Effects of carbon sources on electrochemical performance of Li_4Ti_5O_(12)/C composite anode materials

Li4Ti5O12/C composite materials were synthesized by two-step solid state reaction method with glucose,sucrose,and starch as carbon sources,respectively.The effects of carbon sources on the structure,morphology,and electrochemical performance of Li4Ti5O12/C composite materials were investigated by SEM,XRD and electrochemical tests.The results indicate that carbon sources have almost no effect on the structure of Li4Ti5O12/C composite materials.The initial discharge capacities of the Li4Ti5O12/C composite materials are slightly lower than those of as-synthesized Li4Ti5O12.However,Li4Ti5O12/C composite materials show better electrochemical rate performance than the as-synthesized Li4Ti5O12.The capacity retention(79%) of the Li4Ti5O12/C composite materials with starch as carbon source,is higher than that of Li4Ti5O12/C composite materials with glucose and sucrose as carbon source at current rate of 2.0C.     

一步固相法制备高性能Li_2MnSiO_4/C锂离子电池正极材料

采用一步固相法合成了Li_2MnSiO_4/C正极材料,利用XRD,EIS和循环伏安测试对该材料进行了结构和电化学性能表征.研究了一步固相法中添加不同比例的葡萄糖对Li_2MnSiO_4材料性能的影响.结果表明:葡萄糖作碳源复合可以提高Li_2MnSiO_4正极材料的充放电比容量和循环性能,同时在一步固相合成法中还能细化Li_2MnSiO_4正极材料颗粒.葡萄糖添加量为6%时,制备得到的Li_2MnSiO_4/C正极材料首次可逆放电比容量为213.1 mAh/g.     

Effects of different iron sources on the performance of LiFePO4/C composite cathode materials

Olivine LiFePO₄/C composite cathode materials were synthesized by a solid state method in N₂ + 5vol% H₂ atmosphere. The effects of different iron sources, including Fe(OH)₃ and FeC₂O₄·2H₂O, on the performance of as-synthesized cathode materials were investigated and the causes were also analyzed. The crystal structure, the morphology, and the electrochemical performance of the prepared samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), laser particle-size distribution measurement, and other electrochemical techniques. The results demonstrate that the LiFePO₄/C materials obtained from Fe(OH)₃ at 800°C and FeC₂O₄·2H₂O at 700°C have the similar electrochemical performances. The initial discharge capacities of LiFePO₄/C synthesized from Fe(OH)₃ and FeC₂O₄·2H₂O are 134.5 mAh·g⁻¹ and 137.4 mAh·g⁻¹ at the C/5 rate, respectively. However, the tap density of the LiFePO₄/C materials obtained from Fe(OH)₃ are higher, which is significant for the improvement of the capacity of the battery.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

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)     

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.     

Synthesis and properties of Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for Li-ion batteries

Carbon was coated on the surface of Li₂MnSiO₄ to improve the electrochemical performance as cathode materials, which were synthesized by the solution method followed by heat treatment at 700 °C and the solid-state method followed by heat treatment at 950 °C. It is shown that the cycling performance is greatly enhanced by carbon coating, compared with the pristine Li₂MnSiO₄ cathode obtained by the solution method. The initial discharge capacity of Li₂MnSiO₄/C nanocomposite is 280.9 mAh/g at 0.05 C with the carbon content of 33.3 wt%. The reasons for the improved electrochemical performance are smaller grain size and higher electronic conductivity due to the carbon coating. The Li₂MnSiO₄/C cathode material obtained by the solid-state method exhibits poor cycling performance, the initial discharge capacity is less than 25 mAh/g.     

The Effect of Bi2O3 on the Structure and Microwave Dielectric Properties of Ba6-3xNd8＋2xTi18O54 System（x=2/3）

The structures and dielectric properties of Ba6-3xNd8＋2xTi18O54 system（x=2/3） doped with different contents of Bi2O3, whose final molecular formula is Ba6-3x（Nd1-yBiy）8＋2xTi18O54 were investigated. It is indicated that the dielectric constant increases greatly whereas Q value（f0=4 GHz） decreases with the increase of Bi2O3 content. However, the temperature coefficient could be controlled below 0±30×10^-6/℃ in the experiment. These phenomena are related to the appearance of a new phase, Bi4Ti3O12, which has high dielectric constant. Also, that Bi^3＋（0.13 nm） substitutes for Nd^3＋（0.099 5 nm） will increase the unit cell volume, which will lead to the enlargement of the octahedron B site occupied by Ti^4＋. So the spontaneous polarization of Ti^4＋ ions will be strengthened. Besides, Bi^3＋ will fill up some vacancies which Ba^2＋ or Nd^3＋ ions leave in two A1 sites and four A2 sites. More positive ions polarize, which also contributes to higher dielectric constant. The samples got with the optimium properties are sintered at 1 200 ℃ for 4 h, when y=0.25, ε≈110, Q≈5 400（f0=4 GHz）, TCC=-4.7×10^-6/℃; When y=0.3, ε≈120, Q≈5 000（f0=4 GHz）, TCC=-24×10^-6/℃.     

双层碳包覆Li4Ti5O12的合成和电化学性能研究

采用固相合成方法制备了双层碳包覆Li_4Ti_5O_(12)复合材料.通过X射线衍射、扫描电子显微镜、循环伏安、电化学阻抗和恒流充放电分析等测试,研究了产物的结构、形貌及电化学性能.结果表明:通过碳包覆改性后,Li_4Ti_5O_(12)的容量可明显提高,碳的包覆对Li_4Ti_5O_(12)的结构没有影响;2 C倍率下首次放电比容量为118.8 mAh/g,300次循环后放电比容量仍为108.5 mAh/g,容量保持率为91.3%,具有非常好的电化学性能.     

TiO2/ML-Ti3C2复合纳米材料的制备及其光催化性能

通过水热技术在二维(2D)多层材料Ti_3C_2 (multi-layer Ti_3C_2, ML-Ti_3C_2)的表面及层间原位晶化和生长锐钛矿相TiO_2纳米球,制备出TiO_2/ML-Ti_3C_2复合纳米材料。采用XRD、SEM、氮吸附等表征技术对TiO_2/ML-Ti_3C_2纳米复合材料进行分析表征,并以亚甲基蓝(MB)为模拟污染物,对纯TiO_2和TiO_2/ML-Ti_3C_2复合纳米材料的光催化性能进行了评价。实验结果表明,两种材料的耦合抑制了Ti O_2中光生电子-空穴对的湮灭,延长了复合光催化剂中载流子寿命,拓宽了复合材料的光谱响应范围。在紫外光照射下,以TiO_2/ML-Ti_3C_2复合纳米材料为光催化剂,200 mg/L的MB溶液在20 min内几乎完全脱色,降解率为98.98%。TiO_2/ML-Ti_3C_2纳米复合材料的光催化性能优于纯TiO_2和Ti_3C_2, Ti_3C_2优异的电子传输能力和超强的吸附性能优化了TiO_2的光催化性能。本研究为使用光催化技术处理废水提供了一种新的思路,具有一定的实际应用前景。     

Overcharge performance of LiMn2O4/graphite battery with large capacity

The LiMn₂O₄/graphite battery was fabricated and its 3 C/10 V overcharge performance was studied. Spinel LiMn₂O₄ was synthesized by solid-state method and 325680-type size full battery was fabricated. The structure and morphology of the powders were characterized by XRD and SEM technique, respectively. The battery explodes after 3 C/10 V overcharged test, and surface temperature of the battery case arrives at 290 °C in 12 s after exploding. Black air is given out with blast. Carbon, MnO, and Li₂CO₃ are observed in the exploded powders. The cathode electrode remains spinel structure with 5.0 V charged. Cracks in the cathode electrode particles are detected with the increase of voltage by SEM technique. The 5.0 V charged electrode can decompose into Mn₃O₄ at 400 °C. It is demonstrated that the decomposition of 5.0 V charged electrode can be promoted and Mn⁴⁺ can be deoxidized to Mn²⁺ by carbon and electrolyte through the simulation of blast process.     

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     

Preparation and electrochemical characterization of C/PANI composite electrode materials

1 INTRODUCTIONRecently , surpercapacitor has attracted greatattention for its unique power performance[1 ,2],while electrode materials ,as one key factor to de-termine the performance of supercapacitor , nowbecome the focus of many researches . The super-capacitor materials can be categorized into threetypes :carbon electrode materials[3], metal oxide e-lectrode materials[4]and conductive polymer elec-trode materials[5].Conductive polymer electrode materials havehigher capacitance than tha…     

Al2O3 coating for improving thermal stability performance of manganese spinel battery

The synthesis of Al₂O₃-coated and uncoated LiMn₂O₄ by solid-state method and fabrication of LiMn₂O₄/graphite battery were described. The structure and morphology of the powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical and overcharge performances of Al₂O₃-coated and uncoated LiMn₂O₄ batteries were investigated and compared. The uncoated LiMn₂O₄ battery shows capacity loss of 16.5% after 200 cycles, and the coated LiMn₂O₄ battery only shows 12.5% after 200 cycles. The uncoated LiMn₂O₄ battery explodes and creates carbon, MnO, and Li₂CO₃ after 3C/10 V overcharged test, while the coated LiMn₂O₄ battery passes the test. The steadier structure, polarization of electrode and modified layer are responsible for the safety performance.     

复合活性钎料钎焊Cu与Al2O3的接头组织及性能

为改善紫铜与Al_2O_3陶瓷的连接强度,采用纳米-Al_2O_3增强的AgCuTi复合钎料(Ag Cu Tip)对紫铜与Al_2O_3陶瓷进行了真空钎焊.采用扫描电镜、能谱分析以及剪切试验对钎焊接头微观组织及力学性能进行了分析.钎焊接头典型界面组织为紫铜/扩散层/铜基固溶体+银基固溶体+Ti_2Cu+Ti_3(Cu,Al)3O/Al_2O_3.纳米-Al_2O_3的添加抑制了Al_2O_3侧反应层的生长,并促进钎缝中形成弥散分布的Ti_2Cu相.随着保温时间的延长,铜侧扩散层和Ti_3(Cu,Al)_3O反应层的厚度逐渐增大.保温时间为20 min时,铜母材向钎料过度溶解,降低了接头性能.当钎焊温度为880°C,保温10 min时,接头抗剪强度最高为82 MPa.纳米颗粒的加入细化了钎缝组织并降低了母材与钎缝热膨胀系数的不匹配,因此提高了接头的连接性能.保温时间可影响界面组织及反应层的厚度,进而影响接头的连接强度.     

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。     

Low-temperature sintering and microwave dielectric properties of Li2MgTi3O8 ceramics doped with BaCu（B2O5）

The influences of BaCu(B₂O₅) (BCB) addition on sintering, microstructure and microwave dielectric properties of Li₂MgTi₃O₈ ceramics were investigated using X-ray diffractometry, scanning electron microscopy and microwave dielectric measurements. The experimental results show that a small amount of BaCu(B₂O₅) addition can effectively reduce the sintering temperature to 900 °C, and induce only a limited degradation of the microwave dielectric properties. Typically, the best microwave dielectric properties of ɛ _r=24.5, Q×f =24 622 GHz, τ _f=4.2×10⁻⁶ °C⁻¹ are obtained for 1.0% BCB-doped Li₂MgTi₃O₈ ceramics sintered at 900 °C for 3 h. The BCB-doped Li₂MgTi₃O₈ ceramics can be compatible with Ag electrode, which may be a strong candidate for low temperature co-fired ceramics applications.     

磷酸铁锂与碳复合材料的电化学制备及性能研究

利用电化学沉积法在铝箔上制备了掺杂导电碳的磷酸铁锂与碳复合的正极材料.通过对比磷酸铁锂市售样品、电化学沉积法制得的样品、电镀液询问沉淀样品这3种样品的物理表面形貌、电化学性能曲线,组装电池后的循环充放电性能曲线,研究了电化学沉积法掺碳对于磷酸铁锂正极材料结构和电化学性能的影响,得出了电化学沉积法制备LiFePO_4/C复合材料的可行性.     

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.     

Preparation and characterization of Bi4Ti3O12 platelets by a novel low-temperature molten salt system

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were prepared by molten salt method in a new salt system of CaC_l2-NaCl at 650–750 °C, using bismuth nitrate pentahydrate (Bi(NO₃)₃―H₂O) and titanium butoxide (Ti (OC₄H₉)₄) as raw materials. The synthesis temperature of Bi₄Ti₃O₁₂ platelets was decreased to 650 °C from 900–1100 °C. The phase compositions and crystalline morphology of Bi₄Ti₃O₁₂ platelets were investigated by XRD and SEM. The experimental results indicate that Bi₄Ti₃O₁₂ platelets containing tetragonal and orthorhombic phase with the size of 1–3 μm can be synthesized at 650 °C for 2 h, and the orthorhombic phase becomes the dominant phase at 750 °C for 5 h. The size and proportion of Bi₄Ti₃O₁₂ platelets increase with the increment of the calcining temperature and holding time. The proportion of platelets increases to about ninety percent, and the platelets grow up to about 3–10 μm at 750 °C for 5 h from 1–2 μm at 650 °C for 2 h. This technical route provides a new low-temperature molten salt system for preparing platelets by molten salt methods.