Synthesis and electrochemical properties of Al-doped LiVPO4F cathode materials for lithium-ion batteries

Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction （CTR） process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction （XRD）,scanning electron microscopy （SEM）,and electrochemical measurements. XRD studies show that the Al-doped LiVPO4F has the same triclinic structure （space group p-↑1 ） as the undoped LiVPO4F. The SEM images exhibit that the particle size of Al-doped LiVPO4F is smaller than that of the undoped LiVPO4F and that the smallest particle size is only about 1 μm. The Al-doped LiVPO4F was evaluated as a cathode material for secondary lithium batteries,and exhibited an improved reversibility and cycleability,which may be attributed to the addition of Al^3＋ ion by stabilizing the triclinic structure.     

Effect of lithium content on the electrochemical properties of solid-state-synthesized spinel LixMn2O4

Lithium-substituted LixMn2O4 (x = 0.98, 1.03, 1.08) spinel samples were synthesized by solid-state reaction. X-ray diffraction (XRD) patterns show that the prepared samples have a spinel structure with a space group of Fd 3 m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. Li1.03Mn2O4 shows high capacity at both low and high current densities, while Li1.08Mn2O4 shows good cycling performance but relatively low capacity when cycled at both room and elevated temperatures. A variety of electrochemical methods were employed to investigate the electro- chemical properties of these series of spinel LixMn2O4.     

Synthesis and electrochemical performances of spherical LiFePO4 cathode materials for Li-ion batteries

Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g -1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g -1.The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.     

Synthesis and electrochemical performance of LiMnPO4/C composites cathode materials

LiMnPO4/C composites were synthesized via solid-state reaction with different carbon sources:sucrose,citric acid and oxalic acid.The samples were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM) and electrochemical performance test.The results of XRD reveal that carbon coating has no effect on the phase of LiMnPO4.The LiMnPO4/C synthesized at 600 ℃ with citric acid as carbon source shows an initial discharge capacity of 117.8 mAh·g-1 at 0.05 C rate.After 30 cycles,the capacity remains 98.2 mAh.g 1.The improved electrochemical properties of LiMnPO4/C is attributed to the decomposition of organic acid during the sintering process.     

A new candidate as the cathode material for intermediate and low temperature SOFCs

In order to develop the new cathode materials suitable for intermediate and low temperature solid oxide fuel cells (IT/LTSOFCs), LaNi1-xFexO3(x=0.4-0.8) (LNF) materials were synthesized using coprecipitation method. Their structures and morphologies were investigated by XRD and SEM, and their electronic conductivities at different temperatures were measured by dc four terminal method. Fuel cells were fabricated to evaluate the electrochemical properties of the LNF materials as cathodes at different temperatures. The performance of 450-497 mW·cm-2 was obtained in the temperature region of 580-650 ℃ for the LaNi0.2Fe0.8O3 cathode, and of 209-227 mW·cm-2 at 400-500 ℃ for the LaNi0.4Fe0.6O3. The excellent fuel cell performances indicate that the LNF materials are good cathodes for IT/LTSOFCs.     

掺F锂离子电池正极材料Li1.03Co0.10Mn1.90FzO4-z的制备及电化学性能

以Li2CO3、Mn2O3、Co2O3及LiF为原料,采用高温固相法合成了掺F的Li1.03Co0.10Mn1.90FzO4?z锂电池正极材料。通过离子发射光谱(ICP)和电位分析法确定了材料的化学组成,用X-射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试仪分析了 F 掺杂量对材料结构、形貌和电池性能的影响。结果表明,掺 F 的Li1.03Co0.10Mn1.90FzO4?z正极材料为尖晶石结构,在F掺入量z≤0.10时,随着掺杂量的增加晶胞参数逐渐增加,当F掺杂量继续增加时,晶胞参数的增幅有所减小。适量的F?与金属离子Li+、Co+的复合掺杂提高了材料的放电比容量,同时增强了材料结构的稳定性。电化学性能测试表明,Li1.03Co0.10Mn1.90F0.15O3.85的首次放电比容量达到111.0 mA·h/g,0.2C倍率下30次循环后容量保持率为97.0%。     

锂离子导体包覆镍锰酸锂正极材料的制备及其电化学性能

采用原位包覆法制备表面包覆Li1.3Al0.3Ti1.7(PO4)3(LATP)的Li Ni0.5Mn1.5O4(LNMO),即LNMO@LATP正极材料。采用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及电化学测试等手段对其物相结构、表面形貌及电化学性能进行研究。结果表明:LATP以无定型态紧密包覆于Li Ni0.5Mn1.5O4的表面,包覆层厚度约为5 nm。由于LATP包覆层具有保护电极材料表面和提高锂离子导电的双重作用,减少了电极过程的副反应,降低了电化学极化,提供了更多的锂离子扩散通道,导致LNMO@LATP具有比LNMO更稳定的循环性能和更好的倍率性能,特别是在高温的情况下。室温下在0.2C放电时,LNMO@LATP和LNMO的首次放电容量分别为141.5和142.6m A·h/g,经80次循环后,二者放电容量保持率分别达到99.2%和98.0%;而在10.0C放电时,LNMO@LATP和LNMO的首次放电容量分别为93.5和70.6 m A·h/g,经80次循环后,二者放电容量保持率分别达到66.1%和49.5%。当循环温度提高到55℃时,LNMO@LATP和LNMO在0.2C循环80次后的放电容量保持率分别为95.5%和79.2%;而在10.0C放电循环80次后,放电容量保持率分别为88.0%和51.0%。     

LiMn2O4正极材料的合成及电化学性能

根据Li2CO3／MnO2混合粉体的TG-DSC分析结果，采用高温固相反应法，在不同的预保温温度下合成出正极材料LiMn2O4。对其进行XRD，SEM表征和电化学性能测试，确定了在600℃预保温和830℃最终合成的优化工艺。该工艺合成的LiMn2O4粉体具有单一的尖晶石相结构和粒度分布均匀的形貌。组装成电池在常温下循环时，初始放电比容量达122mAh／g，20次循环后容量保持在96％左右。其循环伏安曲线经过20次循环后仍可保持较好的形状。     

Structure and electrochemical properties of LiMn2O4

LiMn2O4, a cathode material of lithium ion battery, was prepared by the citric acid complexing method using lithium acetate and manganese acetate as raw materials. The type of atom location confused degree, the confused degree and judgement method in LiMn2O4 were analyzed. The effect of sintering temperature on structure and electrochemical properties of LiMn2O4 was also investigated. The results show that the atom location confused degree increases with the decrease of the X-ray diffraction peak intensity ratio of LiMn2O4, Ⅰ111/Ⅰ311. The type of atom location confused degree depends on the variation tendency of Ⅰ111/Ⅰ311 and Ⅰ311/Ⅰ400 value. If the variation tendency is the same, it belongs to the 16c type location confusion, however, if the variation tendency is contrary, it belongs to the anti-spinel type location confusion. When the sintering temperature is low, it is apt to produce the anti-spinel location confusion in LiMn2O4. With the increase of sintering temperature, the confused degree with the anti-spinel type gradually reduces, however, the confused degree with 16c type increases to some extent. When the atom location confusion with the anti-spinel type appears in LiMn2O4, both the initial discharging capacity and cycling properties of LiMn2O4 reduce. However, the atom location confusion with 16c type does not affect the charge and discharge properties of LiMn2O4.     

Synthesis and electrochemical properties of Li[NixCoyMn1-x-y]02 (x, y=2/8, 3/8) cathode materials for lithium ion batteries

The uniform layered Li(Ni2/8Co3/8Mn3/8)O2, Li(Ni3/8Co2/8Mn3/8)O2, and Li(Ni3/8Co3/8Mn2/8)O2 cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of calcination temperature and transition metal contents on the structure and electrochemical properties of the Li-Ni-Co-Mn-O were systemically studied. The results of XRD and electrochemical performance measurement show that the ideal preparation conditions were to prepare the Li(Ni3/8Co3/8Mn2/8)O2 cathode material calcined at 900℃ for 10 h. The well-ordered Li(Ni3/8Co3/8Mn2/8)O2 synthesized under the optimal conditions has the I003/I104 ratio of 1.25 and the R value of 0.48 and pedance of 558 Ω after the first cycle. The decrease of Ni content results in the decrease of discharge capacity and the bad cycling perform-ance of the Li-Ni-Co-Mn-O cathode materials, but the decreases of Mn content and Co content to a certain extent can improve the electro-chemical properties of the Li-Ni-Co-Mn-O cathode materials.     

Influence of Ti^4＋ doping on electrochemical properties of LiFePO4/C cathode material for lithium-ion batteries

To improve the performance of LiFePO4, single phase Li1-4xTixFePO4/C (x=0, 0.005, 0.010, 0.015) cathodes were synthesized by solid-state method. A certain content of glucose was used as carbon precursor and content of carbon in every final product was about 3.5%. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy observations(SEM), charge/discharge test, carbon analysis and electrochemical impedance spectroscopy(EIS). The results indicate that the prepared samples have ordered olivine structure and doping of the low concentration Ti~(4+) does not affect the structure of the samples. The electrochemical capabilities evaluated by charge-discharge test show that the sample with 1% Ti~(4+) (molar fraction) has good electrochemical performance delivering about an initial specific capacity of 146.7 mA·h/g at 0.3C rate. Electrochemical impedance spectroscopy measurement results show that the charge transfer resistance of the sample could be decreased greatly by doping an appropriate amount Ti~(4+).     

Ni-F共掺纳米LiMn2O4正极材料及电化学性能

采用熔盐燃烧合成了Ni-F共掺的纳米LiNi_(0.03)Mn_(1.97)O_(3.95)F_(0.05)(LNMOF)正极材料。结果表明,Ni-F共掺显著提高了材料的倍率性能、循环稳定性及初始比容量,在5、10、15和20 C倍率下,首次放电比容量分别为101.4、92.5、89.4和66.8 mAh?g~(-1),循环1000次后容量保持率分别为77.9%、70.8%、70.9%和72.9%。循环伏安和电化学阻抗测试结果表明,与LiMn_2O_4样品相比,LNMOF正极材料有较低的表观活化能24.72 kJ?mol~(-1)与较大的锂离子扩散系数1.174×10~(-8)cm~2?s~(-1)。对循环前后极片进行XRD分析,发现LNMOF晶体结构基本没有变化。适量的镍和氟共掺杂能够有效抑制Jahn-Teller畸变,稳定晶体结构,在材料的比容量提高的同时,也改善了材料的循环性能。     

Effect of annealing temperature on structure and electrochemical properties of LiCoO2 cathode thin films

LiCoO2 thin films, which can be used as a cathode material in microbatteries, were deposited using radio frequency (r.f.) magnetron sputtering system from a LiCoO2 target and in an O2+Ar atmosphere.The films were characterized by various methods such as XRD, SEM and AFM.The LiCoO2 films were annealed in air at 300, 500, 700 and 800 ℃ respectively.The effect of the annealing temperature on the structure, the surface morphology and the electrochemical properties of the films were investigated.The LiCoO2 thin film deposited at room temperature is amorphous and has smaller grain size.With increasing of annealing temperature, the crystallinity of the films is promoted.When the annealing temperature increases to 700 ℃, the films have a perfect crystalline LiCoO2 phase.The LiCoO2 thin film without annealing has no discharge plateau and small discharge capacity (about 27 μAh·cm-2μm).The discharge capacity increases with the increasing of annealing temperature and reaches 47 μAh·cm-2μm for the film annealed with 700 ℃, which also shows the typical discharge plateau of 3.9 V.The cycle performance of LiCoO2 thin films of as grown and annealed at different temperatures were studied.In the case of the film without thermal treatment, the capacity fading is much faster than that of the film annealed at different temperature, showing about 40% capacity loss only after 25 cycles.However, in the case of the film annealed at 700 ℃, the capacity reaches to steady state gradually and maintained constantly with cycling.After 25 times cycling, the discharge capacity of the film annealed at 700 ℃ decreases to about 36.9 μAh·cm-2·μm, only 0.8% capacity loss per cycle.     

Effects of Na+ doping on crystalline structure and electrochemical performances of LiNi0.5Mn1.5O4 cathode material

Pristine LiNi_0.5Mn_1.5O₄ and Na-doped Li_0.95Na_0.05Ni_0.5Mn_1.5O₄ cathode materials were synthesized by a simple solid-state method. The effects of Na⁺ doping on the crystalline structure and electrochemical performance of LiNi_0.5Mn_1.5O₄ cathode material were systematically investigated. The samples were characterized by XRD, SEM, FT-IR, CV, EIS and galvanostatic charge/discharge tests. It is found that both pristine and Na-doped samples exhibit secondary agglomerates composed of well-defined octahedral primary particle, but Na⁺ doping decreases the primary particle size to certain extent. Na⁺ doping can effectively inhibit the formation of Li_xNi_1–xO impurity phase, enhance the Ni/Mn disordering degree, decrease the charge-transfer resistance and accelerate the lithium ion diffusion, which are conductive to the rate capability. However, the doped Na⁺ ions tend to occupy 8a Li sites, which forces equal amounts of Li⁺ ions to occupy 16d octahedral sites, making the spinel framework less stable, therefore the cycling stability is not improved obviously after Na⁺ doping.     

利用新颖的三层电极提高LiFePO4／C正极材料的电化学性能

对常用的两层电极（活性材料层｜集电极）进行改进,提出一种新颖的夹心状三层电极（导电材料层｜活性材料层｜集电极）以提高 LiFePO4/C 的电化学性能。充放电测试表明：相比两层电极,三层电极中 LiFePO4/C 表现出更优的倍率性能。循环伏安和电化学阻抗测试表明：相比两层电极,三层电极中LiFePO4/C材料中的Fe3＋/Fe2＋氧化还原电对表现出更快的氧化还原速度。更好的可逆性能以及更低的电荷转移阻抗。在三层电极中,活性材料层表层中与LiFePO4/C颗粒尺寸相当的孔洞被粒径小得多的乙炔黑微粒填充,形成LiFePO4/C颗粒间的导电连接,为暴露在电解液主体LiFePO4/C颗粒中的LiFePO4晶体提供更多运输电子到达或离开的路径。     

锂离子电池高镍单晶正极材料的合成与性能

通过高温固相焙烧法合成高镍单晶正极材料LiNi0.88Co0.09Al0.03O2。采用XRD、XPS、TEM等技术研究初始样品和脱锂化高镍单晶材料的物理化学性能;采用长循环测试、循环伏安法和原位阻抗分析表征其电化学性能。研究结果表明:在高温处理过程中,样品的内部和表面发生锂氧损失和相转变现象,材料在固相合成反应过程中会加剧相转变,并在单一颗粒上形成多相共存状态;高温可以促进一次颗粒生长,但对单晶颗粒的稳定层状结构有一定的损害。     

Preparation, characterization and electrochemical properties of mesoporous LiFe0.99Mo0.01PO4/C

A mesoporous LiFe0.99Mo0.01PO4/C composite was synthesized by the sol-gel method using (NH4)2MoO4 as a doping starting material. The formation of conductive carbon, metal doping and mesopores was achieved simultaneously in the prepared material. The characterizations of crystal structures and microstructures were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), extended X-ray-absorption free-structure (EXAFS) and X-ray-absorption near-structure spectroscopy (XANES), while the surface area was determined using N2 adsorption techniques. Cyclic voltammetry (CV) and charge-discharge cycling performance were used to characterize its electrochemical properties. The sample possessed uniformly distributed mesopores with an average pore size of 4 nm and the specific surface area was about 69.368 m2/g. The results show that the reversible capacity of mesoporous LiFe0.99Mo0.01PO4/C is about 160 mAh/g at 0.1C, 135 mAh/g at 1C and 90 mAh/g at 5C, respectively. The capacity fading is neglectable.     

Synthesis and electrochemical performance of 5V spinel LiNi0.5Mn1.5O4 prepared by solid-state reaction

Spinel compound LiNi0.5Mn1.5O4 with high capacity and high rate capability was synthesized by solid-state reaction. At first, MnCl2·4H2O and NiCl2·6H2O were reacted with (NH4)2C2O4·H2O to produce a precursor via a low-temperature solid-state route, then the precursor was reacted with Li2CO3 to synthesize LiNi0.5Mn1.5O4. The effects of calcination temperature and time on the physical properties and electrochemical performance of the products were investigated. Samples were characterized by thermal gravimetric analysis(TGA), scanning electron microscopy(SEM), X-ray diffractometry(XRD), charge-discharge tests and cyclic voltammetry measurements. Scanning electron microscopy(SEM) image shows that as calcination temperature and time increase, the crystallinity of the samples is improved, and their grain sizes are obviously increased. It is found that LiNi0.5Mn1.5O4 calcined at 800 ℃ for 6 h exhibits a typical cubic spinel structure with a space group of Fd3m. Electrochemical tests demonstrate that the sample obtained possesses high capacity and excellent rate capability. When being discharged at a rate as high as 5C after 30 cycles, the as-prepared LiNi0.5Mn1.5O4 powders can still deliver a capacity of 101 mA-h/g, which shows to be a potential cathode material for high power batteries.     

中低温用Sm1-2xEuxBaxB6阴极材料的制备及性能

采用硼/碳热还原-热压烧结集成工艺(BCTR&HP)制备了高纯致密的Sm_1-2xEu_xBa_xB₆(x=0.1,02,0.3)多晶块体,系统研究Eu&Ba掺杂SmB₆对其结构、力学性能与电学特性的影响。结果表明,BCTR&HP制备的Sm_1-2xEu_xBa_xB₆呈CsC1型简单立方单相结构,晶格常数随Eu&Ba掺杂量的增加而增大,贡献于力学性能的提高和电阻率的下降。热电子发射性能结果表明,Eu&Ba掺杂能够改善SmB₆阴极材料的发射特性,在测试温度1773 K,外加电压1 kV条件下,Sm_0.4Eu_0.3Ba_0.3B₆阴极的发射电流密度达到35.1 mA·cm^-2,零场电流密度达到21.4 mA·cm^-2,在1523~1773 K其平均有效功函数为3.6 eV,其固有的高电阻率可作为"直热式"阴极简化热子结构,具有很大的应用前景。     

Preparation and electrochemical characteristics of CO3（PO4）2-coated LiNi0.8Co0.2O2 by solid-state reaction at room temperature

LiNi0.8Co0.2O2 particles were modified by Co3（PO4）2 coating. The effects of the Co3（PO4）2 coating on the structure and electrochemical properties of the LiNi0.8Co0.2O2 cathode material were investigated. The Co3（PO4）2 coating forms a thin layer on the surface of the LiNi0.8Co0.2O2 material and a solid solution by interacting with the LiNi0.8Co0.2O2 core material during calcination at 700℃ for 4 h. Charge-discharge experiment results show that the Co3（PO4）2 coating improves the cycling stability of the LiNi0.8Co0.2O2 cathode material. The capacity retention of the pristine LiNi0.8Co0.2O2 cathode after 50 cycles is 83.6%, whereas it is 91.7% in the case of the LiNi0.8Co0.2O2 cathode coated with 1 wt.% Co3（PO4）2. Storage tests of the 4.35 V charged electrode at 60℃ after a month show that the Co3（POg）2-coated sample exhibits good storage properties compared with the pristine sample.