不同碳源掺杂磷酸亚铁锂正极材料电化学性能研究

采用液相共沉淀-固相焙烧合成了橄榄石型磷酸亚铁锂(LiFePO4)正极材料,用X射线衍射(XRD)、扫描电镜(SEM)和恒流充放电测试等方法对产物物相结构、表观形貌和电化学性能进行了表征和分析.纯相材料首次放电比容量达到90.6 mA·h/g,循环5次后,放电比容量为75.94 mA·h/g.为解决首次放电比容量低下以及材料循环性能差的问题,采取不同碳源掺杂对材料进行改进,最后得到LiFePO4/C复合正极材料,0.05 C首次放电比容量达到158.8 mA·h/g.     

基于Li_3PO_4水热法制备LiFePO_4及其改性

以自制Li3PO4为前驱体,在水热条件下与FeSO4.7H2O反应制备得到纯相LiFePO4,并通过碳包覆和Cu2+掺杂对其进行了有效改性,获得了适合高电流密度放电的LiFePO4正极材料。采用X射线衍射(XRD)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)对产物进行了物相和形貌表征。实验研究了水热反应温度对产物的形貌及其电化学性能的影响,同时探讨了掺杂Cu2+对材料常温和低温电化学性能的影响。结果表明:在200℃、24h水热条件下制得的产物,经碳包覆后的复合材料LiFePO4/C(LFP200/C),以1C(150mA.g-1)电流放电,放电比容量达140.7mAh.g-1;对材料进行Cu2+掺杂得到的Cu-LFP200/C材料的放电比容量及倍率性能得到进一步提高,常温下1C倍率的放电比容量为150.3mAh.g-1,10C倍率的放电比容量为108.7mAh.g-1,在-30℃条件下的放电比容量依然达到97mAh.g-1。     

液相法合成高容量LiFePO4/C复合正极材料

采用液相共沉淀法合成了纯相橄榄石型LiFePO4和LiFePO4/C复合正极材料。利用原子吸收(AAS)、X射线衍射(XRD)、扫描电镜(SEM)、振实密度测定等方法对其进行表征,并组装成电池研究其电化学性能。结果表明:LiFePO4和LiFePO4/C都具有单一的橄榄石型晶体结构,且前者的振实密度可达1.67 g/cm2,掺碳后制成的LiFePO4/C振实密度有所降低,但充放电平台非常平稳。与纯相LiFePO4相比,LiFePO4/C具有更高的放电比容量和循环性能,室温下以0.2 mA/cm2和0.4 mA/cm2电流密度充放电,首次放电比容量分别达到158.1 mA.h/g、150.0 mA.h/g。充放电循环20次后放电比容量仍分别保持在154.2 mA.h/g,137.2 mA.h/g。     

共沉淀法合成磷酸铁锂掺碳复合正极材料

采用共沉淀法合成了纯相橄榄石型磷酸铁锂(LiFePO4)和磷酸铁锂掺碳(LiFePO4/C)复合正极材料.利用X射线衍射(XRD)、原子吸收(AAS)、扫描电镜(SEM)、红外吸收(FT-IR)、振实密度测定等方法对其进行表征,并组装成电池研究其电化学性能.结果表明:HFePO4和LiFePO4/C具有单一的橄榄石型晶体结构,前者的振实密度可达1.58 g/cm2,LiFePO4/C振实密度有所降低,但充放电平台非常平稳.与纯相LiFePO4相比,LiFePO4/C具有更高的放电比容量和循环性能,室温下以0.05 C和0.1 C倍率电流充放电,首次放电比容量达到158.1,150.0 mA·k/g.充放电循环20次后放电比容量仍保持在154.2,137.2 mA·h/g.     

碳源及加入量对LiFePO_4/C性能的影响

以不同的有机物(蔗糖、柠檬酸、聚乙烯吡咯烷酮K30、聚乙二醇2000、酒石酸)为碳源合成LiFePO4/C复合材料,研究了不同碳源对复合材料晶型结构与电化学性能的影响。结果表明,不同的碳源对LiFePO4材料的晶型结构没有影响,但对电化学性能影响较明显,其中采用蔗糖为碳源制得的复合正极材料电化学性能最好。进一步研究了蔗糖加入量对复合材料的形貌、粒径分布、电导率及电化学性能的影响,发现当蔗糖加入量为铁与碳的物质的量比为1∶1时,样品颗粒细小、分布均匀,电导率明显提高,电化学性能最好,0.1C首次放电比容量为154.53 mA.h/g,0.5C首次放电比容量也高达141.14 mA.h/g,循环10次后,仍保持在137.62 mA.h/g。     

锂离子电池LiNi_xFe_(1-x)PO_4正极材料的制备及其电化学性能

本文以蔗糖为碳源,采用固相法合成了锂离子电池LiNixFe1-xPO4(x=0、0.05、0.1、0.2和0.3)正极材料,通过XRD和SEM等表征所合成的产物为多孔炭和LiFePO4相以恒电流充放电和电化学阻抗谱研究了材料的电化学性能,结果LiNi0.1Fe0.9PO4的性能最佳,其粒径大小在500～1000nm左右,在2C的充放电条件下,其放电比容量为70.3mAh·g-1,15次循环后容量保持率达90%。     

高密度LiFePO4正极材料的合成与性能

以高温固相法制备了高密度的LiFePO4正极材料,利用XRD、SEM、粒度分析、交流阻抗以及充放电测试等方法研究了前驱体Li3PO4和FePO4的比例与LiFePO4的物理性能和电化学性能的关系。其中,在Li3PO4与FePO4物质的量比为3：2时,制备的LiFePO4正极材料振实密度高达1.4g／cm^3,以0.1C放充电时,其首次放电比容量为159.0mA·h／g,体积比容量为222.6A·h／L,循环25次后,容量保持率达94.0％。     

中空八面体锂离子电池正极材料LiFePO_4的制备及电化学性能

以醋酸锂、磷酸、七水合硫酸亚铁为原料,聚乙二醇为分散剂,通过一步水热法制备得到中空八面体LiFePO_4锂离子电池正极材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学性能测试仪对样品晶型、形电化学性能进行了表征测试。研究结果表明,在2.5~4.2 V电压范围内,以0.1 C(17 mA/g)倍率进行充放电,样品首次放电比容量为129.6 mA·h/g;0.2、0.5、1、2和5 C的充放电倍率时,首次放电比容量分别达到123.6、119.7、114.1、99.5g和90.6 mA·h/g。10 C的充放电倍率时首次放电比容量为84.3 mA·h/g,说明中空八面体LiFePO_4在高倍率下表现出优异的电化学性能。     

改进固相法合成LiNixCoyMn1-x-yO2正极材料及性能研究

采用同相法制备正极材料LiNi1/3Co1/3Mn1/3O2,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)/透射电镜(TEM)分析材料的结构和形貌特征,用LAND电池测试系统测试材料的电化学性能(充放电容量和循环性能等).以LiOH·H2O,H2C2O4·2H2O,Ni(AC)2·4H2O,Co(AC)2·4H2O和Mn(AC)2·4H2O为原料,采用固相法在不同煅烧温度和煅烧时间下制备的层状正极材料LiNi1/3Co1/3Mn1/3O2具有典型的α-NaFeO2型层状结构特征,晶型结构完整.电化学性能测试结果表明,在850℃下保温15 h合成的正极材料电化学性能最优,在电流密度为120 mA/g、充放电电压在2.75～4.5 V时,经30次循环后放电比容量为163.5 mA·h/g,容量保持率为94%;50次循环后为157.2 mA·h/g,容量保持率为90.8%.     

磷酸亚铁锂-磷酸钒锂复合材料制备方法研究

以固相法制备出了磷酸亚铁锂-磷酸钒锂复合正极材料.采用X-射线衍射仪(XRD)、电子扫面电镜(SEM)、激光粒度分析仪、碳硫分析仪以及X-光电子能谱仪等对制备出的复合材料进行表征,发现该材料以磷酸亚铁锂和磷酸钒锂的晶形结构为主,其中有少量的杂质成分;该材料颗粒粒度较细、粒度分布窄且均匀,颗粒表面光滑、碳包裹状况良好,同其它方法制备的复合材料比较在碳含量差不多的情况下具有较优的导电率.对材料进行了电化学性能表征认为该材料的电化学性能比较优异,0.1C放电容量达到190 mA·h·g-1以上,10C可以达到120 mA·h·g-1,20C放电容量仍有85 mA·h·g-1且循环稳定性均较好;1C进行1000次循环之后仍然保持120 mA·h·g-1的容量,具有较高的实用价值.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Al_2(SO_4)_3/FeCl_3催化合成乙酸异戊酯

以冰乙酸和异戊醇为原料,Al_2(SO_4)_3/FeCl_3为催化剂,对催化合成乙酸异戊酯的条件进行研究。考察催化剂用量、乙酸与异戊醇物质的量比以及反应时间对乙酸酯化率的影响。结果表明,Al_2(SO_4)_3/FeCl_3具有良好的催化活性,在乙酸物质的量为0.1 mol、乙酸与异戊醇物质的量比为1∶4、催化剂用量1.0 g、反应时间2.0 h和带水剂环己烷用量10 m L反应条件下,重复实验3次,平均乙酸酯化率为93.50%。     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

V2O5-WO3-MoO3/TiO2催化剂用于NH3选择性还原减排NOx的性能（英文）

The V2O5-WO3-MoO3/TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM) and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass percentage of V:W:Mo:TiO2 :fiber glass= 1:4.5:4.5:72:18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to rutile by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3 . The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615-1640 mg·m-3 . Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.     

K_2SO_4对V_2O_5/TiO_2脱硝催化剂表面形态的影响

采用XRD和XPS对新鲜的和K2SO4掺杂的V2O5/TiO2脱硝催化剂的表面形态进行了分析。结果表明,K2SO4的掺杂未对V与Ti之间的相互作用造成显著的影响,但是引起催化剂表面V和Ti的浓度降低,V5+在催化剂表面消失。K与钒氧物种上的晶格氧发生了强烈的相互作用。     

稀土固体超强酸SO2-4/TiO2/La3+催化合成醋酸丁酯

研究了以固体超强酸SO24-/TiO2/La3+催化剂,醋酸和正丁醇为原料合成醋酸丁酯,并考察了影响反应的因素.结果表明醇酸物质的摩尔比为1.61、催化剂用量0.6 g、带水剂甲苯7 mL、反应时间2.5 h是最适宜的反应条件,其酯化率可达96.2%.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Synthesis of LiNi0.9Co0.1O2 from Li2CO3, NiO or NiCO3, and CoCO3 or Co3O4 and their electrochemical properties

Cathode active materials with a composition of LiNi_0.9Co_0.1O₂ were synthesized by a solid-state reaction method at 850 °C using Li₂CO₃, NiO or NiCO₃, and CoCO₃ or Co₃O₄, as the sources of Li, Ni, and Co, respectively. Electrochemical properties, structure, and microstructure of the synthesized LiNi_0.9Co_0.1O₂ samples were analyzed. The curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂ for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in Li_xNi_0.9Co_0.1O₂. The LiNi_0.9Co_0.1O₂ sample synthesized from Li₂CO₃, NiO, and Co₃O₄ had the largest first discharge capacity (151 mA h/g), with a discharge capacity deterioration rate of −0.8 mA h/g/cycle (that is, a discharge capacity increasing 0.8 mA h/g per cycle).