Na掺杂对锆酸锂吸收CO2性能的影响

By using Li₂CO₃, ZrO₂, and Na₂CO₃ as starting materials, sodium-doped Li_2(1-x)Na_2xZrO₃ absorbents were prepared by high-temperature solid-state reaction. The crystal structure of the lithium zirconate material was analyzed using a X-ray powder diffractometer (XRD), the microstructure of all the samples was observed using the method of scanning electron microscopy (SEM) and the CO₂-absorption ability of the lithium zirconate material was studied using a thermogravimetric analyzer (TG). It was found that Li_2(1-x)Na_2xZrO₃ absorbent with x=0.02 possesses the best performance. As much as (25 ± 0.4)% (wt) of CO₂ was absorbed by such an absorbent in an atmosphere consisting of 20% (wt) CO₂ and 80% (wt) air at 500 ℃ within 3 h. After 10 cycles of absorption-desorption this absorbent lost only 0.9% of its CO₂-absorption capacity. No remarkable change in particle size and pH was observed.     

钴掺杂镍酸锂的密度泛函计算及电化学性能

LiNiO₂ and LiNi_0.5Co_0.5O₂ cathodes for lithium-ion batteries were synthesized with co-precipitation method and their electrochemical property was characterized by Galvanostatic cycling. Meanwhile, plane-wave pseudopotential method base on density functional theory was used to calculate average cell voltage and the electronic structure of LiNiO₂ and LiNi_0.5Co_0.5O₂. The experimental and computational results showed that the average voltage of the cell decreased as Li-ion intercalated to the host cathode (discharge); The potential of Li_xNi_0.5Co_0.5O₂ was higher than that of Li_xNiO₂ (when 0.25≤x≤0.5). The calculations also indicated that the distortion of the NiO₆ octahedron in Li_xNiO₂ was decreased by Co-doped. During the Li-ion intercalates to the host cathode, the micro-structures of NiO₆ and CoO₆ in the Li_xNi_0.5Co_0.5O₂ were mutually stabilized, the Jahn-Teller effect was weakened and the electrochemical properties of the materials were enhanced.     

多元掺杂尖晶石型Li1.02MxMn2-xQyO4-y正极材料的电化学特性

The effect of doping on the electrochemical performance was studied for spinel type Li_1.02M_xMn_2-xQ_yO_4-y used as cathode material in lithium-ion battery. TG/DTA curves of the precursor(the raw materials) doped with different elements were studied. The spinel materials Li_1.02Mn₂O₄, Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98, Li_1.02Co_0.02Cr_0.01 La_0.01Mn_1.96Cl_0.02O_3.98, Li_1.02Co_0.02La_1.02Mn_1.97Cl_0.02O_3.98, Li_1.02Co_0.02Cr_0.01Mn_1.97O₄, were prepared by solid-state reaction method after the pretreatment of conversion under low temperature and uniform mixing. X-ray diffraction patterns showed that all the samples had perfect spinel structure. SEM indicated that the particles of the samples had uniform size and were distributed evenly. The results of the charge/discharge curves showed that Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98 had better performance than other materials according to the inhibition of decline of reversible capacity of spinel Li_1.02M_xMn_2-xQ_yO_4-y. Therefore, cycle performance had been improved so obviously that 93.9% of the initial capacity were preserved after 100 cycles. Furthermore, electrochemical impedance tests were carried out with the spinel Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98 as working electrode, Lithium as counter electrode and reference electrode. Results showed that this material possessed good charge/discharge reversible capability and had the lowest impedance in 3.95～4.25 V range (on the stage of charge / discharge).     

锂离子电池正极材料LiNi1-xCoxO2的合成及电化学性能研究

LiNi_1-xCo_xO₂ cathode materials for lithium ion batteries were synthesized by the co-precipitation and solid-state reaction methods with LiOH·H₂O, Ni(NO₃)₂·6H₂O and Co(NO₃)₂·6H₂O as raw materials. The materials were characterized by XRD, SEM and electrochemical tests. The results showed that synthesized cathode materials were with layered structure similar to α-NaFeO₂ and uniform morphology and nearly normal grain size distribution and better electrochemical performance when x was 0.18. The first charge and discharge capacity of the cathode material was 224.3 mAh·g^-1 and 194.2 mAh·g^-1, respectively. 88.5% of the first discharge capacity remained at the 20th cycle.     

SnO2/ 石墨复合材料作为锂离子电池负极材料研究

Nano-scale SnO₂ powders were prepared by hydrolyzation. Graphite was poured into the SnCl₄ solution during hydrolyzation. After drying and calcining at 360 ℃, the negative electrode composite material of nanosized SnO₂ and graphite was obtained. The composite materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The average crystallite size was in the range of 15～20 nm. Electrochemical lithium insertion/extraction was studied preliminarily on the obtained composite. The discharge capacity of nanosized SnO₂ / graphite composite was found to have a high electrochemical reversible capacity for Li-ion insertion and extraction, which possessed the advantages of both higher discharge capacity of SnO₂ and lower discharge potential of graphite. In addition, the cycle capability was also improved due to the inhibiting effect of the composite against pulverization and agglomeration to a certain extent during Li-ion insertion and extraction.     

VOx / Titanate复合材料纳米棒的水热合成及其电化学性能研究

Vanadium oxide/titanate composites nanorods (VO_x/ Titanate-CNRs) were synthesized in high yield by using titanate nanotubes as templates and V₂O₅·nH₂O sol as the precursors under hydrothermal conditions (200 ℃, 48 h). Samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive analysis by X-ray (EDAX). X-ray diffraction structure determination showed that this new phase had the composition of V₃O₇·H₂O and crystallized with orthorhombic symmetry. SEM and TEM tests showed that the samples were uniform straight rods with the diameter range from around 100 to 300 nm and the length over 10 μm. The chemical compositions of the samples were determined with EDXA. The electrochemical tests of samples (titanates nanotubes, V₂O₅ and VO_x/ Titanate-CNRs) prove that VO_x/ Titanate-CNRs exhibit a better electrochemical performance.     

掺钇锆酸锶-TiO2复合光催化剂的制备及性能研究

SrZrO₃ particles were prepared by a co-precipitation method and Sr(Zr_1-xY_x)O_3-δ -TiO₂ composite particles were then synthesized by Sr(Zr_1-xY_x)O_3-δ and titanium dioxide. The composite particles were characterized by XRD, SEM, FTIR and TG-DTA techniques. The photocatalytic degradation of methylene blue (MB) in aqueous solution was used as a probe reaction to evaluate the photocatalytic activity of the composite particles. The effect of the preparation method for SrZrO₃, doping content of yttrium and TiO₂ amount in the composite particles on the photocatalytic activity of composite particles was also discussed. The results show that the methylene blue solution could be completely degraded by Sr(Zr_1-xY_x)O_3-δ -TiO₂ composite particles under UV-light or visible light irradiation. The photocatalytic activity of composite particles was higher than that of pure TiO₂. The fast recombination of photogenerated electrons and holes were restrained by the heterojunction formed in composite particles. The particle of SrZrO₃ prepared by co-precipitation was small, and the photocatalytic activity of composite particles prepared from this kind of SrZrO₃ was higher than that of particles prepared by solid sintering method. The best doping content of yttrium is 5%. The optimal content of TiO₂ in composite particles is 90wt%, 70wt%, respectively under UV-light and visible light irradiation, the degradation rates of MB are 98.8% and 93.5% , respectively after 50 min irradiation.     

锂离子电池用Li4Ti5O12-碳复合材料的制备与电化学性能

Li₄Ti₅O₁₂-C composite was prepared by sol-gel method using ethyl alcohol as solvent, lithium acetate and tetrabutyl titanate as raw materials, and graphite as carbon source. Li₄Ti₅O₁₂-C composites were characterized by thermogravimertric(TG) analysis and differential thermal analysis(DTA), X-ray diffraction(XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical tests. Results show that Li₄Ti₅O₁₂-C composite with 5% carbon containing can be obtained by annealing the precursor at 600 ℃ for 6 h in N₂ atomsphere. The composites can deliver a specific capacity of 167.1 mAh·g^-1, 99.0% and 105.1% of the capacity can be retained after discharged for 80 times at 0.1C and 2.0C, respectively. Compared with pure Li₄Ti₅O₁₂, Li₄Ti₅O₁₂-C composite shares larger discharge capacity, better cyclability and rate performance.     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

纳米尖晶石LixMn2O4的制备与电化学性能表征

Nano-spinel Li_xMn₂O₄(0.6 ≤x≤ 1.0) was synthesized by two steps of coprecipitation and calcination. The influences of calcination temperature, time and Li/Mn ratio on the crystal structure and the particle size of Li_xMn₂O₄ were investigated. It was shown that the higher the calcination temperature, the more complete the crystal structure, and the larger the particle size. Moreover, the influence of calcination time on the crystal structure was insignificant when it was more than 3h at 700℃. With the increase of x in Li_xMn₂O₄ in the range of 0.6～1.0, the d111 and lattice parameter a increased first and then decreased. The electrochemical properties of nano-spinel LiMn₂O₄ using as cathode material of lithium-ion battery were studied. The low discharge capacity might be due to the irreversible capacity loss brought by the large surface area and lattice vacancies of the nano-spinel.     

P(VDF-HFP)-PMMA/CaCO3(SiO2)复合聚合物电解质的电化学性质

采用激光扫描共焦显微镜、X射线衍射、循环伏安和交流阻抗等方法对由聚(偏二氟乙烯-六氟丙烯)(P(VDF-HFP))、聚甲基丙烯酸甲酯(PMMA)以及纳米碳酸钙(二氧化硅)制备的几种复合聚合物电解质(CPE)膜P(VDF-HFP)-PMMA/CaCO3(SiO2)的性能进行了研究. 结果表明, PMMA的加入能提高CPE的吸液率, 从而增大其离子导电率. 在P(VDF-HFP)与PMMA质量比为1:1条件下制得的CPE性能最佳. 用P(VDF-HFP)-PMMA为聚合物基体与纳米级SiO2、CaCO3进行复合制成的聚合物膜, 无机粒子的加入没有破坏原来聚合物非晶结构; 室温下CPE的电导率达到3.42 mS·cm-1; 电化学稳定窗口为4.8 V. 电池Li/CPE/GMS(石墨基材料)的测试证明, CPE与石墨负极有很好的相容性. 聚合物电池Li/CPE(CaCO3)/LiCoO2比Li/CPE)(SiO2)/LiCoO2具有更优越的倍率放电性能.     

锂离子电池正极材料Li2FeSiO4/C的改性研究

采用改进的溶胶-凝胶法合成了Li2Fe1-xMnxSiO4/C(x=0, 1/4, 1/3, 1/2)复合材料. 用X射线衍射(XRD)、拉曼光谱和扫描电子显微镜(SEM)对材料的结构和形貌进行了表征. 通过恒流充放电对材料的电化学性能进行了测试. 结果表明, 在室温、1.5~4.8 V电压范围内, 于C/16倍率下进行充放电测试时, Li2Fe3/4Mn1/4SiO4/C具有较高的首次放电比容量(201.0 mA·h/g), 具有良好的电化学性能.     

Effects of Co~（2＋）Doping on the Crystal Structure and Electrochemical Performance of LiFePO_4

Co2+-doped LiFePO4/C composite material was prepared by solid-state synthesis method using Fe2O3,Li2CO3 and NH4H2PO4 as the starting materials.The structures and elec-trochemical performance of samples were studied by XRD,SEM and constant current charge-discharge method.The results showed that the Co2+ doping did not change the crystal structure of LiFePO4.The unit cell volume changed with the increase of Co2+,and reached the maximum at x = 0.04.The LiFe0.96Co0.04PO4/C sample proved the best electrochemical properties.Its initial discharge capacity was 138.5 mA·h /g at 1 C rate.After 30 cycles,the capacity remained 127.7 mA·h /g,and the capacity retention rate was 92.2%.     

球磨参数对锂离子正极材料Li2FeSiO4电化学性能的影响

以碳酸锂、草酸亚铁、纳米二氧化硅为原料,采用机械球磨和固相法相结合的方法制备了Li2FeSiO4正极材料(F)。研究了球磨参数对F电化学性能的影响。结果表明,在球磨速度为500 rad.min-1,球料比[m钢球∶m原料]为15∶1,球径为3 mm的条件下制备的F具有较好的电化学性能。     

Li2MnSiO4/CNTs复合正极材料的合成与电化学性能

采用水热辅助溶胶-凝胶工艺,通过原位复合的方法合成了锂离子电池用Li2MnSiO4/CNTs复合正极材料.分析了复合正极材料的形貌和组成特征,并对每摩尔分别复合5,10,20和30 g碳纳米管(CNTs)及未复合CNTs的样品进行了电化学性能测试.结果显示,所合成的Li2MnSiO4颗粒尺寸分布均匀,粒径在100 nm左右,易团聚.但随着CNTs复合量的增加,团聚现象逐渐改善.合成的Li2MnSiO4材料结晶度良好,属于正交晶系Pmn21空间群.电化学测试结果表明,每摩尔复合20 g CNTs的样品电化学性能最佳,在10 mA/g电流密度下,首周放电容量为150 mA.h/g,循环20周后仍保持在80 mA.h/g;CNTs的原位复合可提高Li2MnSiO4材料的导电性能,并改善其电化学性能.     

碳包覆Li3V2(PO4)3:溶胶-凝胶法合成及性能

利用V₂O₅、LiOH·H₂O、H₂O₂、NH₄H₂PO₄与柠檬酸为原料,通过溶胶-凝胶法合成了碳包覆的Li₃V₂(PO₄)₃复合正极材料。采用XPS、XRD、SEM、TEM、拉曼光谱和电化学方法对材料的性能进行了研究。还研究了其结构与焙烧温度、样品电导率和电化学性能的关系。研究表明复合材料具有空间群为P2₁/n的单斜结构,表面包覆粗糙多孔的碳层。在800 ℃下制备的碳包覆样品的电子导电率高达9.81×10^-5 S·cm^-1,约为高温固相氢气还原法制备的未包覆碳Li₃V₂(PO₄)₃的10000倍。测试结果表明碳包覆Li₃V₂(PO₄)₃的电化学性能远优于未包覆碳的样品。在3.0～4.3 V电压范围内,以0.1C和2C倍率充放电时,碳包覆的Li₃V₂(PO₄)₃具有高比容量(分别为128和109 mAh·g^-1)和优异的循环性能。     

锂离子电池复合正极材料xLiFePO4·yLi3V2(PO4)3的复合机制

以FePO4·xH2O、V2O5、NH4H2PO4和Li2CO3为原料, 以乙二酸为还原剂, 通过湿化学还原-低温热处理方法制备出锂离子复合正极材料xLiFePO4·yLi3V2(PO4)3. X射线衍射(XRD)结果表明, 合成的材料中橄榄石结构的LiFePO4和单斜晶系的Li3V2(PO4)3两相共存; 从复合材料中LiFePO4、Li3V2(PO4)3相对于相同条件下制备的纯相LiFePO4和Li3V2(PO4)3的晶格常数变化以及结合高分辨透射电子显微镜(HRTEM)、能量散射X射线(EDAX)的结果可以看出, 在复合材料xLiFePO4·yLi3V2(PO4)3中存在部分V和Fe, 分别掺杂在LiFePO4和Li3V2(PO4)3中, 并形成固溶体; X射线光电子能谱(XPS)结果表明, Fe/V在复合材料中的价态与各自在LiFePO4和Li3V2(PO4)3中的价态保持一致, 分别为+2 和+3价. 充放电测试表明, 制备出的复合正极材料电化学性能明显优于单一的LiFePO4和Li3V2(PO4)3; 循环伏安测试表明, 复合正极材料具有优良的脱/嵌锂性能.     

P(VdF-HFP)-基离子液体复合聚合物电解质的阴极稳定性及热稳定性

以聚偏氟乙烯-六氟丙烯P(VdF-HFP)聚合物为基体, 制备了含离子液体1-甲基-3-乙基咪唑六氟磷酸盐(EMIPF6)、用于锂离子电池的离子液体复合聚合物电解质[P(VdF-HFP)/LiPF₆/EMIPF₆/EC(碳酸乙烯酯)-PC(碳酸丙烯酯)]. 采用热重分析法以及燃烧实验测试了复合聚合物电解质的热稳定性. 离子电导率测试表明, 离子液体的存在显著改善了复合聚合物电解质的离子传输; 循环伏安测试表明, 添加剂EC和PC的加入提高了复合电解质的阴极稳定性, 制得的离子液体复合聚合物电解质在0.3-4.3 V 电压范围内稳定存在. Li₄Ti₅O₁₂ 和LiCoO₂为电极材料、P(VdF-HFP)/LiPF₆/EMIPF₆/EC-PC 为电解质的半电池表现出优良的循环性能, 0.1C充放电倍率下, Li/LiCoO₂和Li/Li₄Ti₅O₁₂半电池的可逆容量分别为130和144 mAh·g^-1. 但EC、PC在一定程度上降低了离子液体复合聚合物电解质的热稳定性.     

Rh基催化剂上CO加氢制C2含氧化物的原位红外光谱研究

 用原位红外光谱考察了Rh-Mn-Li-Fe/SiO2和Rh/SiO2催化剂表面上CO的吸附态及CO加氢反应过程中吸附物种的变化. 结果表明,CO在Rh/SiO2催化剂上仅有线式吸附态存在,而CO在Rh-Mn-Li-Fe/SiO2催化剂上既有线式吸附态存在,又有孪生吸附态存在. 这说明Rh-Mn-Li-Fe/SiO2催化剂中Rh的分散度较高. 经CO加氢反应(3.0 MPa,593 K)后,在Rh-Mn-Li-Fe/SiO2催化剂上可观测到C2含氧化物前驱物种的吸收谱带,而在Rh/SiO2催化剂上未观测到相应的谱带; CO在这两种催化剂上主要以线式吸附态存在,孪生吸附态基本消失. 结合催化剂对CO加氢的催化性能,可以认为线式吸附的CO对生成C2含氧化物有贡献. Rh-Mn-Li-Fe/SiO2催化剂的高活性是由于助剂的存在削弱了其表面吸附CO的 C-O键,促进了CO的活化,从而有利于C2含氧化物前驱物的生成.     

Rh-Mn-Li/SiO2催化剂的吸附量热和红外研究

通过在最优Rh含量基础上对金属配比的再优化,成功地改进了Rh-Mn-Li/SiO2催化剂的CO加氢性能;并采用微量吸附量热和红外等表征手段,考察了助剂Mn和Li促进作用的本质.结果表明:助剂Mn和Li的添加,使孪式和线式吸附CO的碳氧键强度增加,并同时削弱了桥式吸附CO的碳氧键或者使其转化为更易于解离的倾斜式CO吸附物种,从而同时增加了Rh基催化剂的CO解离和插入能力,提高了其活性和C2含氧化合物选择性.另一方面,Mn和Li的添加显著地降低了Rh基催化剂表面H的数量和稳定性.催化剂加氢能力显著降低极大地抑制了CH4的生成,从而有利于C2含氧化合物选择性的进一步提高.