锂离子电池掺钴正极材料电子结构的DV-Xa研究

采用原子基表示的第一原理赝势方法，计算了正极材料LiMn2O4的电子结构，发现LiMn2O4的价带主要是由Mn(8)和Mn(9)的3d轨道和O(7)、O(6)、O(4)的2p轨道构成，导带主要是由Mn(8)和Mn(9)的3d轨道和O(7)的2p轨道构成．通过计算Li5Mn2C0O8的电子结构，发现在LiMn2O4中用钴离子取代16d位锰离子将使电极材料的费米能减小，放电电压降低；锂离子的净电荷增大，锂离子与氧离子的相互作用增强，可逆容量降低；同时由于价带宽度变窄，Co-O键间的相互作用比Mn-O键间的相互作用强，所以，结构稳定性增加，电极循环性能改善．     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

采用原子基表示的第一原理赝势方法 ,计算了正极材料LiMn2 O4的电子结构 ,发现LiMn2 O4的价带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)、O(6 )、O(4 )的 2p轨道构成 ,导带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)的 2 p轨道构成 .通过计算Li5Mn7CoO8的电子结构 ,发现在LiMn2 O4中用钴离子取代 16d位锰离子将使电极材料的费米能减小 ,放电电压降低 ;锂离子的净电荷增大 ,锂离子与氧离子的相互作用增强 ,可逆容量降低 ;同时由于价带宽度变窄 ,Co-O键间的相互作用比Mn -O键间的相互作用强 ,所以 ,结构稳定性增加 ,电极循环性能改善 .     

FAAS测定锂离子电池正极材料LiMn2O4中的杂质钠

采用火焰原子吸收光谱法测定锂离予电池正极材料LiMn2O4中杂质Na的含量.综合考虑了消电离剂氯化铯、盐酸浓度、基体对测Na产生的影响,通过控制酸的浓度和在标准溶液中加入定量基体和消电离剂氯化铯来消除测定误差.由实验结果可知本方法简便易行,灵敏度和准确度高,精密度好,回收率在96.2%-103.8%之间,相对标准偏差(RSD)小于2%(n=10),能够满足锂离子电池正极材料分析的要求.     

锂离子电池正极材料Li2FeSiO4的电子结构与输运特性

采用基于密度泛函理论第一性原理方法, 研究了对称性为Pmn2₁的正交结构聚阴离子型硅酸盐Li₂FeSiO₄及其相关脱锂相LiFeSiO₄的电子结构, 并进一步采用玻尔兹曼理论对其输运性质进行计算. 电荷密度分析表明, 由于强Si–O共价键的存在使Li₂FeSiO₄晶体结构在嵌脱锂过程中始终保持稳定, 体积变化率只有2.7%. 能带结构与态密度计算结果表明, 费米能级附近的电子结构主要受Fe-d轨道中电子的影响, Li₂FeSiO₄ 的带隙宽度明显小于LiFeSiO₄, 说明前者的电子输运能力优于后者. 输运性质计算表明, 电导率在300–800 K时对温度的变化并不敏感, 同时也证明了Li₂FeSiO₄晶体的电导率大于LiFeSiO₄晶体, 与能带和态密度分析结论一致.     

磷酸铁锂正极材料的研究进展

锂离子电池正极材料磷酸铁锂(LiFePO4)的理论比容量为170mAh·g-1,电压平台为3.5V(vs.Li/Li+),安全性好,原材料来源丰富,成本低,对环境友好,因此成为当前研究热点之一.文章从LiFePO4的晶体结构和充放电机制入手,分析了其导电性和倍率性能差的原因,回顾了其充放电机制研究的进展,综述了各种改善LiFePO4导电性、提高其倍率性能的方法,最后对LiFePO4正极材料的研究方向进行了展望.     

纳米储锂材料和锂离子电池

简单综述了锂离子电池的基本原理和发展现状，对中国科学院物理研究所固体离子学课题组在纳米储锂材料方面的研究进展做了介绍。用HRTEM等手段研究了纳米SnO、纳米Si以及纳米SnSb合金在Li入脱嵌过程中结构的变化。着重介绍了一种具有纳米微孔的球形硬碳材料和纳米SnSb合金钉扎的复合负极材料，在高功率密度和高能量密度锂离子电池方面具有广阔应用前景。     

新型锂离子电池正极材料LiMPO_4(M=Fe,Mn)的谱学和电化学研究

采用固相反应与液相反应,合成了新型锂离子电池正极材料LiMPO4(M=Fe,Mn)。粉末X光衍射表明材料均为纯相。对材料的显微拉曼光谱和红外光谱进行了研究和指认。循环伏安研究表明,含锂磷酸盐是一类有潜力的锂离子电池正极材料。     

锂离子电池LiMn1-xFexPO4(0<x<1)正极材料的制备及性能研究

本文采用固相法制备了纯相LiMn_1-xFe_xPO₄/C (x=0.2,0.4,0.6)正极材料,并用X射线衍射(XRD)和扫描电镜(SEM)进行表征,用高精度电池测试系统进行充放电和循环伏安测试.结果表明不同Mn和Fe原子比的电极材料具有很大的性能差异,其中当x=0.4时,材料具有优异的循环稳定性和较高的可逆容量.首次充电容量和放电容量分别达到141.5 mAh/g和125.7 mAh 关键词： 锂离子电池 固相法 1-xFe_xPO₄')" href="#">LiMn_1-xFe_xPO₄ 正极材料     

以碳粉为负极材料制备锂离子电池及电池性能测试

在能量存储技术中,锂离子电池是高能量密度的电化学电源.以碳为负极材料,涂膜制备了负极片,以锂片为正极片制备了CR2016锂离子电池,并对其性能进行了测试,分析了碳粉为锂电负极材料的特性.     

锂离子电池电极材料的第一性原理研究进展

文章综述了第一性原理计算在锂离子电池电极材料模拟与设计方面的研究进展.电极材料的研究包括电极材料的电子结构和电子导电性的研究,嵌锂电位、锂离子输运特性、嵌锂过程中局部结构弛豫与相变以及材料表面特性研究等方面,第一性原理计算在上述诸方面的研究都取得了一定的进展.这些理论上的研究成果,可以帮助人们加深对材料性能与机理的理解,同时对材料的设计也具有指导意义.     

Silicon Monoxide Carbonized by Fluorocarbon As a Composite Material for Anodes of Lithium-Ion Batteries

Technical Physics - Disperse composite materials based on silicon monoxide and carbon (SiO/C) have been obtained by thermal treatment of a powder mixture consisting of 40 wt % SiO and 60 wt %...     

Negative Electrodes for Lithium-Ion Batteries Obtained by Photoanodization of Solar-Grade Silicon

Technical Physics - Negative electrodes for lithium-ion batteries prepared by electrochemical etching of single-crystalline silicon crystals demonstrate a high specific capacity per gram of the...     

First Principles Study on NaxLi1-xFePO4 As Cathode Material for Rechargeable Lithium Batteries

The electronic structure and ionic dynamic properties of pure and Na doped （Li site） LiFePO4 have been investigated by first-principles calculations. The band gap of the Na doped material is much narrow than that of the undoped one, indicating of better electronic conductive properties. First-principles based molecular dynamic simulations have been performed to examine the migration energy barriers for the Li ion diffusion. The results shown that the energy barriers for Li diffusion decreased a little along the one-dimensional diffusion pathway, indicating that the ionic conductive property is also improved, as compared with the high valance doping （such as CF） cases.     

通过掺杂V和F提高碳包覆的磷酸铁锂锂离子电池的电化学性能

在原位聚合合成方法的基础上,结合两步烧结过程制得LiFe_1-xV_x(PO₄)_(3-y)/₃F_y/C.V和F掺杂对碳包覆的磷酸铁锂材料的结构、形貌和电化学性能有影响.通过XRD、FTIR、SEM、充/放电测试和电化学阻抗谱对材料的结构、形貌和电化学性能进行了表征.结果表明,V和F的掺杂并没有破坏橄榄石结构中的LiFePO₄/C,但可以提高晶体结构的稳定,降低电荷的转移阻抗,提高锂离子扩散速度,改善了LiFePO₄/C材料的循环性能和高倍率性能.     

Nano-composite LiMnPO4 as new insertion electrode for electrochemical supercapacitors

Nano-composite olivine LiMnPO₄ (nC-LMP) was found to exhibit facile pseudo-capacitive characteristics in aqueous as well as non-aqueous electrolytes. We demonstrated employing nC-LMP as positive electrode in hybrid electrochemical capacitors namely Li-Ion hybrid capacitors (LIC). Adapting a simple CVD technique, nano-crystallites of LiMnPO₄ were coated with carbon monolayers of ∼2 nm thick to circumvent its poor intrinsic electronic conductivity. The novelty is that the single crystallites were intimately covered with carbon ring and networked to the neighboring crystallites via the continuous carbon wire-like connectivity as revealed from HRTEM analysis. Single electrode faradic capacitance of 3025 Fg⁻¹ (versus standard calomel reference electrode) was deduced for carbon coated LMP, the highest reported hitherto in Li⁺ aqueous electrolytes. Employing nC-LMP as working electrode versus an activated carbon (AC), we obtained a high specific energy of 28.8 Wh kg⁻¹ with appreciable stability in aqueous electrolytes whereas in nonaqueous electrolyte there is an obvious increase in energy density (35 Wh kg⁻¹) due to wider potential window. That is, a full cell version of LIC, AC|Li⁺|LMP, was fabricated and demonstrated its facile cycling characteristics via removal/insertion of Li⁺ within nC-LMP (positive electrode) and the electrosorption of Li⁺ into mesoporous carbon (AC) (negative electrode). Such cells ensured a typical battery-like charging and EDLC-like discharging characteristics of LIC type electrochemical capacitors (ECs) which are desired to enhance safety and energy densities.     

First Principles Calculations of Mössbauer Spectra of Intermetallic Anodes for Lithium-Ion Batteries

Changes in ¹¹⁹Sn and ¹²¹Sb Mössbauer spectra due to lithium insertion in tin and antimony based anode materials for lithium-ion batteries are analysed. Due to the complexity of the spectra linear augmented plane wave calculations of the electronic density were used to evaluate the electron density and the electric field gradients at the nucleus. The ¹¹⁹Sn Mössbauer spectrum of SnO+3.5 Li was evaluated from the theoretical spectra of the Li–Sn alloys. The observed good agreement between experimental and ab initio spectra is consistent with the reversible lithium insertion mechanism based on the formation of Li–Sn alloys. The analysis of the ¹²¹Sb Mössbauer spectra for Li insertion into CoSb₃ is somewhat more complex but calculations of the Mössbauer parameters clearly indicate the existence of Li₃Sb at the end of the first discharge.

     

Enhanced high-temperature performances of LiMn2O4 cathode by LiMnPO4 coating

Ionics - LiMnPO4/LiMn2O4 (LMP/LMO) composite cathodes with LMP coating on the surface of LMO were synthesized by hydrothermal method at 180&nbsp;°C for 10&nbsp;h. The crystal...     

Enhanced conductivity and electrical relaxation studies of carbon-coated LiMnPO4 nanorods

Lithium manganese phosphate (LiMnPO₄) nanorods were synthesized using the modified polyol method. Polyvinylpyrrolidone was used as a stabilizer to control the shape and size of LiMnPO₄ nanorods. Resin coating process was used to coat the carbon over the LiMnPO₄ nanorods. X-ray diffraction and Fourier transform infrared spectroscopy results showed the formation of LiMnPO₄ crystalline phase. The TEM image shows a uniform coating of the nano size (2.3 nm) carbon over the surface of LiMnPO₄ nanorods and the EDS spectrum of the carbon-coated LiMnPO₄ nanorods confirming the presence of carbon element along with the other Mn, P, and O elements. Impedance measurements were made on pure and carbon-coated LiMnPO₄ nanorods, and their conductivities were evaluated by analyzing the measured impedance data using the WinFIT software. More than two orders of magnitude of conductivity enhancement was observed in the carbon-coated LiMnPO₄ nanorods compared to pure ones, and the conductivity enhancement may be attributed to the presence of carbon over LiMnPO₄ nanorods. Temperature dependence of conductivity and ac conductivity were calculated using impedance data of pure and carbon-coated LiMnPO₄ nanorods. CR2032 type lithium ion coin cells were fabricated using pure and carbon-coated LiMnPO₄ nanorods and characterized by measuring charge–discharge cycles between 2.9 and 4.5 V at room temperature. More than 25 % of improved capacity was achieved in the carbon-coated LiMnPO₄ nanorods when compared to pure ones synthesized using modified polyol and resin coating processes.     

Structural,electrical and dielectric studies of nanocrystalline LiMnPO4 particles

Olivine-structured LiMnPO₄ nanoparticles were prepared by microwave-assisted solvothermal method. The as obtained LiMnPO₄ sample was characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and impedance spectroscopy techniques. The XRD pattern confirms the formation of LiMnPO₄ phase with an orthorhombic structure. The electrical conductivity of the sample at room temperature is found to be 1.2654?×?10^?7 S cm^?1. Dielectric spectra show an increase in dielectric constant with increase of temperature. The dielectric loss spectra reveal the predomination of DC conduction in the sample. The modulus studies indicate the non-Debye nature of the sample which corresponds to the distribution of elements in the sample. Galvanostatic battery testing showed that LiMnPO₄ nanoparticles displayed good cycleability in 30 cycles.