Surface modification of carbon anodes for secondary lithium battery by fluorination

Recent results on the surface modification of petroleum cokes and their electrochemical properties as anodes of secondary lithium batteries are summarized. The surface of petroleum coke and those heat-treated at 1860-2800 °C were fluorinated by elemental fluorine (F₂), chlorine trifluoride (ClF₃) and nitrogen trifluoride (NF₃). No surface fluorine was found except only one sample when ClF₃ and NF₃ were used as fluorinating agents while surface region of petroleum coke was fluorinated when F₂ was used. Transmission electron microscopic (TEM) observation revealed that closed edge of graphitized petroleum coke was destroyed and opened by surface fluorination. Raman spectra showed that surface fluorination increased the surface disorder of petroleum cokes. Main effect of surface fluorination with F₂ is the increase in the first coulombic efficiencies of petroleum cokes graphitized at 2300-2800 °C by 12.1-18.2% at 60 mA/g and by 13.3-25.8% at 150 mA/g in 1 mol/dm³ LiClO₄-ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1, v/v). On the other hand, main effect of the fluorination with ClF₃ and NF₃ is the increase in the first discharge capacities of graphitized petroleum cokes by ∼63 mAh/g (∼29.5%) at 150 mA/g in 1 mol/dm³ LiClO₄-EC/DEC.     

Surface and bulk properties of severely fluorinated carbon fibres

The development of ultra-inert composites using fluorinated carbon fibres as the reinforcement requires fluorinated carbon fibres with a durable surface composition. Here we report the effect of direct fluorination using an F₂/N₂ mixture at 653 K on the surface and bulk properties of two types of high strength carbon fibres. These were treated up to a surface fluorine content of ∼64 at.% and a bulk fluorine content of ∼15 mass%. A colour change was observed after fluorination caused by the changes in the graphitic band structure of the carbon fibres by the introduction of carbon sp³ hybridisation. The tensile strength and Young's modulus decrease after fluorination by up to 33 and 22%, respectively. XRD shows marginal changes in the interlayer distance but the crystallite size increases. Changes in the electrical conductivity of the fluorinated carbon fibres indicate that the modification is confined to the near surface volume. Predominantly covalent C-F bonds are formed as shown by X-ray photoelectron spectroscopy (XPS) and measured zeta (ζ)-potentials. Hence the fluorinated fibres are hydrophobic and have low surface tensions. This and the large increase in fibre surface area, as determined by nitrogen adsorption, is expected to facilitate interfacial interaction between fluorinated carbon fibres and fluoropolymers.     

Carbon nanotube assisted synthesis of CeO2 nanotubes

CeO₂ nanotubes have been synthesized facilely using carbon nanotubes (CNTs) as templates by a liquid phase deposition method. The properties of the CeO₂ nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) as well as thermogravimetry and differential thermal analysis (TG-DTA). The obtained CeO₂ nanotubes with a polycrystalline face-centered cubic phase have a uniform diameter ranging from 40 to 50 nm. The CeO₂ nanotubes are composed of many tiny interconnected nanocrystallites of about 10 nm in size. The pretreatment of CNTs and calcination temperature were confirmed to be the crucial factors determining the formation of CeO₂ nanotubes. A possible formation mechanism has been suggested to explain the formation of CeO₂ nanotubes.     

微波原位法制备碳点/壳聚糖荧光复合物及其应用研究

选择壳聚糖水溶液作为唯一反应物,利用简单方便的微波原位法制备碳点/壳聚糖荧光复合物,该复合物无需经过产物分离提纯等步骤就能够直接进行后续应用.测试结果表明,碳点/壳聚糖复合物溶液呈黄棕色,透明均一,在365 nm紫外光下显示出明显的蓝色荧光.此外,碳点/壳聚糖复合物中的碳点分散良好,尺寸比较均一.重要的是,该碳点/壳聚糖复合物具有新的综合性能特点,即不仅被赋予了碳点的多色荧光性能,而且还保留了壳聚糖的成膜性能和p H刺激响应性能,可以十分方便地直接进行多种应用,包括利用该复合物制备荧光复合膜和复合球,以及采用电沉积方法制备具有特定形状的荧光涂层,还可以直接应用于细胞成像.因此,这种微波原位法制备的碳点/壳聚糖复合物在荧光材料、荧光涂层、生物成像和生物标记等领域具有潜在的应用价值.     

双电极法现场快速检测地下水和湖水中碳酸氢根和碳酸根

地下水和湖水中碳酸氢根( HCO-3)和碳酸根( CO2-3)含量是地球化学碳行为和碳循环的重要表征,但两种离子的浓度易受环境影响而改变,因此,地下水和湖水中HCO-3和CO2-3真实含量的测定一直是个难题。实验利用CO2的水解平衡,通过pH电极和二氧化碳电极联用,建立了HCO-3和CO2-3现场快速测定的新方法,解决了地下水和湖水中HCO-3和CO2-3真实含量的测定难题。研究结果表明,在pH=4.8±0.1的底液中, HCO-3和CO2-3的线性范围分别为0.027~570 mg/L和1.25×10-8~39.7 mg/L。共存的金属离子、强酸阴离子(K+、Na+、Mg2+、Cl-、SO2-4,100 mg/L)、弱酸阴离子和弱酸(HSO-3、NO-2、HOAc,50 mg/L)对测定干扰小于5%。实际水样加标实验回收率在95.2%~99.2%之间,相对标准偏差为2.6%~3.7%。与酸碱滴定法进行对比,本方法的准确性良好。但方法受温度影响,因此标准溶液与样品应在同一温度下测量。总体而言,双电极法灵敏、快速、经济且电极携带方便、操作简单、对环境要求不高,十分适合现场和室内一般自然水体的快速检测。本方法已成功应用于青海省地下水和青海湖湖水中HCO-3和CO2-3的现场测定。实验表明,海东地区地下水样品pH在6.4~7.4之间,HCO-3含量为234~4096 mg/L,CO2-3含量为0.16~1.89 mg/L;青海湖湖水样品pH≈8.7,HCO-3含量范围在1.36~1.86 g/L,CO2-3含量在32.3~43.9 mg/L,与文献结果吻合。     

Electroactive shape memory cyanate/polybutadiene epoxy composites filled with carbon black

Electroactive shape memory composites were synthesized using polybutadiene epoxy(PBEP) and bisphenol A type cyanate ester(BACE) filled with different contents of carbon black(CB). Dynamic mechanical analysis(DMA), scanning electron microscopy(SEM), electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.     

离子液体在CO_2电还原反应过程中的催化作用与机理研究

在1-丁基3-甲基咪唑三氟甲基磺酸盐([Bnlim][CF_3SO_3])/碳酸丙烯酯(PC)溶液中,采用循环伏安曲线、交流阻抗谱及阻抗模拟方法,研究了CO_2在Au上发生电还原反应的速率控制步骤与离子液体的催化作用.结果表明,在CO_2电还原反应过程中,吸附态CO_2经单电子还原生成CO_2~-自由基是速率控制步骤.由于离子液体的催化作用,CO_2在[Bmim][CF_3SO_3]/PC溶液中电还原的过电位比在四丁基三氟甲基磺酸铵([Bu_4N][CF_3SO_3])/PC溶液中降低了239 mV.交流阻抗测试结果表明,离子液体中的阳离子[Bmim]~+吸附在Au电极表面,形成离子液体吸附层,吸附态的CO_2分子经单电子还原后生成CO_2~·-)自由基,与周围离子液体发生相互作用,形成中间体[Bmim-CO_2]_(ad),降低了CO_2~(·-)的能量状态,使得CO_2电还原反应的过电位大幅度降低.     

恒电量瞬态扰动测量Tafel斜率及数据积分处理

提出了一个三参数积分法拟合恒电量强极化数据以测定Tafel斜率的新方法.实验证明,恒电量瞬态扰动测量碳钢在酸溶液中的腐蚀,获得的Tafel斜率与消除了溶液电阻影响的Tafel外推结果有很好的一致性,说明恒电量法有效地消除了溶液电阻对该体系测量结果的影响,并且通过电化学和失重实验验证表明,这种快速测量可以获得准确的腐蚀速率.这种新的恒电量强极化积分算法相对微分法的优势体现在算法简捷和用于数值计算的数据具有较高的信噪比,因此能够提高测量精度.     

CnBδ(δ=0, ±1; n =1～6)团簇的结构、稳定性和光谱

采用密度泛函理论(DFT)的B3LYP方法,在6-31G*和6-311＋G(3df)水平上对C_nB(n=1～6)团簇及其阴离子和阳离子的几何构型和电子结构进行了优化和振动频率计算.得到了C_nB(n=1～6)团簇的电离能,绝热电子亲合势以及C_nB^δ(δ=0,±1)团簇的能隙.结果表明C_nB^－(n=1～6)团簇的基态构型均为线形,这与等电子的C_n簇合物的结构是一致的; C_nB(n=1～6)团簇的基态构型中,除C₂B为不对称的三角形,C₆B为具有C_2v对称性的环状结构外,其余均为线形结构.阳离子团簇中n=2、3、6的基态结构具有C_2v对称性外,其它几个均为线形结构.从几何参数和振动频率上发现,采用密度泛函B3LYP方法在6-311＋G(3df)和6-31G*两种基组上计算得到的键长参数和振动频率非常接近,说明B3LYP方法在计算C_nB簇合物结构参数上对于基组的选择是不太敏感的.通过对C_nB(n=1～6)的光电子能谱性质的研究发现,C₄B容易获得一个电子形成阴离子团簇,但失去一个电子是很困难的,这与实验上观测到的结果非常吻合.     

具有平整表面的定向纳米碳管膜的制备

为了获得表面平整的定向纳米碳管，通过化学及物理的方法将纳米碳管膜进行反转，使其原来的AAO模板底面成为新的表面，用溶液逐步去除表面的铝和氧化铝后，获得了平整的定向纳米碳管膜表面，从而可将其作为工作面使用. 还比较了5％NaOH和6%H₃PO₄＋1.8%H₂CrO₄溶液去除氧化铝的效果.