to synthesize Olivline LiFePO4 powders by direct ball milling the stoichiometric mixture of Fe, Li3PO4 , and FePO4 powders. XRD and TEM measurements revealed that the as-prepared LiFePO4 powder have a homogeneous Olivine structure and a uniform size distribution of ca. 50 nm. Based on this material, a LiFePO4/C composite was prepared and used for the cathode material of Li-ion batteries. The charge-discharge experiments demonstrated that the LiFePO4/C composite material has a high capacity of 132 mAh/g at 0.1 C and a quite highrate capability of 95 mAh/g at 1 C. This new ball-milling method may provide a completely green synthetic route for preparing the materials of this type cost-effectively and in large volume.     

Low temperature synthesis of NiO/Co3O4 composite nanosheets as high performance Li-ion battery anode materials

NiO/Co3O4 composite nanosheets have been synthesized via a facile method at low temperature for the first time.The as prepared materials were characterized by X-ray powder diffraction(XRD) and transmission electron microscopy(TEM),and the performance of Li-ion batteries(LIBs) as anode materials were also studied.By controlling the atom ratio of Ni:Co,not only the size of the nanosheets can be controlled,the electrode’s conductivity and stability could also be greatly improved.The composite material showed a stable capacity retention during cycling(87% of the second capacity was retained after 15 cycles) even at a relatively large current rate(400 mA/g).The NiO/Co3O4 nanosheet might be promising candidate anode materials in high performance Li-ion batteries.     

A novel Co(phen)2/C catalyst for the oxygen electrode in rechargeable lithium air batteries

A novel Co(phen)2/C catalyst was prepared by coating cobalt(II) phenanthroline (phen) chelate on BP2000 carbon black and then heat treating in an inert atmosphere. The obtained Co(phen)2/C product with 1.0 wt% cobalt loading exhibits similar morphology and porosity characteristics to those of the bare BP2000. X-ray diffraction measurements demonstrate a face-centered cubic (fcc) α-Co phase embedded in the carbon support after pyrolysis. Charge/discharge tests of the lithium-oxygen cells using the prepared Co(phen)2/C catalyst show high discharge capacities of 4870 mAh g-1 (0.05 mA cm-2 ), 3353 mAh g-1 (0.1 mA cm-2 ) and 3220 mAh g 1 (0.15 mA cm-2 ), respectively. The Co(phen) 2 /C cathode exhibits reasonable reversibility with capacity retention of 1401 mAh g-1 ( 0.1 mA cm-2 ) after 10 cycles. The superior electrochemical performance of the prepared Co(phen)2/C catalyst and low cost of the phenanthroline chelating agent indicate that Co(phen)2/C is a promising cheap catalyst for lithium-air batteries.     

Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries are lithiumion batteries with solid-state electrolytes instead of liquid electrolytes.They are hopeful in solving the safety problems of lithium-ion batteries,once their large capacity and long life are achieved,they will have broad application prospects in the field of electric vehicles and large-scale energy storage.The working potential window of solid electrolytes is wider than that of liquid electrolytes,so high-voltage cathode materials could be used in all-solidstate lithium-ion batteries to get higher energy density and larger capacity by elevating the working voltage of the batteries.The spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithium-rich cathode materials can be expected to be applied to all-solid-state lithium-ion batteries as cathode materials due to their highvoltage platforms.In this review,the electrochemical properties and structures of spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithiumrich cathode materials are introduced.More attentions are paid on recent research progress of conductivity and interface stability of these materials,in order to improve their compatibility with solid electrolytes as cathode materials in all-solid-state lithium-ion batteries and fully improve the properties of all-solid-state batteries.Finally,the existing problems of their application in all-solid-state lithium-ion batteries are summarized,the main research directions are put forward and their application prospects in all-solid-state lithium-ion batteries are discussed.     

锂-空气电池研究进展

 锂-空气电池是通过金属锂与空气中的O₂反应产生电能,它的理论比容量高达3828mAh/g,在电动汽车等领域展现出重要的应用前景。本文综述了近年来锂-空气电池领域的最新研究进展,对有机体系、有机-水混合体系与固态体系三类锂-空气电池的结构与原理进行了分析。总结了有机体系的多孔碳空气电极、催化剂、电解液等方面的研究工作。多孔碳的孔容是决定空气电极比容量最重要的结构参数,具有高孔容的多孔碳可以为放电过程中生成的氧化锂提供更多的储存空间,从而表现出高的比容量,多孔碳的比表面积与平均孔径对比容量也有重要的影响;合适的电催化剂可以有效的降低氧还原反应与析氧反应的过电压,从而提高能量效率;具有高极性、低黏度、低吸湿性、高溶解氧的电解液有利于改善电池的相关性能。总结了有机-水混合体系的隔膜、电解液等方面的研究工作。对有机相与水相电解液均具有良好抗化学腐蚀性的超级锂离子导通玻璃膜是目前有机-水混合体系研究的关键。总结了固态体系最新的研究进展。此外,展望了锂-空气电池领域今后的发展方向。     

One Step Ball-Milling Synthesis of LiFePO_ 4 Nanoparticles as the Cathode Material of Li-Ion Batteries

0 IntroductionLik-eito nsh baartete irnie sre (ceLnItB sy)ea hrasv ien r athpiedl pyo retxapbalend eeldec tthroeinric m daer--vices and are also considered as preferred power sources forelectric vehicles[1 ,2]. These require the LIBs to be made ofcheaper ,safer andenvironmentallyfriendly materials ,particu-larly of the cathode materials .In past fewyears ,LiFePO4hasbeen extensively studied as the most promising cathode mate-rial due toits sufficient cycling capacity,lowcost andthermalstabi…     

MgFeSiO4 prepared via a molten salt method as a new cathode material for rechargeable magnesium batteries

Well-crystallized MgFeSiO₄ microparticles were synthesized at different temperatures by a simple molten salt method using KCl flux. As a new cathode for rechargeable magnesium batteries, the material shows a reversible Mg²⁺ intercalation-deintercalation process. In 0.25 mol/L Mg(AlCl₂EtBu)₂/THF electrolyte, MgFeSiO₄ synthesized at 900??C can deliver a 125.1 mAh/g initial discharge capacity and a 91.4% capacity retention on the 20th cycle at a rate of 0.1C (about 15.6 mA/g). The results show that MgFeSiO₄ could be a good host for Mg²⁺ intercalation, and a potential cathode material for high-energy rechargeable magnesium batteries.     

高温固相法合成锂离子电池正极材料LiNi0.8Co0.2O2研究

研究了高温固相法合成锂离子电池正极材料LiNi0.8Co0.2O2时原材料、气氛、温度、时间、Li:(Ni Co)化学计量比例、氧气流量、二次烧结等参数对制备电极活性材料结构和电性能的影响，使用其优化后的工艺参数，制备出容量为170mAb/g的LiNi0.8Co0.2O2,并对此正极材料组成的电池性能进行了测试。     

Synthesis of LiFePO4 in situ vapor-grown carbon fiber （VGCF） composite cathode material via microwave pyrolysis chemical vapor deposition

One of the most important factors that limits the use of LiFePO 4 as cathode material for lithium ion batteries is its low electronic conductivity.In order to solve this problem,LiFePO 4 in situ vapor-grown carbon fiber (VGCF) composite cathode material has been prepared in a single step through microwave pyrolysis chemical vapor deposition.The phase,microstructure,and electrochemical performance of the composites were investigated.Compared with the cathodes without in situ VGCF,the initial discharge capacity of the composite electrode increases from 109 to 144 mA h g-1 at a 0.5-C rate,and the total electric resistance decreases from 538 to 66.The possible reasons for these effects are proposed.     

Optimizing the Synthetic Conditions of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 from a Carbonate Co-precipitation Method

1 Introduction As a promising cathode material for lithium ion batteries,LiNi1/3Co1/3Mn1/3O2 attracted intensive attentions.Owing to high specific capacity,long circle life and excellent safety,it may be an alternative candidate for LiCoO2.As a complex composite,however,it is difficult to synthesize phase-pure LiNi1/3Co1/3Mn1/3O2 by a simple mixed calcination method[1].From this concern,carbonate co-precipitation method,which can prepare homogeneous LiNi1/3Co1/3Mn1/3O2 with typical layered structure,bec...     

α-MnO2 hollow clews for rechargeable Li-air batteries with improved cyclability

Lithium-air(Li-air) batteries have attracted worldwide attention due to their high energy density(11140 Wh kg-1) comparable to gasoline.In this work,we have synthesized the α-MnO2 hollow clews via a simple method and characterized them by X-ray diffraction and scanning electron microscope.Interestingly,cycle performance of Li-air batteries is improved greatly when using the α-MnO2 hollow clews as the catalyst.The first discharge capacity is 596 mAh g-1,and the charge capacity is 590 mAh g-1 at the current density of 0.1 mA cm-2 between 2.0 and 4.2 V using the Vulcan XC-72 as the carbon material.Additionally,by re-assembling new batteries with the used lithium foil,separators and cathode separately,we find that the cathode is the key role to end the Li-air battery life.     

锂离子电池用正极材料Li(Co0.2-XNi0.8MnX)O2的合成制备研究

研究了一种制备新型锂离子电池正极材料的工艺方法．通过采用溶胶凝胶法(sol-gel法合成了新型电池正极材料Li(Co0．2-XNi0．8MnX)O2。并采用XRD方法分析了材料的相变过程、烧结温度、烧结时间对材料相合成的影响及不Mn／Co比掺杂对材料相变的影响；通过SEM照片可见，Li(Co0．2-XNi0．8MnX)O2粉末元素分布均匀、粒径为1～4微米．为今后进行充放电性能的测试工作做准备．     

CoO/SnO2@NC/S复合材料的制备及其应用于高稳定性锂硫电池正极材料

To improve the sulfur loading capacity of lithium-sulfur batteries (Li–S batteries) cathode and avoid the inevitable “shuttle effect”, hollow N doped carbon coated CoO/SnO₂ (CoO/SnO₂@NC) composite has been designed and prepared by a hydrothermal-calcination method. The specific surface area of CoO/SnO₂@NC composite is 85.464 m2·g–1, and the pore volume is 0.1189 cm3·g–1. The hollow core-shell structure as a carrier has a sulfur loading amount of 66.10%. The initial specific capacity of the assembled Li–S batteries is 395.7 mAh·g–1 at 0.2 C, which maintains 302.7 mAh·g–1 after 400 cycles. When the rate increases to 2.5 C, the specific capacity still has 221.2 mAh·g–1. The excellent lithium storage performance is attributed to the core-shell structure with high specific surface area and porosity. This structure effectively increases the sulfur loading, enhances the chemical adsorption of lithium polysulfides, and reduces direct contact between CoO/SnO₂ and the electrolyte.     

电动汽车用动力锂离子二次电池系统性能的研究

采用尖晶石锰酸锂和以锰为主的多元金属氧化物正极材料分别研制了Mn 系正极高功率和高容量动力锂离子二次电池, 研究并比较了Mn 系动力电池与海内外几家公司制造的LiFePO₄动力电池的电化学性能。结果表明Mn 系高容量和高功率动力电池不仅具有高能量密度、优越 的高低温与倍率充放 电特性、热稳定性良好, 同时电池的 SOC-OCV 线性关系还有利于管理系统的控制, 因此该类动力电池会成为今后动力电池的一个重要发展方向。     

干湿交替对砂岩断裂特性影响试验研究

周期性的水岩相互作用对岩石的物理力学性能有较大的影响,被认为是影响岩土工程安全稳定性的重要因素之一。以典型的均质青砂岩为试验对象,利用中心裂纹圆盘试件开展了砂岩I~II复合型断裂试验,研究了干湿交替作用对砂岩I~II复合型断裂特性的影响;通过观测干湿交替后砂岩微观结构的变化特征,探讨了干湿交替作用的劣化机理;并结合复合型断裂则对试验结果进行了有效评估。研究表明,砂岩的纯I型,纯II型以及I~II复合型断裂韧度均随着干湿交替次数的增加而逐渐减小;其劣化趋势基本一致,但劣化程度略有不同。当加载角较大或II型分量主导时,干湿交替作用对砂岩断裂韧度的劣化影响更为显著。考虑了T应力影响的广义最大周向应变准则和广义最大周向应力准则都能对试验结果进行很好的预测。在纯II型时,基于广义最大周向应变准则的理论预测值比基于广义最大周向应力准则的理论值更接近试验值。