Capacitance performance enhancement of TiO<Subscript>2</Subscript> doped with Ni and graphite

Nano-amorphous TiO₂ was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO₂-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO₂. The electrochemical properties of TiO₂-NiO-C, such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO₂-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO₂-NiO-C shows excellent capacity and cycling performance.     

Electrochemical hydrogen storage performance of AB<Subscript>5</Subscript>-CoB composites synthesized by a simple mixing method

AB₅ (MlNi_4.0Al_0.3Cu_0.5Zn_0.2) alloy and CoB alloy were prepared by arc melting. AB₅-CoB composites were synthesized by simple mixing of AB₅ alloy powders and CoB alloy powders, and their electrochemical hydrogen storage properties were studied as negative electrodes in KOH aqueous solution. The maximum discharge capacity of the AB₅-CoB(50%) composite (the content of CoB in the composite is 50 wt.%) reached 365.3 mAh·g⁻¹. After 100 charge-discharge cycles, the discharge capacity of the AB₅-CoB(50%) composite was still much higher than that of the AB₅ alloy. The high rate discharge capability (HRD) and potentiodynamic polarization were also tested.     

Electrochemical hydrogen storage of NdMg12–Ni composites modified with carbon nanotubes and BN particles

In this work, the electrochemical performance of NdMg₁₂–Ni composite electrode in alkaline solution and the effect of the surface modification with carbon nanotubes (CNTs) and boron nitride (BN) particles on the NdMg₁₂–Ni composite were investigated. The NdMg₁₂ alloy was synthesized by a salt-cover-melting and a subsequent quenching process. The NdMg₁₂–Ni–BN and NdMg₁₂–Ni–CNTs composites were prepared by ball-milling NdMg₁₂ alloy, Ni powders and CNTs or BN particles. It is found that CNTs or BN particles are mainly attached onto the surface of the NdMg₁₂–Ni composite after the ball-milling process. The electrochemical experiment results indicate that the NdMg₁₂–Ni composites modified with CNTs or BN particles have the improved electrochemical performance. In particular, the NdMg₁₂–Ni–5 wt.% CNTs and NdMg₁₂–Ni–3 wt.% BN composites have the higher initial discharge capacity of 416.6 mAh/g and 442.9 mAh/g, respectively, larger than the original NdMg₁₂–Ni composite. The large amount of grain boundaries and crystalline defects, induced during the ball-milling process, can accelerate the bulk hydrogen diffusion and provide more surface active sites for the electrochemical reaction of the composites. However, the cycle stability of the composites modified by CNTs or BN particles is still not satisfactory for the practical application.     

Morphology control and electrochemical properties of nanosize LiFePO4 cathode material synthesized by co-precipitation combined with in situ polymerization

Nanosize carbon coated LiFePO₄ cathode material was synthesized by in situ polymerization. The as-prepared LiFePO₄ cathode material was systematically characterized by X-ray diffraction, thermogravimetric-differential scanning calorimetry, X-ray photo-electron spectroscopy, field-emission scanning electron microscopy, and transmission electron microscopy techniques. Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images revealed that the morphology of the LiFePO₄ consists of primary particles (40-50 nm) and agglomerated secondary particles (100-110 nm). Each particle is evenly coated with an amorphous carbon layer, which has a thickness around 3-5 nm. The electrochemical properties were examined by cyclic voltammetry and charge-discharge testing. The as-prepared LiFePO₄ can deliver an initial discharge capacity of 145 mAh/g, 150 mAh/g, and 134 mAh/g at 0.2 C, 1 C, and 2 C rates, respectively, and exhibits excellent cycling stability. At a higher C-rate (5 C) a slight capacity loss could be found. However after being charge-discharge at lower C-rates, LiFePO₄ can be regenerated and deliver the discharge capacity of 145 mAh/g at 0.2 C.     

Effect of graphite content on electrochemical performance of Sn-SnSb/graphite composite powders

Sn-SnSb alloy was synthesized by reducing a aqueous solution containing Sn（Ⅱ） and Sb（Ⅲ） salts with NaBH4 in the presence of sodium citrate. The product was characterized by X-ray diffractometry（XRD） and scanning electron microscopy（SEM）. Sn-SnSb/graphite composite powders were prepared by mechanical milling and the mass fraction of graphite was increased from 20% to 50%. The effect of graphite content on the electrochemical performance of Sn-SnSb/graphite composite electrode was investigated. The results show the increase of graphite content is in favor of enhancing the first charge-discharge efficiency and improving the cycle performance, but the capacity of the composite electrode decreases with increasing content of graphite.     

Improving the performance of hydrogen storage electrodes based on mechanically alloyed Mg61Ni30Y9

Amorphous Mg₆₁Ni₃₀Y₉ powder was produced by mechanical alloying using a Retsch planetary ball mill under liquid nitrogen cooling. Additional gentle milling with graphite powder resulted in a thin graphite coating of powder particles. Further milling with a high energy SPEX mill transferred the alloy into a fully nanocrystalline state. The morphological and microstructural changes were followed by means of XRD, SEM, TEM and DSC. Hydrogen storage electrodes based on those alloy powders were fabricated and their cathodic and anodic polarization behaviour and their charge–discharge cycling behaviour in 6 M KOH solution were investigated. It was found that the alloy modification from a non-defective amorphous to a highly defective nanocrystalline state is more effective for improving the hydrogen sorption properties of the alloy than the graphite coating, but is detrimental for the alloy passivation. Accordingly, a SPEX-milled powder electrode exhibits with C_max = 570 mAh/g a higher maximum discharge capacity than a coated Retsch-milled powder electrode with C_max = 435 mAh/g, but degrades faster during repeated cycling. Using graphite powder supporting material for electrode preparation on a nickel foam carrier was found to be much more beneficial than nickel powder for achieving maximum discharge performance.     

Effects of B, Fe, Gd, Mg, and C on the structure, hydrogen storage, and electrochemical properties of vanadium-free AB2 metal hydride alloy

The structural, gaseous phase hydrogen storage, and electrochemical properties of a series of vanadium-free AB₂ Laves phase based metal hydride alloys with various modifiers (Ti₅Zr₃₀Cr₉Mn₁₉Co₅Ni_32−xM_x, M = B, Fe, Gd, Mg, and C) were studied. While B and Fe completely dissolve in the main AB₂ phases, Gd, Mg, and C form individual secondary phases. The solubilities of Gd, Mg, and C in the AB₂ phases are not detectable, 0.3 at.%, and very low, respectively. The C14 crystallite sizes, C15 phase abundances, and Zr₇Ni₁₀ phase abundances of modified alloys are larger than those of the base alloy. All modified alloys show decreases in plateau pressure, reversible gaseous phase storage capacity, formation activity, electrochemical capacity, and cycle life. A small amount of boron (0.2 at.%) and carbon in the alloy improve the half-cell high-rate dischargeability and bulk hydrogen diffusion. All modifiers, except for boron, reduce the surface exchange reaction current densities of the alloys. Both Mg and C show improvement in charge retention. Full-cell high-rate performance is improved by adding only a small amount of boron (0.2 at.%). Fe, Gd and 0.2 at.% of boron improve the low-temperature performance of the sealed batteries.     

Hydrogen storage characteristics of nanocrystalline and amorphous Mg2Ni-type alloys prepared by melt spinning

In order to improve the hydrogen storage characteristics of the Mg₂Ni-type alloys, Ni in the alloy is partially substituted by element Mn, and melt-spinning technology is used for the preparation of the Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The microstructures of the as-cast and spun alloys are characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys are measured by an automatically controlled Sieverts apparatus. The electrochemical performances are tested by an automatic galvanostatic system. The results show that the as-spun Mn-free alloy holds typical nanocrystalline structure, whereas the as-spun alloys containing Mn displays a nanocrystalline and amorphous structure. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with rising spinning rate. Additionally, melt spinning markedly improves the electrochemical hydrogen storage capacity and cycle stability of the alloys containing Mn. With an increase in the spinning rate from 0 (As-casts is defined as spinning rate of 0 m/s) to 30 m/s, the discharge capacity of the (x = 0.3) alloy mounts up from 92.3 to 211.1 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle grows from 36.21% to 76.02%.     

Improvement in the low-temperature performance of AB5 metal hydride alloys by Fe-addition

The structures and electrochemical properties of a series of annealed AB₅, La_10.5Ce_4.3Pr_0.5Nd_1.4Ni_64.3−xCo_5.0Mn_4.6Al_6.0Cu_3.2Zr_0.2Fe_x (x = 0.0, 0.5, 1.0, and 1.5), metal hydride alloys were studied for improvement in the low-temperature performance of nickel/metal hydride batteries. As the Fe-content in the alloy increases, the following was observed: lattice constant a first increases and then decreases; lattice constant c and c/a ratio increase; unit cell volume increases monotonically; the main AB₅ phase becomes hyper-stoichiometric containing no Zr and its Fe-content is close to the target composition; an additional AB₇ phase appears; maximum gaseous hydrogen storage, PCT plateau pressure, and hysteresis first increase and then decrease while the trend of reversible hydrogen storage is the opposite; enthalpy and entropy of hydride formation remain unchanged; electrochemical full capacity decreases while the high-rate dischargeability and surface reaction exchange current increase; and bulk hydrogen diffusion increases first and then decreases by very small amounts. The product of charge-transfer resistance and double-layer capacitance measured at −40 °C indicates an improvement in the surface catalysis with Fe-addition. In the sealed cell, the addition of Fe improves both the specific power and −10 °C low temperature performance, slightly reduces the charge retention, and first marginally improves and then deteriorates the cycle life performance.     

Characterization and electrochemical properties of carbon-coated Li4Ti5O12 prepared by a citric acid sol-gel method

Since carbon coating can effectively improve electrical wiring of Li₄Ti₅O₁₂ and thus enhance its high rate performance, a novel and simple citric acid sol-gel method for in situ carbon coating is employed in this study. The effects of the amount of the carbon source in the starting xerogel on the particle size, the resistance and the electrochemical performance of the synthesized Li₄Ti₅O₁₂ samples are systematically studied. The physical and electrochemical properties of the obtained samples have been characterized by XRD, TG-DSC, SEM, TEM, BET, A.C. impedance, galvanostatically charge-discharge and cyclic voltammetry tests. The results show that the initial amount of the carbon source in the starting xerogel is a critical factor which determines the content of the coated carbon and the pore volume, therefore governs the high rate performance of the Li₄Ti₅O₁₂/C composites. The Li₄Ti₅O₁₂/C composite with in situ carbon coating of 3.5 wt% exhibits the best electrochemical performance which delivers delithiation capacities of 143.6 and 133.5 mAh g⁻¹ with fairly stable cycling performance even after 50 cycles at 0.5C and 1C rate, respectively.     

Nanostructured MgFe2O4 as anode materials for lithium-ion batteries

Transition metal oxides in the nano size region are enormous attention as a new generation of anode materials for high energy density Li-ion batteries. MgFe₂O₄ is used for the first time as active electrode vs. lithium metal in test cells. The research has been focused on the effect of grain size of MgFe₂O₄ and their electrochemical performance studied. In this studies, nanostructured milled MgFe₂O₄ (grain size 19 nm) sample have been compared with relatively large-sized as-prepared sample (grain size 72 nm). From the result, the 19 nm grain size sample delivered an improved discharge capacity of around 850 mAh/g, whereas it is only 630 mAh/g for as-prepared sample (72 nm). These values are two times higher than that of a carbon anode (372 mAh/g). The anomalous capacity may be associated with the formation of oxygen rich MgFe₂O₄ samples.     

Capacitance performance enhancement of TiO2 doped with Ni and graphite

Nano-amorphous TiO2 was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO2-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO2. The electrochemical properties of TiO2-NiO-C,such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO2-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO2-NiO-C shows excellent capacity and cycling performance.     

Sol-gel synthesis and electrochemical performance of Li4Ti5O12/graphene composite anode for lithium-ion batteries

Li₄Ti₅O₁₂/graphene composite was prepared by a facile sol-gel method. The lattice structure and morphology of the composite were investigated by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The electrochemical performances of the electrodes have been investigated compared with the pristine Li₄Ti₅O₁₂ synthesized by a similar route. The Li₄Ti₅O₁₂/graphene composite presents a higher capacity and better cycling performance than Li₄Ti₅O₁₂ at the cutoff of 2.5-1.0 V, especially at high current rate. The excellent electrochemical performance of Li₄Ti₅O₁₂/graphene electrode could be attributed to the improvement of electronic conductivity from the graphene sheets. When discharged to 0 V, the Li₄Ti₅O₁₂/graphene composite exhibited a quite high capacity over 274 mAh g⁻¹ below 1.0 V, which was quite beneficial for not only the high energy density but also the safety characteristic of lithium-ion batteries.     

Ni-B-C对La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20储氢合金电化学性能的影响研究

为提高新型AB₃型储氢合金La_0.94Mg_0.06Ni_3.49Co_0.73Mn_0.12Al_0.20的电化学性能,将球磨法制备的Ni-B-C粉末按不同重量比添加到合金中。采用X-射线粉末衍射仪(XRD)和扫描电子显微镜(SEM)分析合金的相结构和表面形貌,添加Ni-B-C粉末后,合金相结构没有变化,仍由LaNi₅相和La₂Ni₇相两个相组成,但合金表面出现了细小颗粒。添加Ni-B-C粉末后,合金电极的最大放电容量和放电容量保持率均提高。当添加重量百分比为10%的Ni-B-C粉末后,电极的最大放电容量从346 mAh/g增加到363 mAh/g,50个循环后的放电容量保持率从70%提高到77%,交换电流密度I₀与极限电流密度I_L分别为106 mA/g和987 mA/g。动电位极化测试表明,电极的抗腐蚀能力也有所增强。研究结果表明,Ni-B-C可以提高AB₃型储氢合金的综合电化学性能。     

复合储氢合金Mg1.8Zr0.2Ni- (1.2-x)Ni -xMgTi3结构和电化学性能研究

为改善Mg₂Ni储氢合金电化学性能,采用机械合金化法(Mechanical Alloying,MA),分别制备出改性合金Mg_1.8 Zr Ni以及MgTi₃,按一定比例和Ni混合球磨,制备出纳米晶或非晶化的Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金。研究结果表明,经部分取代改性和包覆修饰后的复合储氢合金,其表面和内部形成较多的纳米级褶皱、空隙层状和多相结构缺陷。随着MgTi₃含量增加,Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金初始放电比容量也逐渐增加,当MgTi₃含量为x=0.5时,合金初始放电比容量为973.3 mAh.g_-1。但MgTi3含量超过x=0.5时,其初始放电比容量又有所下降,研究表明添加MgTi₃却不利于复合储氢合金的循环稳定性和高倍率放电性能。通过对Mg_1.8Zr_0.2Ni- (1.0-x)Ni -xMgTi₃复合储氢合金进行线性极化、阳极极化和交流阻抗测试,进一步研究了系列合金电极的表面电化学反应、电荷转移过程、氢在合金中的扩散情况以及它们的电化学性能。     

Electrochemical fabrication of a porous nanostructured nickel hydroxide film electrode with superior pseudocapacitive performance

A porous nickel film is prepared by selectively anodic dissolution of copper from an electrodeposited Ni-Cu alloy film. A porous nanostructured nickel hydroxide film electrode is further fabricated by the cathodic electrodeposition of Ni(OH)₂ film on the obtained porous nickel film. The specific capacitances of the as-prepared porous nanostructured Ni(OH)₂ film electrode at current densities of 2, 5 and 10 A/g are 1634, 1563 and 1512 F/g, respectively. The nanoporous Ni substrate significantly improves the electrochemically cyclic stability of the electrodeposited nickel hydroxide film in 1.0 M KOH solution. The superior pseudocapacitive properties such as large specific capacitance, excellent rate capability and improved electrochemically cyclic stability of the as-prepared nickel hydroxide electrode suggest its potential application in electrochemical capacitors.     

Structural and electrochemical hydrogen storage properties of Mg2Ni-based alloys

Four different methods, i.e. hydriding combustion synthesis + mechanical milling (HCS + MM), induction melting (followed by hydriding) + mechanical milling (IM(Hyd) + MM), combustion synthesis + mechanical milling (CS + MM) and induction melting + mechanical milling (IM + MM), were used to prepare Mg₂Ni-based hydrogen storage alloys used as the negative electrode material in a nickel-metal hydride (Ni/MH) battery. The structural and electrochemical hydrogen storage properties of the Mg₂Ni-based alloys have been investigated systematically. The XRD results indicate that the as-milled products show nanocrystalline or amorphous-like structures. Electrochemical measurements show that the as-milled hydrides exhibit higher discharge capacity and better electrochemical kinetic property than the as-milled alloys. Among the four different methods, the HCS + MM product possesses the highest discharge capacity (578 mAh g⁻¹), the best high rate dischargeability (HRD) and the highest exchange current density (58.8 mA g⁻¹). It is suggested that the novel method of HCS + MM is promising to prepare Mg-based hydrogen storage electrode alloy with high discharge capacity and activity.     

Effects of Mo additive on the structure and electrochemical properties of low-temperature AB5 metal hydride alloys

After an annealing treatment at 960 °C for 8 h, the molybdenum added into previously designed AB₅ alloys for −30 °C applications segregates into spheres with diameters between 1 and 10 μm. A secondary phase with Zr-to-other elements ratio of about 1-to-5, over- (AB₇), and under-stoichiometric (AB₄) phases were observed in most of the alloys regardless of Mo-content. As the Mo-content increases, the AB₇ phase disappears while the AB₄ phase grows in size and abundance. Regarding the gaseous absorption properties, a small amount of Mo (0.2 at.%) in the main phase reduces the plateau pressure and hydride heat of formation uniformly for all Mo-containing alloys. The reduction in main phase abundance causes a decrease in both the total and the reversible hydrogen storage capacities. In electrochemical testing, the addition of Mo decreases the discharge capacity, high-rate dischargeability, and hydrogen diffusion in the bulk. The influence of Mo-addition to general battery performance is very minor. However, the low-temperature AC impedance measured at −40 °C shows reduced charge transfer resistance and increased double layer capacitance in the Mo-containing alloys. Mo was found to assist the surface reaction at very low temperatures, and the effect is proportional to the amount of addition as noted by the increasing surface area and catalytic ability, which is similar to the case of AB₂ alloys.     

An investigation on hydrogen storage kinetics of nanocrystalline and amorphous Mg2Ni1−xCox (x = 0-0.4) alloy prepared by melt spinning

In order to improve the hydrogen storage kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Co, and melt-spinning technology was used for the preparation of the Mg₂Ni_1−xCo_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The structures of the as-cast and spun alloys are characterized by XRD, SEM and TEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys is tested by an automatic galvanostatic system. The hydrogen diffusion coefficients in the alloys are calculated by virtue of potential-step method. The electrochemical impedance spectrums (EIS) and the Tafel polarization curves are plotted by an electrochemical workstation. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg₂Ni-type alloy. Furthermore, the substitution of Co for Ni, instead of changing major phase Mg₂Ni, leads to forming secondary phases MgCo₂ and Mg. Both the melt spinning treatment and Co substitution significantly improve the hydrogen absorption and desorption kinetics. The high rate discharge ability, the hydrogen diffusion coefficient and the limiting current density of the alloys significantly increase with raising both the spinning rate and the amount of Co substitution.     

An electrochemical study of the effect of Li on the corrosion behavior of Ni3Al intermetallic alloy in molten (Li + K) carbonate

A study of the effect of lithium content (1, 3 and 5 wt.%) and heat treatment (400 °C during 144 h) on the corrosion behavior of Ni₃Al alloy has been carried out in a 62 mol.%Li₂CO₃-38 mol.%K₂CO₃ mixture at 650 °C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active-passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni₃Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.