交联剂的引入对碳负极材料性能的影响

研究了引入的交联剂二乙烯基苯对作为锂离子二次电池负极材料的聚合物裂解碳性能的影响.结果表明交联剂引入到聚丙烯腈中后,在热处理过程中有利于该聚合物的碳化,导致层间距d002减少及石墨微晶尺寸增加;交联剂的固定作用使碳材料的有序性得到了提高;同时微孔数目也得到了增加.这些因素的影响导致了聚合物裂解碳的可逆储锂容量随交联剂的量的增加而提高.对于别的加聚物如聚4乙烯吡啶而言,同样也使所得到的聚合物裂解碳的可逆储锂容量得到了提高.最大可逆容量可达600mAh·g-1.     

由微孔棒状羟基磷灰石为模板合成的新型层次孔炭材料的电化学电容性能

电化学电容器已经成为极具潜力的可满足高功率需求的储能系统器件. 多孔炭具有大比表面积、高导电性、化学惰性、廉价及可调孔结构等优势, 因此成为电化学电容器最为常用的电极材料. 本文报道由微孔棒状羟基磷灰石为模板及蔗糖为碳源合成的新型具有层次孔道结构的孔炭材料的电化学电容器的性能. 采用X射线衍射分析仪、扫描电子显微镜、透射电子显微镜、X射线光电子能谱及BET表面分析仪表征了合成的多孔炭的形貌及表面特性. 采用循环伏安法、交流阻抗图谱分析及恒流充放电评价多孔炭材料在1 mol·L^-1硫酸中的电化学电容性能. 多孔炭具有高的比表面积(719.7 m²·g^-1)和大的孔容(1.32 cm³·g^-1), 其无序的孔道由任意分布的微孔、坍塌的中孔及类模板形状的相互交织的棒状中孔组成. 随着炭化温度的增加, 微孔及棒状中孔的密度随之降低, 在炭化温度高达900℃时, 孔径分布图上出现了三个峰. 正是由于这些特殊的结构特征, 由900℃炭化得到的多孔炭制成的电极展示出很好的电化学电容性能.     

Correlation between crystal texture and microporous structure of carbon adsorbents

A correlation of adsorption and X-ray data for a series of both initial and modified active carbons (AC) was performed. The AC were modified by thermal treatment and progressive activation. A linear correlation between the sizes of crystallites and micropore widths of AC was established. It was shown that the adsorption of water vapor results in an increase in the parameterL _aof crystallites of active carbons.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2159–2162, November, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09550).     

Hierarchical porous carbon/selenium composites derived from abandoned paper cup as Li-Se battery cathodes

Paper cup composed of crude cellulose is a common waste in daily life. In this paper, hierarchical porous carbons have been successfully prepared by an initial hydrothermal treatment and subsequent activation route from abandoned paper cup, and then paper cup derived carbons are used as scaffolds to fabricate serial carbon/Se composites. The optimal composite presents unique 3D porous structure, with amorphous selenium uniformly confined into the micropores of carbon. As the cathode materials of Li-Se battery, this composite reveals an initial reversible discharge capacity of 517.2 mAh g⁻¹ at 0.2C, and a capacity value of 431.9 mAh g⁻¹ can be retained after 60 cycles. Even at a high rate of 4C, a capacity value of 295.8 mAh g⁻¹ can be obtained. By comparison, the improved electrochemical performance of the optimal composite should be attributed to reasonable porous structure and effective encapsulation of amorphous selenium.     

Sol–gel derived nano-crystalline CaSnO3 as high capacity anode material for Li-ion batteries

CaSnO₃ with the distorted-perovskite structure was prepared by sol–gel and high temperature solid-state reaction and electrochemical properties were studied in cell with Li as counter electrode. The sol–gel method gave uniform nano-crystallites (200–300 nm) of CaSnO₃ and was shown to deliver a reversible capacity of 380 mAh/g (0.005–1.0 V; 60 mA/g) with good cycling stability up to 45 cycles. The observed capacity involved in the first-discharge and the reversible capacity values during subsequent charge–discharge cycles show that the electrochemical process in CaSnO₃ is similar to other Sn-containing mixed oxide systems, viz., an initial structural reduction with Sn-metal formation followed by reversible Li–Sn alloy formation. The performance with respect to the attainable capacity, its retention on charge–discharge cycling and rate capability is better than the previously reported best-performing bulk Sn-oxide or ATCO starting materials which reveals that the perovskite structure and Ca-ion play a beneficial role.     

水溶性壳聚糖制备多孔碳/氧化镍复合材料及其电化学电容行为

将水溶性壳聚糖碳化得到多孔碳材料, 然后制备了多孔碳/NiO复合材料. 透射电子显微镜(TEM), X射线衍射(XRD)和N₂吸-脱附实验等结构表征显示, 材料具有富含介孔的孔道结构. 循环伏安(CV), 恒流充放电等电化学测试表明, 复合材料具有良好的电化学电容性能. 其中Ni/C质量比为2:20时, 复合材料在0.1 A·g^-1电流密度下比容量可达355 F·g^-1, 而且经过1500次循环比容量仍保持99%左右, 表现出良好的循环稳定性.     

Hierarchical porous carbon derived from rice straw for lithium ion batteries with high-rate performance

Porous carbons with a high surface area have been prepared from rice straw. The hierarchical porous network with large macroporous channels and micropores within the channel walls enable the porous carbons to provide the pathways for easy accessibility of electrolytes and fast transportation of lithium ions. These porous carbons which show a particular large reversible capacity are proved to be promising anode materials for high-rate and high-capacity lithium ion batteries.     

Anode materials for lithium ion batteries obtained by mild and uniformly controlled oxidation of natural graphite

Modification of natural graphite for anode materials has been a recent focus of research and development. Here we report that a common natural graphite, whose electrochemical performance is very poor, can be modified by solutions of (NH₄)₂S₂O₈, concentrated nitric acid solution, or green chemical solutions such as aqueous solutions of hydrogen peroxide and ceric sulfate. All treatments result in marked improvement of the electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior. The main reason is the effective removal of active defects in natural graphite, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. As a result, these changes inhibit the decomposition of electrolytes, prevent the movement of graphene planes along the a-axis direction, and provide more passages and storage sites for lithium. They are mild and the uniformity of the product can be well controlled. Pilot experiments show economic promise for their application in industry to manufacture anode materials for lithium ion batteries.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

Tannin-based hard carbons as high-performance anode materials for sodium-ion batteries

The demand for efficient and cheap electrochemical storage devices is very high today. Na-ion batteries are emerging as a promising alternative to Li-ion batteries for large-scale applications because of the much larger abundance of sodium. Among the different negative electrode materials allowing Na insertion at low potentials, hard carbons are the materials with the best electrochemical performances reported so far. Here we investigate the synthesis of hard carbons from tannins, an abundant and cheap bio-sourced carbon precursor made of polyphenolic molecules. We show that by a well-controlled synthesis method and high-temperature pyrolysis (1600°C), a hard carbon with developed ultra-microporosity is obtained. This hard carbon delivers a reversible capacity of 306 mAh g^?1 at C/20 with a first-cycle coulombic efficiency of 87%. To our knowledge, these electrochemical performances are among the best ever reported in the literature for biomass-derived hard carbons.     

Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

聚合物热裂解碳材料结构对电化学性能的影响

近年来 ,对各种碳材料如天然石墨、焦炭、碳纤维、非石墨碳、裂解碳、掺杂型碳等用于锂离子二次电池的负极已进行了广泛的研究[17].随着碳材料来源和制备方法的不同 ,其形态和结构差异很大 ,这些宏观和微观结构的变化对锂离子电池碳负极的电化学性能有很大影响 .也就是说锂离子在碳负极材料中的嵌入与脱出能力与碳负极的种类 (石墨碳或非石墨碳 )、形态 (如结晶或非结晶碳 )及比表面积、Ｈ/Ｃ原子比率、粒径大小及其分布、聚集态以及微晶尺寸ｄ0 0 2 、Ｌａ、Ｌｃ 等物理参数均有密切关系 .由于碳材料本身结构的复杂性及其形态的多样性 ,目…     

Efficient thermal conversion of polyyne-type conjugated polymers to nano-structured porous carbon materials

Summary Some aromatic based conjugated polymers having carbon-carbon triple bonds moiety were synthesized and carbonized. The polymers were efficiently carbonized by heating up to 900°C under an argon atmosphere, affording porous carbons in high yields. The polymer characteristics were appropriate to form nano-structured carbons in the pyrolytic carbonization process. The carbon materials were consisted of 2-4 nm sized graphitic crystallites and had slit-shaped micropores with ca. 0.7 nm pore width. Structural defects in the pre-carbon materials caused generation of mesopores with ca. 4 nm pore width after carbonization.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Density of He adsorbed in micropores at 4.2K

The density of He adsorbed in the cylindrical micropores of zeolites NaY and KL has been determined by He adsorption at 4.2K. He adsorption isotherms were then compared with N₂ adsorption isotherms at 77K. Crystallographic considerations of the micropore volumes gave the density of the He adsorbed layer, which is necessary for assessment of ultramicroporosity of less-crystalline microporous solids, such as activated carbons. The determined density of He adsorbed in the cylindrical micropores of the zeolite was in the range 0.22 to 0.26 gml^–1, greater than that of He adsorbed on a flat surface (0.202 gml^–1). A value for the density of He between 0.20 to 0.22 gml^–1 is recommended for evaluation of ultramicroporosity of a slit-shaped microporous system such as activated carbon.     

纳米锡锌复合氧化物贮锂材料的合成和性质

用液相沉淀-热解法合成了一系列结构和组成不同的锂离子电池纳米锡锌复合氧化物贮锂材料, 通过XRD、TEM和电化学测试对材料进行了表征. 测试结果表明, 非晶态ZnSnO3负极材料的初始可逆贮锂容量为844 mA·h/g, ZnO·SnO2负极材料的初始可逆贮锂容量为845 mA·h/g, SnO2·Zn2SnO4复合物负极材料初始可逆贮锂容量为758 mA·h/g, 循环10周后, 三者的充电容量分别为695, 508和455 mA·h/g, 表明非晶态结构的锡锌复合氧化物具有较好的电化学性质, 随着样品中晶体的形成, 该类型负极材料的贮锂性能下降.     

Synthesis and properties of nanosized tin-zinc composite oxides as lithium storage materials

After preparing the precursor by a liquid precipitation method, a series of tin-zinc composite oxides with different components and structures were synthesized as the anode materials for lithium ion batteries when the precursor was pyrolyzed at different temperatures. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and electrochemical measurements. The reversible capacity of amorphous ZnSnO₃ is 844 mA · h/g in the first cycle and the charge capacity is 695 mA · h/g in the tenth cycle. The reversible capacity of ZnO · SnO₂ is 845 mA · h/g in the first cycle and the charge capacity is 508 mA · h/g in the tenth cycle. The reversible capacity of SnO₂ · Zn₂SnO₄ is 758 mA · h/g in the first cycle and the charge capacity is 455 mA · h/g in the tenth cycle. Results show that amorphous ZnSnO₃ exhibits the best electrochemical property among all of the tin-zinc composite oxides. With the formation of crystallites in the samples, the electrochemical property of the tin-zinc composite oxides decreases. Translated from Chem J Chin Univ, 2006, 27(12): 2252–2255 [译自: 高等学校化学学报]     

Small-angle X-ray scattering study of precipitation of carbon in active carbons

Conclusion Using the method of small-angle x-ray scattering, it was shown that precipitation of carbon in the micropores of active carbons does not take place in thermal decomposition of methane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 991–994, May, 1988.     

Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials

We report the synthesis of zeolite-like carbon materials that exhibit well-resolved powder XRD patterns and very high surface area. The zeolite-like carbons are prepared via chemical vapor deposition (CVD) at 800 or 850 degrees C using zeolite beta as solid template and acetonitrile as carbon precursor. The zeolite-like structural ordering of the carbon materials is indicated by powder XRD patterns with at least two well-resolved diffraction peaks and TEM images that reveal well-ordered micropore channels. The carbons possess surface area of up to 3200 m2/g and pore volume of up to 2.41 cm3/g. A significant proportion of the porosity in the carbons (up to 76% and 56% for surface area and pore volume, respectively) is from micropores. Both TEM and nitrogen sorption data indicate that porosity is dominated by pores of size 0.6-0.8 nm. The carbon materials exhibit enhanced (and reversible) hydrogen storage capacity, with measured uptake of up to 6.9 wt % and estimated maximum of 8.33 wt % at -196 degrees C and 20 bar. At 1 bar, hydrogen uptake capacity as high as 2.6 wt % is achieved. Isosteric heat of adsorption of 8.2 kJ/mol indicates a favorable interaction between hydrogen and the surface of the carbons. The hydrogen uptake capacity observed for the zeolite-like carbon materials is among the highest ever reported for carbon (activated carbon, mesoporous carbon, CNTs) or any other (MOFs, zeolites) porous material.     

Surface modification of activated carbon and fullerene black by Diels–Alder reaction

Activated carbon and fullerene black react with cyclopentadiene at room temperature or slightly elevated temperature. At higher temperature a retro-Diels–Alder reaction takes place. The reaction with the diene and the retro-Diels–Alder reaction could be repeated. As a consequence of the reaction with cyclopentadiene or other suitable dienes and the retro reaction, the surface structure of different carbons changed considerably. The surface area of micropores on fullerene black was much higher than for the original sample. The influence on the surface area of porosity is reported for two different types of carbon.     

含磷活性炭作为双电层电容器电极材料的电化学性能

采用磷酸活化和磷酸改性制备了不同种类的含磷活性炭,采用元素分析、X射线光电子能谱(XPS)和氮气吸附等手段分析了活性炭的元素含量、表面化学性质和孔隙结构,采用恒电流充放电、循环伏安和交流阻抗分别考察了活性炭在KOH和H₂SO₄电解质溶液中作为超级电容器电极材料的电化学性能,采用自由截距多元线性回归拟合统计分析研究了活性炭电极比电容量的影响因素,应用三电极体系分析了磷元素对活性炭电化学性能的影响机理。研究结果表明,活性炭掺杂的磷引入了赝电容,提高了活性炭电极的比电容量,磷元素含量为5.88%(w)的活性炭的比电容量在0.1 A·g^-1下达到185 F·g^-1。统计分析结果显示,活性炭的中孔有利于电解质离子向微孔内的扩散。在6 mol·L^-1 KOH电解质溶液中,孔径在1.10-1.61 nm、2.12-2.43nm及3.94-4.37 nm范围内是电解质离子在活性炭孔隙内部形成双电层的主要场所;在1 mol·L^-1 H₂SO₄电解质溶液中,孔径在0.67-0.72 nm范围内有利于双电层电容的形成。