掺杂金属氧化物贮氢电极的电化学性能

研究了掺杂金属氧化物Fe3O4和Cr2O3贮氢电极MmNi3.5Mn0.4Co0.7Al 0.4(Mm: 混合稀土)的电化学性能.结果表明,Fe3O4和Cr2O3的掺杂均使贮氢电极的放电容量增大和充电效率提高,且活化性能得到改善,活化次数减少到3～5次.Cr2O3的掺杂可使贮氢电极的放电过电位减少3.0 mV、快速放电能力(放电电流密度为500 mA*g-1)提高8.1%,同时改善了电极的循环稳定性;在同样条件下,Fe3O4的掺杂使电极过电位增大50.2 mV、快速放电能力降低11.6%,并导致电极的电荷保持能力下降.从MmNi3.5Mn0.4Co0.7Al 0.4电极的综合性能考虑,Cr2O3的掺杂对改善贮氢电极的电化学性能是有利的.     

锂离子电池正极材料磷酸钒锂的掺杂

为了降低磷酸钒锂(Li3V2(PO4)3)材料成本并提高材料中活性元素V的利用率,该文采用溶胶凝胶/碳热还原法合成了球形锂离子电池正极材料Li3V2(PO4)3及其掺杂不同金属离子(Al3+、Cr3+、Y3+、Ti4+)的衍生物。电化学测试结果表明,经摩尔分数x为5%的金属离子掺杂修饰后的Li3V2(PO4)3材料的首次充放电容量及循环性能均优于经x=10%的金属离子掺杂的材料。其中Al3+和Ti4+的掺杂更加有效,在3.0~4.8 V、0.5 mA下、摩尔分数为5%的Al3+和Ti4+掺杂后的Li3V2(PO4)3样品中首次充电容量分别为178 mAh.g-1和174.9mAh.g-1。80次循环后放电容量均保持在123 mAh.g-1左右。     

Fe-B在碱性电池中的电化学性能研究

采用化学还原法制备Fe-B,并对其进行了P元素的掺杂以作为对比.所合成的硼化物在KOH碱性溶液中具有较高的一次放电容量.在30 mA/g的电流密度下,Fe-B和Fe-P-B的首次放电容量分别为247 mAh/g和278 mAh/g,表明P元素的掺杂提高了Fe-B的首次放电比容量.     

掺杂Mo对Li1+xV3O8物相和高温阴极放电性能的影响

利用固相反应法制备Li1 xV3-yMoyO8(0≤y≤0.6)并对其进行了500 ℃和550 ℃时的放电性能测试. 采用X射线衍射测定掺杂Mo对Li1 xV3O8物相的影响, 用电子扫描电镜观察粉末的形貌, 用函数记录仪记录电压随时间的变化. 研究结果表明: 当y＞0.2时, 物相为Li1 xV3O8和V2O5;当y≤0.2时, 物相为Li1 xV3O8;掺杂Mo后的粉末形貌基本不发生变化;当放电电流密度为100 mA/cm2, 终止电压为1.8 V时, Mo的掺杂使Li1 xV3O8在500 ℃的最高电压提高约0.3 V, 比容量提高约300 A·s/g;550 ℃时嵌入Li 的量最多可达x=3.8, 接近Li1 xV3O8嵌锂量的理论值x=4.     

化学共沉淀法制备铝掺杂α-Ni(OH)2的控制条件

采用化学共沉淀法制备掺杂Al的α-Ni(OH)2,用正交实验研究pH值、掺杂Al的含量、陈化时间、反应温度等制备因素对活性物质放电比容量的影响,并用极差法分析各制备因素影响的显著性。结果是,制作性能优良的掺杂Al的α-Ni(OH)2的最佳条件为:反应温度40~50℃,掺杂10%摩尔含量的Al,陈化12~16h,pH值7.5~9.5;各因素对活性物质放电比容量影响的显著性顺序为:掺杂Al的含量>pH值>反应温度>陈化时间,在选择合成条件下制备的样品电极具有较好的充放电效率和活性物质利用率,电化学阻抗较小,最大放电比容量为345.2mAh·g-1。     

MnOx-M/AC(M=La,Ce,Co,Ni)氧还原催化材料的制备及性能

用热解法制备了掺杂La、Ce、Co、Ni等元素的氧还原催化材料MnOx/AC,并采用XRD和电化学方法对所制备材料的性质和电化学反应性能进行了表征。结果表明,掺杂适量的La、Ce、Co和Ni等元素可改善电极的氧还原反应性能。掺杂La和Co元素的MnOx/AC氧催化还原性能最好,其中,在50mA/cm2的电流条件下,使用这两种掺杂材料所制备的模拟锌-空气电池的放电电压分别为1.1236V和1.1246V。     

La(Ⅲ)和Co(Ⅱ)复合掺杂非晶态氢氧化镍的电化学性能研究

采用微乳液快速共沉淀法制备出稀土La（Ⅲ）和Co（Ⅱ）复合掺杂非晶态氢氧化镍粉体,采用XRD、SAED和Raman光谱测试分析其结构形态和形貌,将样品合成镍电极材料并组装成MH-Ni电池,研究样品电极的不同掺杂比例对其电化学性能的影响及其相应的电化学效应作用。结果发现,样品材料的微结构无序性强,质子缺陷较多,呈现明显非晶材料结构特征 在80 mA.g-1恒电流充电5h,40 mA.g-1恒电流放电,终止电压为1.0 V的充放电制度下,复合掺杂4 wt.%La（Ⅲ）2 wt.%Co（Ⅱ）样品的放电平台为1.273 V,放电容量高达348.43mAh.g-1,电极材料在充放电循环30次,放电比容量衰减率仅为2.86%,循环可逆性较好。     

Gd/Nd掺杂对BiFeO3结构和铁电性能的影响

采用快速液相烧结工艺制备了多铁陶瓷材料Bi1-xGdxFeO3(x=0.00,0.05,0.10,0.15)和Bi1-xNdxFeO3(x=0.00,0.05,0.10),研究了稀土离子Gd/Nd掺杂对多铁材料BiFeO3相结构和铁电性能的影响.X射线衍射谱显示对于Gd/Nd掺杂Bi1-xRxFeO3体系,适量掺杂有助...     

LiFe1-x Mgx PO4/C的制备和性能研究

以乙酸镁为掺杂元素、蔗糖为碳源,采用固相反应法制备镁掺杂磷酸铁锂包覆碳复合材料LiFe1-xMgxPO4/C(x=0.01,0.02,0.03,0.04).利用X射线衍射(XRD)分析其结构,扫描电镜(SEM)观察其形貌,恒电流法测定其电化学性能.研究结果表明镁离子掺杂没有影响材料的结构,而是提高了其放电容量和循环性能.在这些样品中,LiFe0.98Mg0.02位PO4/C的容量最高,首次放电达到140.0 mAh/g;并且在80次循环后容量没有衰减反而增加到148.6 mAh/g左右.     

沸腾回流法制备Al元素掺杂ZnO及表征

采用液相沸腾回流法,制备出不同含量Al元素掺杂的ZnO半导体材料,并对产物进行了XRF,XRD,SEM及其导电性能的表征.实验结果表明:Al元素掺杂后产物ZnO的结构仍然为六方晶系纤锌矿结构;Al元素掺杂量不是无限增大的,当Al元素掺杂量达到24.0 mmol/L时,就会趋于饱和;Al元素掺杂的ZnO的导电性能比纯ZnO有所提高,因此证明了这是一条比较优化的工艺合成路线.     

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.     

Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO4 batteries has received extensive attention due to its environmental impact and economic benefit. In the pretreatment process of spent LiFePO4 batteries, the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality. In this work, a facile and efficient pretreatment process is first proposed. After only freezing the electrode pieces and immersing them in boiling water, LiFePO4 materials were peeled from the Al foil. Then, after roasting under an inert atmosphere and sieving, all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils. The active materials were subjected to acid leaching, and the leaching solution was further used to prepare FePO4 and Li2CO3. Finally, the battery-grade FePO4 and Li2CO3 were used to re-synthesize LiFePO4/C via the carbon thermal reduction method. The discharge capacities of re-synthesized LiFePO4/C cathode were 144.2, 139.0, 133.2, 125.5, and 110.5 mA·h·g?1 at rates of 0.1, 0.5, 1, 2, and 5 C, which satisfies the requirement for middle-end LiFePO4 batteries. The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.     

结晶态FePO4在锂电池中的应用

在不同的温度、物质的量比和煅烧时间等条件下,分别制备FePO4正极材料,并进行X射线衍射(XRD)测试、准开路电压(QOCV)和恒流充放电(CCV)等电化学测试.经湿法研磨后,结晶态FePO4的充放电容量有很大提高,有良好循环特性,表明结晶态FePO4可以通过控制颗粒特性提高比容量,可成为低成本环保型锂电池正极材料.     

锌锰电池正极材料的改进研究

对商业锌锰电池正极材料进行了修饰,改进后电池放电性能有较大改善。在75ohm负载下连续放电至0．8V时与Duraeell Ultra（AAA）电池相比,放电时间为90．95h,平均延长31．1％;电池能量为1．555Wh,增加23．4％。     

Na0.54Bi0.46Ti0.96Al0.04O2.94氧离子导体制备与性能研究

采用传统的固相反应法合成Na0.54Bi0.46Ti0.96Al0.04O2.94氧离子导体,借助于交流阻抗谱和介电弛豫谱分别研究了钠和铝的双掺杂对Na0.5Bi0.5TiO3材料电学性能及氧离子扩散的影响。在400℃时,Na0.54Bi0.46Ti0.96Al0.04O2.94材料的晶粒电导率可以达到1.51×10-3 S/cm,是Na0.5Bi0.5TiO3材料电导率的5.5倍。在Na0.54Bi0.46Ti0.96Al0.04O2.94材料中观察到一个与氧离子弛豫相关的介电弛豫峰,弛豫参数为E= 0.80 eV和t0= 6.12×10-13 s,氧离子在Na0.54Bi0.46Ti0.96Al0.04O2.94材料中主要通过Na-Bi-Ti的路径进行扩散迁移的。结合结构参数容忍因子及自由体积的分析,钠和铝的双掺杂改善了氧离子在Na0.5Bi0.5TiO3材料中的扩散通道,但是铝的引入一定程度上提高了氧空位扩散的能量壁垒。     

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。     

用“Polymer-in-Salt”电解质制作固体电池

以 NH2 CONH2 -Li Cl O4和 NH2 CONH2 -NH4SCN为主体的“Polym er-in-Salt”作电解质 ,Zn作负极 ,Mn O2 ,Pb O2 和 PAn作正极制成多种二次电池 ,经测试该类电池有不同的开路电压和闭路电流以及能量密度     

不同空气阴极表面结构之锌-空气燃料电池性能

本论文主要针对锌-空气燃料电池之空气阴极表面结构进行改善.锌-空气燃料电池主要以氢氧化钾为电解液,利用不同空气电极表面结构进行空气阴极性能与寿命研究.实验中进行了开回路电压性能测试与定电流放电测试,并讨论其两者电压-电流性能及功率密度差异,比较不同表面结构阴极的对电解液的抗蚀能力,针对放电完的电池电极进行材料分析.由实验结果得知,如此类似保护膜功用之电极表面结构在电池反应时,能够减少电解液本身以及阳极金属氧化物对空气电极表面的影响,提供较长时间稳定电流输出,大大地提升锌-空气燃料电池空气电极之使用寿命.     

电极表面电位、电流分布的模型辨识

本文以起动型铅酸蓄电池为例,建立了电极表面电位、电流分布的数学模型。模型计算值和实验值吻合良好,表明模型的可靠性和适用性。该数学模型可用于予测电池放电过程中,电池端电压和电极表面电位、电流分布,活性物质利用率的分布等,并可用于分析不同板栅结构对这些主要参数的影响,为优化设计提供理论依据。     

Capacity fading of spinel LiMn2O4 during cycling at elevated temperature

A normal spinel LiMn2O4 as cathode material for lithium-ion cells was cycled galvanostatically (0.2 C) at 55℃. To determine the contribution of each voltage plateau to the total capacity fading of the cathode upon repeated cycling, the capacities in each plateau were separated by differentiation of voltage vs. capacity. The results showthat the capacity fading in the upper voltage plateau is more rapidlythan that in the lower during discharging, while in charging process,it fades slower than that in the lower voltage range. The increased capacity shift and aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fading rate in the upper step. Capacity shift also takes place during charging process, which again enhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a result of an increase in polarization of the cell, plays a major role in determining the fading rate in each voltage plateau, further reflecting the thickening of the passivation layer on the active particles, and the accumulation of electrolyte decomposition. The relative capacity loss for modified spinels is well correlated withthe relative increase in the polarization of the half-cells, confirming the above causes for capacity fade of this kind of cathode material.