SiO_2/C复合负极材料的制备及其性能

采用在纳米SiO2表面包覆聚苯胺,并经过热处理后,制备了SiO2/C纳米复合材料.通过X射线衍射(XRD)、热重分析(TGA)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对材料的晶体结构和表观形貌进行了表征.同时也对材料的电化学性能进行了测试,结果表明,50 mA/g电流密度下,SiO2/C纳米复合材料首次放电比容量达到830.5 mAh/g,100次循环后,放电比容量仍然保持在510 mA/g以上.电化学交流阻抗测试表明,SiO2表面包覆的碳层能显著减小电极的界面阻抗,提高电池的电化学性能.     

高稳定性水系锌离子电池正极材料MnO2@MgO的制备与性能

采用共沉淀法和热分解法合成了具有核壳结构的MnO2@MgO微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等手段对材料进行表征,结果发现包覆MgO不改变MnO2的结构,包覆层由纳米颗粒组成,厚度约为50 nm。电化学性能结果显示,包覆后材料的放电比容量明显提高,在100 mA·g^-1电流密度下,最大放电比容量为274.3 mAh·g^-1,比未包覆材料提高了12.8%。在1000 mA·g^-1电流密度下经过500次循环后,包覆后材料的放电比容量保持率高达84.1%,表现出优异的循环稳定性。MgO包覆层的存在避免了MnO2与电解液之间直接接触,抑制了电极材料在充放电过程中锰的溶解,从而显著提高MnO2的循环性能。     

铜包覆多孔硅基材料p-Si@Cu(x)的制备与性能

在球形SiO_2颗粒表面包覆适量的CuO,经还原得到铜包覆的多孔硅复合材料[p-Si@Cu(x)].利用X射线衍射、扫描电子显微镜、透射电子显微镜和比表面积分析等手段对样品的组成、物相结构、微观形貌和孔结构进行分析,并初步研究了材料的循环性能和倍率性能.结果表明,铜包覆量x=0.05时,在100 mA/g电流密度下,样品的首次放电容量为3596.9 mA·h/g,首次充电容量为2590.7 mA·h/g,首次库仑效率为72.03%;在1C倍率下可逆容量为1004.9 mA·h/g,0.1C倍率下循环100周后的可逆容量仍为1706.5mA·h/g,容量保持率为76.1%.     

α-PbO纳米粉体的固相合成及其对MnO2电极材料的改性作用

利用Pb(Ⅱ）盐与NaOH在室温下进行固相反应制备的纳米级α－PbO粉体（桔红色）,借助X射线衍射、透射电镜测试对合成的纳米粉体试样拨乱反正了表征,初步探讨了反庆机理,将合成的试样用于改性MnO2电极,1次深度放电测试结果表明,样品的掺杂量在1.25％－5.00%之间对MnO2有良好的改性效果,中等负荷放电时,纳米PbO改性的MnO2电极的放电容量比常粒径PbO改性的MnO2电极的放电容量高出20％以上,比纯国际1^#电解锰样（γ-MnO2）的放电容量平均高出约50％,在重负荷放电时,改性MnO2电极的放电容量提高幅度更大。     

磷酸钐包覆对高电压镍锰酸锂正极材料电化学性能的影响

尖晶石型镍锰酸锂(LiNi_0.5Mn_1.5O₄)因制备成本低、 放电平台高及循环寿命长等优点, 越来越多地应用于大型储能设备、 能量转换设备、 动力汽车等领域. 然而LiNi_0.5Mn_1.5O₄在高电压(5 V)充电状态下电解液易分解, 从而导致比容量降低以及循环性能衰退. 针对以上问题, 采用水热法制备磷酸钐(SmPO₄)表面包覆改性LiNi_0.5Mn_1.5O₄正极材料, 研究了SmPO₄包覆量对LiNi_0.5Mn_1.5O₄材料电化学性能的影响. 结果表明, 当SmPO₄包覆量为0.5%(质量分数)时, 改性材料(LNMO@SP-0.5)的电化学性能最优, 在0.2C和5C倍率下的放电比容量分别为129.2和90.9 mA?h/g, 而未包覆的材料Pristine LNMO的放电比容量分别仅有114.2和77.7 mA?h/g. 在常温1C倍率下循环200次后, LNMO@SP-0.5的容量保持率为93.4%, 而Pristine LNMO的容量保持率仅为86.6%. 这归因于SmPO₄包覆能够有效缓解LiNi_0.5Mn_1.5O₄材料与电解液之间的副反应, 降低电极的极化程度和电荷转移电阻, 增加了Li⁺的扩散系数.     

聚(3-己基噻吩)包覆富锂层状正极材料Li1.18Ni0.15Co0.15Mn0.52O2的制备与电化学性能

采用溶胶-凝胶法合成了Li_1.18Ni_0.15Co_0.15Mn_0.52O₂富锂层状正极材料, 并使用聚(3-己基噻吩)对其进行了表面包覆. 采用多种光谱学和电化学手段对材料的形貌结构和电化学性能进行了分析. 结果表明, 聚(3-己基噻吩)溶液浸泡后在富锂材料表面形成厚约1.5 nm的均匀包覆层. 表面包覆后富锂层状正极材料的极化和阻抗明显减小. 在0.2C倍率下, 经过100次充放电循环后, 未包覆的富锂材料放电比容量衰减为170 mA·h/g, 而经过0.3%聚(3-己基噻吩)包覆的材料的放电比容量则保持在205 mA·h/g, 容量保持率由68%提高到82%; 10C倍率下的放电比容量由72 mA·h/g提高到116 mA·h/g.     

水系锂离子电池负极材料LiTi_2(PO_4)_3/C的合成与电化学性能

采用Pechini法合成了纳米LiTi2(PO4)3,以聚乙烯醇(PVA)为碳源,探讨了不同碳源分散方式下制备的碳包覆LiTi2(PO4)3电极电化学性能的影响因素.结果表明,纳米LiTi2(PO4)3的电化学性能主要取决于本身晶相的纯度和结晶度,其次为LiTi2(PO4)3颗粒表面碳包覆层的均匀程度.采用旋转蒸发的碳源分散方式制得的纳米LiTi2(PO4)3晶相纯度高,结晶度好,LiTi2(PO4)3颗粒表面碳包覆层均匀,电化学性能最优.4C倍率下首次放电容量达到123mA·h/g,充放电循环200次容量保持率在85%以上.     

TiO2包覆对LiCO1/3Ni1/3Mn1/3O2材料的表面改性

为了提高材料LiCo1/3Ni1/3MnO2的循环件能,采用浸渍-水解法对其进行TiO2包覆.用X射线衍射(XRD)、电化学交流阻抗谱(EIS)、电感耦合等离子体发射光谱(ICP-OES)和恒流允放电测试研究包覆材料的结构和电化学性能.TiO2仅在材料表面形成包覆层,并未改变材料的结构.TiO2包覆能提高材料LiCo1/3Ni1/3Mn1/3O2的倍率性能和循环性能,TiO2包覆后的材料在5.0C(1.0C=160 mA·g-1)下的放电容量达到0.2C下的66.0%,而包覆前的材料在5.0C下的放电容量仅为其0.2C下的31.5%.包覆后的材料在2.0C下循环12周后的容最没有衰减,而未包覆的材料容量保持率仅为94.4%.EIS测试表明包覆材料性能的提高是由于循环过程中材料的界面稳定性得到了提高.循环后材料的XRD和ICP-OES测试表明,包覆层能提高材料LiCo1/3Ni1/3Mn1/3O2的结构稳定性.     

ZnO包覆LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的表面结构和电化学性能

在LiNi1/3Co1/3Mn1/3O2正极材料表面包覆ZnO,通过X射线衍射(XRD)和光电子能谱(XPS)分析包覆层对正极材料表面状态的改变,并考察了改性后材料的放电容量、首次不可逆容量等电化学性能变化.结果表明:ZnO主要存在于材料表面并影响着材料表面组成和电化学性质,材料表面镍和锰的含量随着包覆量的增加而增大;400oC热处理可使过渡金属与锌在材料表面形成复合氧化物,过渡金属的结合能增大;包覆2%(by mass,下同)的ZnO可有效抑制55 oC下充放电时3.6 V附近的不可逆反应,提高了材料的首次库仑效率;包覆2%ZnO的电池材料在55oC/0.5C的放电比容量和循环寿命最佳.     

ZnO包覆LiNi1/3Co1/3Mn1/3O2的表面结构和电化学性能

在LiNi_1/3Co_1/3Mn_1/3O₂正极材料表面包覆ZnO,通过X射线衍射（XRD）和光电子能谱（XPS）分析包覆层对正极材料表面状态的改变,并考察了改性后材料的放电容量、首次不可逆容量等电化学性能变化. 结果表明：ZnO主要存在于材料表面并影响着材料表面组成和电化学性质,材料表面镍和锰的含量随着包覆量的增加而增大;400 ^oC热处理可使过渡金属与锌在材料表面形成复合氧化物,过渡金属的结合能增大;包覆2%（by mass,下同）的ZnO可有效抑制55 ^oC下充放电时3.6 V附近的不可逆反应,提高了材料的首次库仑效率;包覆2% ZnO的电池材料在55 ^oC/0.5C的放电比容量和循环寿命最佳.     

悬浮液中制备电解MnO2

电解MnO_2(EMD)是制造锌锰干电池的基本原料,它的放电性能比较好。在使用金属钛作电解阳极时,为获得性能良好的MnO_2和防止金属钛表面钝化,电解电流密度一般在0.6A/dm~2以下。为提高电流密度,Misawa等进行了新的溶液体系研究。本工作用化学     

Preparation and lithium storage performance of silicon and carbon microrods by chemical vapor co-deposition

Silicon/carbon microrods are co-deposited on copper substrate and graphite spheres surface using dimethyl dichlorosilance as carbon and silicon precursor. The obtained composites are characterized by X-ray diffraction and scanning electron microscopy. The experimental results show that silicon/carbon microrods deposited on the copper substrate, whose diameter is about 500 nm, are accumulated into sisallike morphology, those deposited on the graphite spheres surface form hedgehog-like feature, whose diameter is about 200 nm and whose top is like cauliflower. When current density of 50 mA/g is applied, charge capacity of silicon/carbon microrods is 1492 mA h/g (deposited on copper substrate) and 693 mA h/g (deposited on the graphite spheres surface). Moreover, silicon/carbon microrods deposited on the graphite spehres and copper substrate respectively deliver the capacity of 592, 985 mA h/g, and display no capacity decay at all after the 20 cycles, when cycled under current density of 500 mA/g.     

Surface fluorination and electrochemical behavior of petroleum cokes graphitized at medium and high temperatures for secondary lithium battery

The surface structure and electrochemical performance have been investigated of petroleum cokes heat-treated at 2100 and 2600 °C (abbreviated to PC2100 and PC2600) and those fluorinated by elemental fluorine at 200 and 300 °C. XPS study indicated that surface fluorine was covalently bonded to carbon and surface fluorine contents were in the range of 4.9-17.8 at.%. Surface oxygen was reduced by fluorination. BET surface areas were nearly the same before and after fluorination. Fluorination enhanced D-band intensity in two Raman shifts observed at 1580 cm⁻¹ (G-band) and 1360 cm⁻¹ (D-band), indicating the increase in the surface disordering. At a high current density of 150 mA/g, the capacity increase was observed for PC2100 fluorinated at 200 °C and for PC2600 fluorinated at 200 and 300 °C. The most interesting result was the increase in first coulombic efficiencies by surface fluorination. First columbic efficiencies for PC2600 fluorinated at 300 °C were increased by 12.1% at 60 mA/g and by 25.8% at 150 mA/g, respectively. The impedance measurements showed that the resistances of surface films on carbon electrodes were increased by fluorination, however, the charge transfer resistances were decreased by 12.3% for PC2100 fluorinated at 200 °C, and by 27.5 and 6.4% for PC2600 fluorinated at 200 and 300 °C, respectively. The reduction of the charge transfer resistances was consistent with increase in the charge capacities for PC2100 fluorinated at 200 °C and PC2600 fluorinated at 200 and 300 °C.     

高功率超级电容器用介孔炭电极材料

以纳米CaCO3为模板、蔗糖为前躯体制备超级电容器用介孔炭电极材料.材料的结构由氮吸附、TEM表征,借助恒流充放电、循环伏安和交流阻抗评价了其在6 mol.L-1KOH电解液中的电化学电容性能.结果表明,蔗糖基介孔炭的比表面积606 m2/g,富含10~30 nm的介孔.恒流放电法测得介孔炭在电流密度50 mA/g下的比电容为125 F/g,大电流倍率性能特别突出.电流密度增大到20 000 mA/g,比电容还保持有88F/g,远高于进口电容炭,该介孔炭是一种很有前景的高功率超级电容器炭电极材料.     

基于聚苯乙烯磺酸的锂金属负极界面保护层的设计

将聚苯乙烯磺酸(PSS)进行锂化处理后, 涂覆在锂箔表面, 在锂金属表面构筑一层均匀的聚苯乙烯磺酸锂(PSSLi)界面保护层, 形成PSSLi@Li复合电极. 通过红外光谱(FTIR)、 电化学阻抗谱(EIS)、 电池性能分析和有限元多物理场仿真模拟等方法, 对该复合电极进行了结构和性能研究. 结果表明, PSSLi界面保护层能有效地避免电解液与锂金属的直接接触, 抑制了“死锂”和锂枝晶的生成. 聚苯乙烯磺酸锂具有整齐排布的磺酸基团, 为锂离子提供了稳定的传输通道, 能够均匀化锂离子的迁移速率, 调节锂离子在电极表面的浓度分布, 并实现均匀的锂金属沉积/剥离. 电化学实验数据表明, 将该PSSLi界面层涂覆在铜箔表面进行库仑效率测试, 循环 350次实验后仍然能够保持在99.5%以上; 利用PSSLi@Li复合电极组装形成的对称电池, 在1 mA/cm²的电流密度、 1 mA·h/cm²的面积容量下, 能够稳定循环1200 h以上; PSSLi@Li与磷酸铁锂正极材料组装的全电池, 在1C倍率下循环500次后, 仍具有115 mA·h/g的容量, 容量保持率可达81%以上; 在8C的高倍率下, 该电池的容量可达到105 mA·h/g.     

Li-ion charge storage performance of wood-derived carbon fibers@MnO as a battery anode

Wood-derived carbons have been demonstrated to have large specific capacities as the anode materials of lithium-ion batteries(LIBs). However, these carbons generally show low tap density and minor volumetric capacity because of high specific surface area and pore volume. Combination with metal oxide is one of the expected methods to alleviate the obstacles of wood-derived carbons. In this work, the composites of Mn O loaded wood-derived carbon fibers(CF@Mn O) were prepared via a simple and envir...     

Improved Electrochemical Kinetic Performances of La-Mg-Ni-based Hydrogen Storage Alloy Modified by Ni-Polypyrrole Complex Surface Treatment

In order to improve the electrochemical kinetic performances of La-Mg-Ni-based alloy, complex surface modification of Ni with excellent catalytic activity and conducting polymer polypyrrole(PPy) was performed via electroless plating method. FESEM images revealed that the complex Ni-PPy treatment resulted in more micropores at the alloy surface, with Ni particles and cotton fiber-shape PPy microspheres attached. Both the larger surface area induced by the micropore and the higher catalytic activity and conductivity on account of the dispersed Ni particles/PPy microspheres promoted the electrode reaction, thereby increasing the discharge capacity of the modified alloy electrode. Electrochemical impedance spectroscopy(EIS) and linear polarization results showed that the Ni-PPy treatment decreased the charge-transfer resistance and increased the exchange current density greatly, far more than the single-component Ni or PPy treatment. Consequently, a notable improvement in high rate dischargeability(HRD) was observed, and at a high discharge current density of 1800 mA/g, the HRD of the modified electrode increased by 10.4% compared with that of the bare electrode.     

1,3-二氧戊环基LiCF3SO3电解液对锂硫电池正极材料单质硫的电化学性能影响

测试了二元和多元溶剂组分的1,3-二氧戊环基LiCF3SO3电解液的粘度、离子电导率和单质硫的溶解度. 研究结果表明, 由较强的给电子能力溶剂组成的低粘度电解液较容易提高单质硫的氧化还原反应活性和可逆性能, 有利于提高单质硫在2.10 V附近的低放电平台电位和放电比容量. DOL-DME LiCF3SO3电解液能够较好地改善单质硫电极的表面钝化层结构, 促进电活性物质离子扩散和降低界面电荷传递阻抗, 从而表现出很好的放电倍率特性. 在室温下充放电流密度分别为0.1和0.2 mA/cm2时, 单质硫的首次放电比容量为792 mA·h/g, 第29次放电比容量达到412 mA·h/g.     

Surface Modification Effect and Electrochemical Performance of LiOH-High Surface Activated Carbon as a Cathode Material in EDLC

This study aimed to improve the performance of the activated carbon-based cathode by increasing the Li content and to analyze the effect of the combination of carbon and oxidizing agent. The crystal structure and chemical structure phase of Li-high surface area activated carbon material (Li-HSAC) was analyzed by X-ray diffraction (XRD) and Raman spectroscopy, the surface state and quantitative element by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) and the surface properties with pore-size distribution by Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH) and t-plot methods. The specific surface area of the Li-YP80F is 1063.2 m²/g, micropore volume value is 0.511 cm³/g and mesopore volume is 0.143 cm³/g, and these all values are higher than other LiOH-treated carbon. The surface functional group was analyzed by a Boehm titration, and the higher number of acidic groups compared to the target facilitated the improved electrolyte permeability, reduced the interface resistance and increased the electrochemical properties of the cathode. The oxidizing agent of LiOH treated high surface area of activated carbon was used for the cathode material for EDLC (electric double layer capacitor) to determine its electrochemical properties and the as-prepared electrode retained excellent performance after 10 cycles and 100 cycles. The anodic and cathodic peak current value and peak segregation of Li-YP80F were better than those of the other two samples, due to the micropore-size and physical properties of the sample. The oxidation peak current value appeared at 0.0055 mA/cm² current density and the reduction peak value at –0.0014 mA/cm², when the Li-YP80F sample used to the Cu-foil surface. The redox peaks appeared at 0.0025 mA/cm² and –0.0009 mA/cm², in the case of using a Nickel foil, after 10 cycling test. The electrochemical stability of cathode materials was tested by 100 recycling tests. After 100 recycling tests, peak current drop decreased the peak profile became stable. The LiOH-treated high surface area of activated carbon had synergistically upgraded electrochemical activity and superior cycling stability that were demonstrated in EDLC.     

蟹壳基氮/氧共掺杂多孔炭的原位制备及其超级电容器性能

采用废弃蟹壳为碳源,KOH为活化剂原位制备了氮/氧共掺杂多孔炭,并研究其作为电极材料在超级电容器中的应用。 固定蟹壳与KOH的质量比为5:3,考察了煅烧温度对所得炭材料产率、孔结构和氮氧含量的影响。 结果表明,蟹壳基炭材料的孔结构和氮/氧含量可通过改变煅烧温度调变。 随着煅烧温度从500 ℃上升至700 ℃,多孔炭的比表面积和孔体积逐渐增大,而氮/氧含量随温度升高则降低。 采用循环伏安和恒流充放电对所得材料的电化学性能进行测试。 结果表明,所得多孔炭的电化学性能取决于其孔结构与氮/氧表面性质的协同作用,其中煅烧温度为600 ℃所得的多孔炭比表面积为612 m²/g,氮和氧含量分别为3.53%和32.8%,在50 mA/g的电流密度下比电容达到310 F/g,循环1000次比电容仍然保持95%以上,展现出良好的电化学性能。