Co_2SnO_4/Graphene复合材料的制备与电化学性能研究

实验首先采用改进的Hummers法制备氧化石墨,然后以氧化石墨烯为前驱体,通过水热法将锡酸钴纳米颗粒均匀镶嵌在石墨烯薄膜基片上,最终获得Co2SnO4/Graphene镶嵌复合材料.采用X射线衍射(XRD)、扫描电子显微镜(SEM)对材料的结构和形貌进行表征,通过恒电流充放电(CC)、循环伏安法(CV)与交流阻抗法(EIS)测试了材料的电化学性能.实验结果表明,石墨烯良好的分散性及较高的电子导电率,可以提高锡酸钴材料的电化学性能,材料首次可逆容量达到1415.2 mA·h/g,50次循环后仍能保持469.7 mA·h/g的放电比容量.     

Ca$lt;sub$gt;2$lt;/sub$gt;Si（O$lt;sub$gt;4-$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;N$lt;sub$gt;$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;）：Eu$lt;sup$gt;2+$lt;/sup$gt;绿色荧光粉的制备及其发光性能

利用在Ca-Si-O干凝胶前驱体中添加Si₃N₄的方法于非还原气氛下合成了含N固溶体Ca₂Si（O_4-xN_x）：Eu²⁺绿色荧光粉. 通过X射线衍射仪、扫描电子显微镜以及荧光分光光度计分别分析了产物的物相结构、颗粒形貌和发光性能. 结果显示,Si₃N₄与前驱体的混合物在非还原气氛（纯氮气）下于1100℃焙烧后获得含N固溶体Ca₂Si（O_4-xN_x）：Eu²⁺荧光粉,特别是其中Eu³⁺被还原为Eu²⁺,产物的晶体结构与βup -Ca₂SiO₄相一致. Ca₂Si（O_4-xN_x）：Eu²⁺能够被270–400 nm 范围内的紫外线有效激发,其发射光谱呈宽带发射. 随着N含量的增加,发射峰出现一定程度红移（501–504 nm）,而且发光强度显著提高. 当Eu²⁺浓度为0.25 mol%时发光强度达最大值,浓度超过0.25 mol%时,发光强度显著降低,出现浓度猝灭 效应. 关键词： 白光LED 荧光粉 溶胶凝胶法 3N₄')" href="#">Si₃N₄     

Sr位Nd掺杂对SrBi$lt;sub$gt;2$lt;/sub$gt;Nb$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;9$lt;/sub$gt;性能的影响及机理研究

采用传统固相法制备了（Sr_1-3x/2A_x/2Nd_x）Bi₂Nb₂O₉（x=0,0.05,0.1和0.2）陶瓷,并系统研究了Nd离子取代Sr离子对SrBi₂Nb₂O₉性能的影响及其作用机理.研究结果表明：Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的介电常数和介电损耗随温度变化的行为具有明显的离子松弛极化特征.Nd³⁺对Sr²⁺的部分取代,导致Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉剩余极化强度P_r稍有下降,但其压电系数d₃₃却有所增加,根据铁电热力学理论,这是Nd³⁺对Sr²⁺取代导致材料介电常数增大所致.Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的居里温度（T_C）没有随Nd含量的增加而变化,拉曼光谱技术分析表明这是其NbO₆八面体畸变程度没有发生变化所致.Nd³⁺取代Sr²⁺提高了材料的介电常数ε_r、压电系数d₃₃、机电耦合系数K_p,同时降低了机械品质因数Q_m,但是谐振频率温度系数C值没有改变. 关键词： 压电陶瓷 介电性能 压电性能 拉曼光谱     

CO$lt;sub$gt;2$lt;/sub$gt;激光烧结合成负热膨胀材料Sc$lt;sub$gt;2$lt;/sub$gt;($lt;i$gt;M$lt;/i$gt;O$lt;sub$gt;4$lt;/sub$gt;)$lt;sub$gt;3$lt;/sub$gt;($lt;i$gt;M$lt;/i$gt;=W,Mo)及其拉曼光谱

用CO₂激光烧结合成了负热膨胀材料Sc₂(WO₄)₃和Sc₂(MoO₄)₃. 实验表明, 激光合成负热膨胀材料Sc₂(WO₄)₃和Sc₂(MoO₄)₃属于快速合成技术, 合成一个样品的时间仅需几秒到十几秒, 具有快速凝固的特征; X射线衍射和拉曼光谱分析表明, 所合成的材料为正交相结构, 且具有较高的纯度; 变温拉曼光谱分析表明, 所合成的材料在室温以上没有相变, 但可能有微弱的吸水性; 在对Sc₂O₃, MoO₃, WO₃, Sc₂(MoO₄)₃和Sc₂(WO₄)₃拉曼光谱分析的基础上, 给出了激光光子能量及原料和合成产物的声子能级图, 分析了激光烧结合成的机理. 激光光子能量转化为激发声子的能量是光热转化的主要通道, 原料在熔池中反应并快速凝固形成最终产物. 关键词： 负热膨胀材料 合成 激光烧结 拉曼光谱     

P掺杂对绿色荧光粉BaMgAl$lt;sub$gt;10$lt;/sub$gt;O$lt;sub$gt;17$lt;/sub$gt;:Mn$lt;sup$gt;2+$lt;/sup$gt;性能的影响

采用高温固相法合成P掺杂的BaMgAl₁₀O₁₇:Mn²⁺荧光粉,其中P通过（NH₄）₂HPO₄引入.利用X射线衍射谱、傅里叶变换红外光谱、扫描电子显微镜、能量色散谱、真空紫外光谱等研究了P掺杂对BaMgAl₁₀O₁₇:Mn²⁺晶体结构、微观形貌、发光性能等的影响.研究结果表明：（NH₄）₂HPO₄具有助熔剂的作用,它的加入有助于荧光粉的晶化,改善荧光粉的形貌.P掺杂进入晶格,使得晶胞参数变小,从而改变了Mn²⁺的晶体场环境,引起发射光谱蓝移,色坐标x值降低.P掺杂能有效提高基质对真空紫外线的吸收,从而提高真空紫外激发下的发光强度. 关键词： P掺杂 10O₁₇:Mn²⁺')" href="#">BaMgAl₁₀O₁₇:Mn²⁺ 晶体结构 真空紫外     

Ca$lt;sub$gt;0.64$lt;/sub$gt;WO$lt;sub$gt;4$lt;/sub$gt;:Eu$lt;sub$gt;0.24$lt;/sub$gt;陶瓷的高温相变机理及其对发光性能的影响

纯的CaWO₄具有优异的耐压、耐热稳定性,化学组成为Ca_0.64WO₄:Eu_0.24的陶瓷也具有CaWO₄结构,但Ca²⁺晶格位置含有12 mol%的肖特基缺陷. 这种缺陷浓度高的CaWO₄ 相是否具有良好的高温稳定性还有待研究. 本文探讨了过度烧结对Ca_0.64WO₄:Eu_0.24陶瓷相结构的影响,揭示了在高温下产生相变的可能原因,并研究了该相变对材料发光性能的影响. 研究表明,当烧结温度超过1100 ℃时,被肖特基缺陷束缚的部分氧离子会解离,造成Ca_0.64WO₄:Eu_0.24陶瓷体相中氧元素含量严重不足,诱发CaWO₄相发生相变,析出单斜晶系的Eu₂WO₆;研究还发现,CaWO₄相的晶面间距在高温相变后会增大;这可能是导致Ca_0.64WO₄:Eu_0.24陶瓷发光强度显著降低的一个重要原因. 关键词： 相变 钨酸钙 铕 发光     

用耦合簇方法及相关一致基研究PH$lt;sub$gt;2$lt;/sub$gt;($lt;i$gt;X$lt;/i$gt;$lt;sup$gt;2$lt;/sup$gt;$lt;i$gt;B$lt;/i$gt;$lt;sub$gt;1$lt;/sub$gt;)自由基的解析势能函数

利用耦合簇方法和Dunning等提出的系列相关一致基对PH₂自由基的基态结构进行优化, 并使用优选出的cc-pV5Z基组对其进行频率计算. 结果表明,平衡核间距R_P—H=0.14185 nm, 键角α_HPH=91.8624°, 离解能D_e（HP—H）=3.483 eV, 对称伸缩振动频率ν₁（a₁）=2399.9781 cm^-1, 弯曲振动频率ν₂（a₁）=1128.4213 cm^-1,反对称伸缩振动频率ν₃（b₂）=2407.8374 cm^-1. 在此基础上采用多体项展式理论导出了PH₂自由基的解析势能函数, 其等值势能图准确再现了PH₂自由基分子的平衡结构特征和动力学特征. 关键词： 2自由基')" href="#">PH₂自由基 多体项展式理论 解析势能函数     

Co掺杂对Mn$lt;sub$gt;3$lt;/sub$gt;Sn$lt;sub$gt;1-$lt;em$gt;x$lt;/em$gt;$lt;/sub$gt;Co$lt;sub$gt;$lt;em$gt;x$lt;/em$gt;$lt;/sub$gt;C$lt;sub$gt;1.1$lt;/sub$gt;化合物的磁性质、熵变以及磁卡效应的影响

利用固态反应法制备了Mn₃Sn_1-xCo_xC_1.1 （x=0.05,0.1,0.2） 系列化合物,研究了Co掺杂对其磁性质、相变、熵变的影响. 随着Co掺杂量的增加,样品的居里温度由283 K先降到212 K （Mn₃Sn_0.9Co_0.1C_1.1） 后又升到332 K （Mn₃Sn_0.2Co_0.8C_1.1）,相变类型由一级相变逐渐转变为二级相变. 增大Co的掺杂量,Mn₃Sn_1-xCo_xC_1.1化合物的熵变峰值逐渐减小,磁熵变温区由9 K展宽到300 K. 当Co掺杂量为0.2时,相对制冷量达到最高,为103 J/kg （磁场强度为1.6 MA/m）. 由于室温附近良好的磁致冷效应,该类材料在磁制冷领域可能具有重要的应用前景. 关键词： 磁性质 相变 磁卡效应 相对制冷量     

Tb$lt;sub$gt;0.3$lt;/sub$gt;Dy$lt;sub$gt;0.6$lt;/sub$gt;Pr$lt;sub$gt;0.1$lt;/sub$gt;(Fe$lt;sub$gt;1-$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;Al$lt;sub$gt;$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;)$lt;sub$gt;1.95$lt;/sub$gt;合金的磁性、磁致伸缩和穆斯堡尔谱研究

系统研究了室温下Tb_0.3Dy_0.6Pr_0.1（Fe_1-xAl_x）_1.95 （x=0.05,0.1,0.15,0.2,0.25,0.3）合金中元素Al替代Fe对结构、磁性、磁致伸缩性能和自旋重取向的影响.测量结果发现,x<0.2时Tb_0.3Dy_0.6Pr_0.1（Fe_1-xAl_x）_1.95合金基本上是纯的单相,x=0.2时出现其他杂相,杂相随Al替代量的增加不断增多.随Al替代量x的增加,点阵常数a接近于线性增大,Curie温度T_C逐渐下降,而矫顽力H_c急剧下降.振动样品磁强计（VSM）测量发现,磁化强度M随Al替代量x的变化较为复杂.VSM计和磁致伸缩效应测量共同表明,少量Al的替代有利于降低磁晶各向异性,而且随着Al替代量x的增多磁致伸缩系数快速减小,x>0.15时巨磁致伸缩效应消失.穆斯堡尔效应研究发现,随Al含量的增加Tb_0.3Dy_0.6Pr_0.1（Fe_1-xAl_x）_1.95合金中易磁化轴可能在{110}面逐渐偏离了立方晶体的主对称轴,发生自旋重取向,从而引起合金宏观磁性、磁致伸缩性能的变化. 关键词： 磁致伸缩 立方Laves相 自旋重取向 穆斯堡尔谱     

钙钛矿型锰氧化物(La$lt;sub$gt;0.8$lt;/sub$gt;Eu$lt;sub$gt;0.2$lt;/sub$gt;)$lt;sub$gt;4/3$lt;/sub$gt;Sr$lt;sub$gt;5/3$lt;/sub$gt;Mn$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;7$lt;/sub$gt;的磁性和电性研究

采用传统固相反应法制备钙钛矿型锰氧化物 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇多晶样品, X-射线衍射分析表明, 样品(La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇结构呈现良好的单相. 通过磁化强度随温度的变化曲线(M-T)、不同温度下磁化强度随磁场的变化曲线(M-H)和电子自旋共振谱发现: 在300 K以下, 随着温度的降低, 样品先后经历了二维短程铁磁有序转变 (T_C^2D ≈ 282 K)、三维长程铁磁有序转变(T_C^3D ≈ 259 K)、奈尔转变(T_N ≈ 208K)和电荷有序转变(T_CO ≈ 35 K); 样品 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇在T_N以下, 主要处于反铁磁态; 在T_C^3D达到370 K时, 样品处于铁磁-顺磁共存态, 在370 K以上时样品进入顺磁态. 此外, 分析电阻率随温度的变化曲线(ρ-T)得到: 样品在金属-绝缘转变温度(T_P ≈ 80 K)附近出现最大磁电阻值, 其位置远离T_C^3D, 表现出非本征磁电阻现象, 其磁电阻值约为61%. 在T_CO以下, 电阻率出现明显增长, 这是由于温度下降使原本在高温部分巡游的e_g电子开始自发局域化增强所致. 通过对 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇的ρ-T 曲线拟合, 发现样品在高温部分的导电方式基本遵循小极化子的导电方式. 关键词： 磁性 电性 金属-绝缘转变温度 电子自旋共振     

锂离子电池SnSb/C复合负极材料的热碳还原法制备及电化学性能研究

采用高温还原技术,以SnO2,SbO3为原料,分别以葡萄糖、中间相碳微球(MCMB)作为还原剂,制备了两种结构的SnSb/C复合材料,并对比了它们的形貌和电化学性能.采用X射线衍射技术、拉曼技术、扫描电子显微镜技术对材料的结构和形貌进行了表征,并且通过测试恒电流充放电曲线、循环伏安曲线和交流阻抗谱分析了材料的电化学性能.实验结果表明:葡萄糖作为还原剂时,形成以合金颗粒为内核,絮状碳壳均匀包裹的微米球状结构,首次放电比容量为793.379 mA·h·g-1,循环50周后仍维持在449.987 mA·h·g-1;而以MCMB作为还原剂时,形成合金颗粒与MCMB混合共存并部分包覆的结构,首次放电比容量为1164.938 mA·h·g-1,50周后的比容量仅有290.807 mA·h·g-1.     

In situ formed FeS2@CoS cathode for long cycling life lithium-ion battery

Pyrite FeS₂ exhibits an ultrahigh energy density (1671 W·h·kg^-1, for the reaction of FeS₂+4Li=Fe+2Li₂S) in secondary lithium-ion batteries, but its poor cycling stability, huge volume expansion, the shuttle effect of polysulfides, and slow kinetic properties limit its practical application. In this work, we synthesize a composite structure material CoS on FeS₂ surface (FeS_x@CoS, 1 < x ≤ 2) by using a cobalt-containing MOF to improve its cycle stability. It is found that CoS inhibits the side reactions and adsorbs polysulfides. As a result, the modified FeS₂ shows a higher discharge capacity of 577 mA·h·g^-1 (919 W·h·kg^-1) after 60 cycles than 484 mA·h·g^-1 (778 W·h·kg^-1) of bare pyrite FeS₂. This efficient strategy provides a valuable step toward the realization of high cycling stability FeS₂ cathode materials for secondary lithium-ion batteries and enriches the basic understanding of the influence of FeS₂ interfacial stability on its electrochemical performances.     

石墨烯改性锡酸锌材料的光谱特性及其光催化性能

半导体光催化氧化技术在处理能源危机和环境污染问题方面有非常重要的应用。选取石墨烯对水热法制备的Zn₂SnO₄进行改性。通过透射电镜(TEM)观察其形貌特征,通过X射线衍射(XRD)、红外光谱(FTIR)、拉曼光谱(Raman)以及X射线光电子能谱(XPS)分析其结构和组成。采用紫外-可见光分光光度计检测石墨烯/Zn₂SnO₄催化降解亚甲基蓝(MB)性能。通过添加自由基捕获剂的光催化实验、电子顺磁共振谱和荧光光谱检测分析石墨烯/Zn₂SnO₄降解MB的光催化机理。通过光催化重复性实验对石墨烯/Zn₂SnO₄的稳定性进行评估。结果表明：加入石墨烯不会对Zn₂SnO₄的结构形貌产生较大影响;当氧化石墨烯(GO)添加量为4 Wt%时,石墨烯/Zn₂SnO₄的光催化活性最高的;光催化过程中·OH是主要的活性物质,存在·OH间接氧化有机污染物的机制。     

Oxygen vacancies and V co-doped Co_3O_4 prepared by ion implantation boosts oxygen evolution catalysis

Introducing heteroatoms and defects is a significant strategy to improve oxygen evolution reaction(OER) performance of electrocatalysts. However, the synergistic interaction of the heteroatom and defect still needs further investigations. Herein, we demonstrated an oxygen vacancy-rich vanadium-doped Co_3O_4(V–O_v–Co_3O_4), fabricated by V-ion implantation, could be used for high-efficient OER catalysis. X-ray photoelectron spectra(XPS) and density functional theory(DFT) calculations show that the charge density of Co atom increased, and the reaction barrier of reaction pathway from O*to HOO*decreased. V–O_v–Co_3O_4 catalyst shows a low overpotential of 329 mV to maintain current density of 10 m A·cm~(-2), and a small Tafel slope of 74.5 m V·dec~(-1). This modification provides us with valuable perception for future design of heteroatom-doped and defect-based electrocatalysts.     

Probing the improved stability for high nickel cathode via dual-element modification in lithium-ion

One of the major hurdles of nickel-rich cathode materials for lithium-ion batteries is the low cycling stability, especially at high temperature and high voltage, originating from severe structural degradation, which makes this class of cathode less practical. Herein, we compared the effect of single and dual ions on electrochemical performance of high nickel (LiNi_0.88Mn_0.03Co_0.09O₂, NMC) cathode material in different temperatures and voltage ranges. The addition of a few amounts of tantalum (0.2 wt%) and boron (0.05 wt%) lead to improved electrochemical performance. The co-modified LiNi_0.88Mn_0.03Co_0.09O₂ displays an initial discharge capacity of 234.9 mAh/g at 0.1 C and retained 208 mAh/g at 1 C after 100 cycles at 45 ℃, which corresponds to a capacity retention of 88.5%, compared to the initial discharge capacity of 234.1 mAh/g and retained capacity of 200.5 mAh/g (85.6%). The enhanced capacity retention is attributed to the synergetic effect of foreign elements by acting as a surface structural stabilizer without sacrificing specific capacity.     

Scalable synthesis and superior performance of TiO<Subscript>2</Subscript>-reduced graphene oxide composite anode for sodium-ion batteries

TiO₂-reduced graphene oxide (RGO) composite was synthesized via a sol-gel process and investigated as an anode material for sodium-ion batteries (SIBs). A remarkable improvement in sodium ion storage with a reversible capacity of 227 mAh g^?1 after 50 cycles at 50 mA g^?1 is achieved, compared to that (33 mAh g^?1) for TiO₂. The enhanced electrochemical performance of TiO₂-RGO composite is attributed to the larger specific surface area and better electrical conductivity of TiO₂-RGO composite. The excellent performance of TiO₂-RGO composite enables it a potential electrode material for SIBs.     

溶剂热制备锂电池负极材料CNT-ZnFe2O4及其电化学性能

为了改善锂离子电池负极材料ZnFe₂O₄导电性差和循环寿命低的缺点,利用溶剂热反应方法制备了ZnFe₂O₄,并通过复合碳纳米管对ZnFe₂O₄进行改性。充放电测试结果表明：经过50次充放电后,碳纳米管复合改性后的ZnFe₂O₄容量保持在860 mA·h·g^-1,具有较好的循环稳定性。碳纳米管具有良好的导电性与导热性,改善了ZnFe₂O₄导电性差的缺点。     

Three-dimensional nitrogen-doped graphene/sulfur composite for lithium-sulfur battery

A three-dimensional nitrogen-doped graphene/sulfur composite (NGS3) was synthesized by a simple hydrothermal method using urea as the nitrogen source and subsequent thermal treatment. The structure and electrochemical performance of the prepared nitrogen-doped graphene/sulfur composite (NGS3) were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), Energy dispersive spectroscopy mapping (EDS), and galvanostatic charge/discharge measurements. SEM and EDS mapping show that NGS3 exhibits a porous structure with uniform distribution of sulfur. Compared with the graphene/sulfur composite (NGS1), NGS3 delivers an outstanding rate capability with 1501, 1278, 1136, and 1024 mAh g^?1 at 200, 400, 800, and 1000 mA g^?1, respectively, and the cycle stability of NGS3 is also wonderful, a reversible discharge capacity of 1330 mAh g^?1 is obtained after 80 cycles under the current rate of 200 mA g^?1. The wonderful electrochemical performance could be attributed to the special three-dimensional conductive structure with the help of nitrogen atom.     

AA-stacked borophene-graphene bilayer as an anode material for alkali-metal ion batteries with a superhigh capacity

As the lightest two-dimensional material, monolayer borophene exhibits great potential as electrode materials, but it suffers from stability issues in the free-standing form. Here, the striped-borophene and graphene bilayer (sB/Gr) is found to be a high-performance anode material for rechargeable alkali-metal ion batteries. The first-principles results show that all the three alkali-metal atoms, Li, Na, and K, can be strongly adsorbed on sB/Gr with ultra-low diffusion barriers than that on pristine borophene/graphene, indicating good charge-discharge rates. Remarkably, high storage capacities are proposed for LIBs (1880 mA·h/g), NIBs (1648 mA·h/g), and KIBs (470 mA·h/g) with relatively small lattice change rate (<2.9%) in the process of alkali-metal atoms intercalations. These intriguing features of sB/Gr make it an excellent choice for batteries.     

SnO2/Co3O4 nanofibers using double jets electrospinning as low operating temperature gas sensor

SnO₂/Co₃O₄nanofibers(NFs)are synthesized by using a homopolar electrospinning system with double jets of positive polarity electric fields.The morphology and structure of SnO₂/Co₃O₄hetero-nanofibers are characterized by using field emission scanning electron microscope(FE-SEM),transmission electron microscope(TEM),x-ray diffraction(XRD),and x-ray photoelectron spectrometer(XPS).The analyses of SnO₂/Co₃O₄NFs by EDS and HRTEM show that the cobalt and tin exist on one nanofiber,which is related to the homopolar electrospinning and the crystallization during sintering.As a typical n-type semiconductor,Sn O₂has the disadvantages of high optimal operating temperature and poor reproducibility.Comparing with Sn O₂,the optimal operating temperature of SnO₂/Co₃O₄NFs is reduced from 350℃to 250℃,which may be related to the catalysis of Co₂O₂.The response of SnO₂/Co₃O₄to 100-ppm ethanol at 250℃is 50.9,9 times higher than that of pure Sn O₂,which may be attributed to the p–n heterojunction between the n-type Sn O₂crystalline grain and the p-type Co₂O₂crystalline grain.The nanoscale p–n heterojunction promotes the electron migration and forms an interface barrier.The synergy effects between Sn O₂and Co₂O₂,the crystalline grain p–n heterojunction,the existence of nanofibers and the large specific surface area all jointly contribute to the improved gas sensing performance.