Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

球形LiMn1.5Ni0.5O4材料的嵌脱动力学

为明晰Li Mn1.5Ni0.5O4正极材料的动力学性能,采用水热辅助共沉淀法合成了尖晶石Li Mn1.5Ni0.5O4正极材料,并采用扫描电镜(SEM)、X射线粉末衍射(XRD)和电化学阻抗(EIS)研究了材料的结构和锂离子嵌脱动力学.实验结果表明:共沉淀法制备的Li Ni0.5Mn1.5O4材料颗粒呈均匀球形,且平均粒径较小,粒度分布较窄.在循环过程中,Li Ni0.5Mn1.5O4的电荷转移电阻增大,锂离子扩散系数减小,进而电子电导率和离子电导率下降.温度升高后,Li Ni0.5Mn1.5O4材料的溶液电阻变化不大,但是电荷转移电阻逐渐增大,锂离子扩散系数逐渐减小;此外,随着温度的升高,Li Ni0.5Mn1.5O4材料的溶解速度加快,从而导致SEI膜的厚度增大.Li Ni0.5Mn1.5O4材料的嵌脱锂动力学与温度和循环次数有密切关系.     

Synthesis and characterization of Li1.05Co0.3Ni0.35Mn0.3M0.05O2 (M=Ge,Sn)cathode materials for lithium ion battery

In order to improve the electrochemical performance and thermal stability of Li_1.05Co_1/3Ni_1/3Mn_1/3O₂ materials,Li_1.05Co_0.3Ni_0.35Mn_0.3M_0.05O₂（M=Ge,Sn）cathode materials were synthesized via co-precipitation method.The structure,electrochemical performance and thermal stability were characterized by X-ray diffraction（XRD）,charge/discharge cycling,cyclic voltammetry（CV）,electrochemical impedance spectroscopy（EIS）and differential scanning calorimetry（DSC）.ESEM showed that Sn-doped and Ge-doped slightly increased the size of grains.XRD and CV showed that Sn-doped and Ge-doped powders were homogeneous and had the better layered structure than the bare one.Sn-doped and Ge-doped improved high rate discharge capacity and cycle-life performance.The reason of the better cycling performance of the doped one was the increasing of lithium-ion diffusion rate and charge transfer rate.Sn-doped and Ge-doped also improved the mateials thermal stability.     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi_0.5Mn_1.5O₄ was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi_0.5Mn_1.5O₄ synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electrochemical test shows that the LiNi_0.5Mn_1.5O₄ calcined at 700 °C for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles. Foundation item: Project (76600) supported by Postdoctoral Science Foundation of Central South University     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

过硫酸铵表面处理对富锂锰基正极材料电化学性能的影响

为了提高锂离子电池富锂锰基正极材料的电化学性能,尤其是倍率性能,采用过硫酸铵作为处理剂对富锂锰基正极材料Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2进行表面处理,诱发化学预活化,形成有利于锂离子迁移的表面尖晶石结构。电化学测试结果显示,当过硫酸铵与Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2质量比为1:5时,经过硫酸铵表面处理后的正极表现出优异的电化学性能:0.2 C下放电容量为257.1 mAh/g,首圈库伦效率高达96.8%, 3 C大倍率下放电容量仍达到157.2 mAh/g。交流阻抗测试结果表明,适量过硫酸铵处理之后材料的界面电荷转移阻抗显著降低,导致锂离子界面迁移速率加快,表现出良好的倍率性能。这种简单易行的改性方法为实现富锂锰基正极在动力锂离子电池领域的应用提供了新思路。     

Direct synthesis of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-modified Li(Ni<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>)O<Subscript>2</Subscript> cathode materials for lithium ion batteries

To improve the cyclic stability at high temperature and thermal stability, the spherical Al₂O₃-modified Li(Ni_0.5Co_0.2Mn_0.3)O₂ was synthesized by a modified co-precipitation method, and the physical and electrochemical properties were studied. The TEM images showed that Li(Ni_0.5Co_0.2Mn_0.3)O₂ was modified successfully with nano-Al₂O₃. The discharge capacity retention of Al₂O₃-modified Li(Ni_0.5Co_0.2Mn_0.3)O₂ maintained about 99% after 200 cycles at high temperature (55 °C), while that of the bare one was only 86%. Also, unlike bare Li(Ni_0.5Co_0.2Mn_0.3)O₂, the Al₂O₃-modified material cathode exhibited good thermal stability.     

Theoretic Diffraction Research on the Order-Disorder Effect of Transition Metal in Li(Ni1/3Co1/3Mn1/3)O2

Li(Ni_1/3Co_1/3Mn_1/3)O₂的(3b)位有序-无序效应研究

曹春晖^1,2, 张建¹, 杨传铮¹, 夏保佳¹

（1.上海微系统与信息技术研究所,上海 200050;

2.中国科学院大学, 北京100049）

创新点说明：

提出了有序度的概念,通过理论模拟了过渡金属在3b位不同有序度下的衍射情况。

研究目的：

借助理论衍射研究镍钴锰在三元材料中的占位情况,为实际得到的衍射数据分析起指导作用。

研究方法和结果：

借助Powercell程序模拟不同结构下的衍射情况。结果表明：对于Li(Ni1/3Co1/3Mn1/3)O2,基体衍射线的强度不随有序度而变化,有序度增加时,超点阵衍射线强度增加,但是即使对于有序度最大时,超点阵线的相对强度只有0.225%和0.043%。

结论：

3b位的有序无序很难通过常规的衍射实验观测到,必须提高X射线源的强度才可能观测到。

关键词：Li(Ni1/3Co1/3Mn1/3)O2, 有序-无序,超结构,衍射

     

Thermal stability of LiFePO<Subscript>4</Subscript>/C-LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> blended cathode materials

Safety is important to lithium ion battery materials. The thermal stability of LiFePO₄/C-LiMn₂O₄ blended cathode materials is characterized by using TG, XRD, and SEM etc. The results show that LiFePO₄/C-LiMn₂O₄ possesses a worse thermal stability than pure spinel LiMn₂O₄ and pure olivine LiFePO₄/C. When LiFePO₄/C-LiMn₂O₄ blended cathode materials are sintered at 500°C under Ar atmosphere, the sintered cathode materials emit O₂, and appear impurity phases (Li₃PO₄, Fe₂O₃, Mn₃O₄). It is deduced that some chemical reactions take place between different materials, which leads to a worse discharge specific capacity. LiFePO₄/C-LiMn₂O₄ blended cathode materials, therefore, need to be managed and controlled strictly for the sake of thermal stability and safety.     

Mn_2O_3/PANI的制备及其防腐性能研究

采用溶剂热法制备Mn_2O_3微球,与化学氧化法制备的聚苯胺按不同比例混合,制得Mn_2O_3/PANI,将其涂覆于Q235碳钢表面制备复合涂层.采用扫描电镜(SEM)、原子力显微镜(AFM)、X射线衍射(XRD)和红外光谱(FTIR)表征Mn_2O_3/PANI的表面形貌和结构,利用动电位极化和电化学阻抗谱研究复合涂层的耐蚀性能.结果表明,当Mn_2O_3在复合材料中的质量分数为10%时,防腐性能最优.在3.5%NaCl溶液中浸泡7天后,相较于Q235裸钢,其自腐蚀电位正移约380 mV,自腐蚀电流密度降低约3个数量级;浸泡37天后,其仍有良好的稳定性和耐蚀性.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript> microstructures decorated with Ag and Cu oxides: Study of photocatalytic and electrochemical properties

Three-dimensional hierarchical Co₃O₄ microstructures decorated with Ag and Cu oxides were prepared via displacement reaction and subsequent annealing treatment. Photocatalytic properties measurements revealed that the photocatalystic activities of CuO/Co₃O₄ composites (Co₃O₄ microstructures decorated with CuO) were enhanced while those of Ag₂O/Co₃O₄ composites (Co₃O₄ microstructures decorated with Ag₂O) were reduced, when compared with those of pure hierarchical Co₃O₄ microstructures toward the degradation of methyl orange. In addition, CuO/Co₃O₄ composites exhibited an excellent recyclability ability of photodegradation. The electrochemical properties test indicated that both of the composite oxide electrodes exhibited excellent pseudocapacitive performance with relatively high specific capacitance and good long-term cycling stability. With the increase of the loaded Ag₂O and CuO dosages deposited on the Co₃O₄ microstructures surface, the specific capacitance values of the composites were increased. Ag₂O/Co₃O₄ composite electrodes showed higher specific capacitance values and better cycling stability than CuO/Co₃O₄ composite ones.     

Solvothermal synthesis and electrochemical properties of octahedral cobalt oxide decorated with Ag<Subscript>2</Subscript>O

Octahedral CoO with nanostructures decorated with Ag nanoparticles was prepared via a facile solvothermal approach. After being annealed at 500 °C for 1 h, an electrochemical capacitor material of Co₃O₄ decorated with Ag₂O was obtained. The cyclic voltammetry and galvanostatic charge-discharge were used to evaluate the electrochemical properties of the as-prepared products. The results indicated that the as-prepared samples exhibited fine pseudo-capacitive performance, and the surface modifications of Ag₂O can significantly increase the capacitance of the Co₃O₄ material. The specific capacitance of Ag₂O/Co₃O₄ composite electrode was up to 217.6 F·g^?1, which was 3.35 times as high as that of pure Co₃O₄. Moreover, Ag₂O/Co₃O₄ composite showed an excellent cycle performance, and 65.3% of specific capacitance was maintained after 200 cycles.     

Preparation and electrochemical properties of Co3O4/graphite composites as anodes of lithium ion batteries

Co₃O₄/graphite composites were synthesized by precipitation of cobalt oxalate on the surface of graphite and pyrolysis of the precipitate, and the effects of graphite content and calcination temperature on the electrochemical properties of the composites were investigated. The samples were characterized by thermogravimetry and differential thermal analysis (TG/DTA), X-ray diffractometry (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge/discharge measurements. With increasing the graphite content, the reversible capacity of the Co₃O₄/graphite composites decreases, while cycling stability improves dramatically, and the addition of graphite obviously decreases the average potential of lithium intercalation/deintercalation. The reversible capacity of the composites with 50% graphite rises from 583 to 725 mA·h/g as the calcination temperature increases from 300 to 500 °C, and the Co₃O₄/graphite composites synthesized at 400 °C show the best cycling stability without capacity loss in the initial 20 cycles. The CV profile of the composite presents two couples of redox peaks, corresponding to the lithium intercalaction/deintercalation for graphite and Co₃O₄, respectively. EIS studies indicate that the electrochemical impedance decreases with increasing the graphite content.     

Structure and electrochemical properties of La, F dual-doped iLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn₂O₄ and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa_0.01Mn_1.99O_3.99F_0.01 and LiLa_0.01Mn_1.99O₄ samples have smaller lattice parameters and unit cell volume than LiMn₂O₄. SEM indicates that LiLa_0.01Mn_1.99O_3.99F_0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn₂O₄, LiLa_0.01Mn_1.99O₄, and LiLa_0.01Mn_1.99O_3.99F_0.01 are 129.9, 122.8, and 126.4 mAh·g⁻¹, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn₂O₄.     

Preparation of microsized single-crystalline Co_3O_4 by high-temperature hydrolysis

Microsized single-crystalline Co3O4 has been synthesized by high-temperature hydrolysis of CoCl2·2H2O at 600 °C.The samples were characterized by powder X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The results reveal that the as-prepared powders are microsized single-crystalline Co3O4 with cubic spinel structure.An increase in the high-temperature hydrolysis time results in the evolution of particle shapes from cube to quasi-sphere,and then to octahedron...     

Synthesis of Lithium-cobalt Oxides by Sol-gel Method and their Cathodical Discharge Behavior at 500

Three kinds of lithium-cobalt oxides with lithium to cobalt atomic ratios of 0.6, 0.8 and 1.0 respectively were prepared using nitrates and citric acid by sol-gel process. During the baking of the dry-gel powder, two exothermic peaks occur, followed by the formation of Li₂O and Co₃O₄ and then the combination of LiCoO₂, which is testified by DTA and XRD. The powder formed from an alkaline sol is finer than that from the acidic one. There are a single phase intercalation of lithium ion and an electrochemical reduction reaction for higher-valence cobalt ion when simulating the discharging process of Li-B/LiCl-KCl/lithium-cobalt oxides at 500 °C, and the voltage and specific capacity are not sensitive to the initial ratios of lithium to cobalt. Foundation item: The Doctoral Foundation of the Education Ministry of China(No. 96053311) Biography of the first author: LI Zhi-you, born in 1968, majoring in materials for thermal battery.     

Structure and stability of Li-Mn-Ni composite oxides as lithium ion sieve precursors in acidic medium

A series of spinel Li-Mn-Ni composite oxides with theoretical chemical formula of LiNixMn2-xO4 (0≤x≤1.0) were synthesized by liquid phase method. Their structure and morphology were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM),respectively. The stability of these Ni-substituted spinel oxides prepared at different temperatures was investigated in acidic medium as well. The results show that Ni can be brought into the spinel framework completely to form well-crystallized ...     

N掺杂Co3O4纳米片的制备以及活化过一硫酸盐的性能研究

采用牺牲模板法合成N掺杂Co₃O₄纳米片（N-Co NS）,通过透射电子显微镜（TEM）、原子力显微镜（AFM）和光电子能谱（XPS）对制备材料的形貌结构、化学组成进行分析,并通过催化活化过一硫酸盐（PMS）降解水中双酚A （BPA）来探究催化剂的催化性能.实验结果表明与Co₃O₄纳米颗粒（Co NP）、Co₃O₄纳米片（Co NS）相比,N-Co NS表现出了较高的催化性能.在PMS浓度为2 mmol·L^-1、BPA初始质量浓度为50 mg·L^-1的反应条件下,N-Co NS在10 min内完全降解水中的BPA,表明N掺杂和二维纳米片结构有利于催化剂性能的提升.通过pH及离子影响实验证实N-Co NS在复杂水化学环境中仍具有较高的活性.此外结合自由基捕获实验和电子顺磁共振（EPR）测试证实反应体系中产生了高氧化活性的羟基自由基和硫酸根自由基.     

Synthesis and Characterization of LiCoxMn2-xO4 Cathode Materials

LiCoxMn2.04 cathode materials for lithium ion batteries were synthesized by mechanical activation-solid state reaction at 750 ℃ for 24 h in air atmosphere, and their crystal structure, morphology, element composition and electrochemical performance were characterized with XRD, SEM, ICP-AES and charge-discharge test. The experimental results show that all samples have a single spinel structure, well formed crystal shape and uniformly particle size distribution. The lattice parameters of LiCo Mn2-xO4 decrease and the average oxidation states of manganese ions increase with an increase in Co content. Compared with pure LiMn2O4, the LiCo Mn2xO4 （x=0.03-0.12） samples show a lower special capacity, but their cycling life are improved. The capacity loss of LiCo009Mn191O4 and LiCo0.1Mn1.88O4 is only 1.85% and 0.95%, respectively, after the 20th cycle. The improvement of the cycle performance is attributed to the substitution of Co at the Mn sites in the spinel structure, which suppresses the Jahn-Teller distortion and improves the structural stability.