Modeling of the impedance response of porous metal hydride electrodes

Porous metal hydride electrodes of the alloy MmNi_3.5-3.7Co_0.7-0.8 Mn_0.3-0.4Al_0.3-0.4 have been characterized by means of impedance spectroscopy. A mathematical model for the impedance response, including effects of diffusion of hydrogen, surface kinetics, conductivity in the metal phase and the solution phase, as well as a continuous, lognormal, particle size distribution, was implemented and fitted to the experimental results by application of a least square fitting routine. The model is based on physical parameters, thus avoiding problems related to the conventional interpretation of impedance spectra in terms of equivalent circuits. Very good agreement between experimental results and model results was obtained for a wide range of frequencies, indicating that physical parameters to a great extent can be determined under realistic operating conditions. The latter was confirmed by independent measurements of the variation in open circuit voltage with respect to the state of charge of the electrode. The model provides an improved methodology for the determination of diffusion coefficients based on electrochemical impedance data. Furthermore, the model can be applied for parametric studies of metal hydride electrodes.     

Nickel dioxide polymorphs as lithium insertion electrodes

Five kinds of nickel dioxide polymorphs, Li_xNiO₂ with x≈0, were prepared by treating LiNiO₂ with sulfuric acid solutions, occasionally followed by low-temperature heating. Here we report their structure and properties as lithium insertion electrodes. Acid-treated Li_0.10NiO₂ with two layered phases turned into a single-layered compound at 160 °C and then to a spinel-related compound at 170 °C. Acid-treated Li_0.04NiO₂ contained a phase with a cadmium iodide structure, which was not observed with Li_0.10NiO₂. Heating this Li_0.04NiO₂ yielded a spinel-related compound on heating. The NiO distances in these compounds suggested that the nickel oxidation state was kept approximately +4. These ‘nickel dioxide’ polymorphs exhibited varied characteristics as lithium insertion electrodes. We discuss the electrode behavior together with the structural changes that occur during lithium insertion. We also examined the effect of the electrode drying condition on the cycling performance.     

Kinetics of carbon dioxide sorption on potassium-doped lithium zirconate

Potassium-doped lithium zirconate (Li₂ZrO₃) sorbents with similar crystallite but different aggregate sizes were prepared by a solid-state reaction method from mixtures of Li₂CO₃, K₂CO₃, and ZrO₂ of different particle sizes. Carbon dioxide sorption rate on the prepared Li₂ZrO₃ sorbents increases with decreasing sorbent aggregate size. It is the size of the aggregate, not the crystallite, of Li₂ZrO₃ that controls the sorption rate. Temperature effect on CO₂ sorption is complex, depending on both kinetic and thermodynamic factors. A mathematical model based on the double-shell sorption mechanism was established for CO₂ sorption kinetics and it can fit experimental data quite well. Above 500°C, the rate-limiting step of CO₂ sorption is the diffusion of oxygen ions through the ZrO₂ shell formed during the carbonation reaction. Oxygen ion conductivities in the ZrO₂ shell were obtained by regression of the experimental CO₂ uptake curves with the model and are consistent with the literature data.     

Electrochemical characterization of the LiCoO2/acetylene carbon ratios for porous electrodes in alkaline lithium aqueous solutions by electrochemical impedance spectroscopy

LiCoO₂ electrodes were fabricated with different acetylene carbon (AC) additions and fixed binder content. Subsequent electrochemical testing showed different processes at the interface that are related to pore distribution and electrode composition. Electrochemical impedance spectroscopy characterized the mechanisms close to open circuit conditions. The active state, combined with diffusion mechanisms within the cylindrical pores, contributed to the functionality of the particles according to the LiCoO₂/AC content, and surface characteristics of the electrode influenced the impedance distribution. The de Levie theory for porous electrode was used to describe the influence of the LiCoO₂/AC ratios in the impedance distribution when exposed to alkaline aqueous electrolytes (LiOH + Li₂SO₄). The pore model helped relate physical properties of the composite material, such as pore count, pore length, and double layer capacitance, with the mechanisms present at the interface. The theoretical model was validated with experimental data and the fitting process resulted in good agreement.     

Enhanced high rate properties of ordered porous Cu2O film as anode for lithium ion batteries

Highly ordered porous Cu₂O film is electrodeposited on copper foil through a self-assembled polystyrene sphere template. Compared with the dense Cu₂O film and the octahedral Cu₂O powder, the ordered porous Cu₂O film exhibits an improved electrochemical cycling stability. The capacity of the porous Cu₂O film can maintain 336 mAh g⁻¹ and 213 mAh g⁻¹ after 50 cycles at the rate of 0.1 C and 5 C, respectively. The reversible capacity holds 63.4% as the discharge-charge rate even increases by 50 times. The enhanced high rate properties of the ordered porous film should be attributed to the sufficient contact surface of Cu₂O/electrolyte and the short diffusion length of Li⁺. Moreover, the direct contact between Cu₂O and current collector and the decreasing inactive interfaces of Cu₂O/polymer binder are also suggested as being responsible for the enhanced high rate property.     

A hierarchical porous carbon material for high power, lithium ion batteries

We synthesize a carbon anode material with unique nanostructure for high power lithium ion batteries. The carbon material is composed of numerous clusters of carbon nanobeads, and shows a macro-meso-micro hierarchical porous structure. This unique nanostructure appears to facilitate the rapid transfer of lithium ions and a very large ion adsorption. It exhibits a reversible capacity of 407.4 mAh g⁻¹ and its rate performance is drastically improved in comparison with that of the commercial graphite. The unique structure enables the anode to combine the advantages of both lithium ion batteries and electrochemical double layer capacitors, resulting in the good electrochemical performance.     

关于多孔电极理论数模及非线性分析

从一般工程理论的基本衡算概念出发,用累积项、散度和化学源（反应项）的概念解释了反应工程理论数模的普遍微分形式,并指出,反应系统中与化学动力学相关的物理量分布,即质量场和能量场,决定了表观的反应结果。作者认为,具有电化学源及传荷过程是电化学反应系统的特点,据此,经合理简化可导出多孔电极稳态操作的普遍化理论数模,其形式为量纲1的非线性二阶微分方程组的边值问题,以描述多孔电极内浓差极化、欧姆极化和活化极化耦联的非线性理论关系;所归纳出的4个量纲1参数s、μ、α和γ,可给出系统动力学和传递过程相似的依据。扼要介绍了非线性数模逼近解析的Adomian分解法,以及自编的符号运算自动执行程序PAMC（parameterized ADM mathematica code）,并例举了柱状和环状多孔电极理论极化曲线的计算结果。总之,非线性和复杂性研究将成为反应工程理论深入探索的方向之一。     

Porous ZnO nanosheets grown on copper substrates as anodes for lithium ion batteries

Porous ZnO nanosheets are grown directly on copper substrates by a chemical bath deposition technique followed by a heat treatment. The materials are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Their electrochemical properties as anodes of lithium ion batteries are examined by cyclic voltammetry (CV) and galvanostatic discharge–charge tests. The results show that porous ZnO nanosheets exhibit higher reversible capacities and better cyclabilities than those of commercial ZnO powders. When cycled at 0.05 A g⁻¹, these nanosheets deliver initial discharge and charge capacities of 1120 and 750 mAh g⁻¹, and at 0.5 A g⁻¹, they keeps stable capacities of 400 mAh g⁻¹ up to 100 cycles, in addition, they also exhibit good rate capabilities. It is believed that the porous sheet nanostructure plays an important role in the electrochemical performance.     

Study on capacity fade factors of lithium secondary batteries using LiNi0.7Co0.3O2 and graphite-coke hybrid carbon

In our previous work, 10 Wh-class (30650 type) lithium secondary batteries, which were fabricated with LiNi_0.7Co_0.3O₂ positive electrodes and graphite-coke hybrid carbon negative electrodes, showed an excellent cycle performance of 2350 cycles at a 70% state of charge charge-discharge cycle test. However, this cycle performance is insufficient for dispersed energy storage systems, such as home use load leveling systems. In order to clarify the capacity fade factors of the cell, we focused our investigation on the ability discharge capacity of the positive and negative electrodes after 2350 cycles. Although the cell capacity deteriorated to 70% of its initial capacity after 2350 cycles, it was confirmed that the LiNi_0.7Co_0.3O₂ positive electrode and graphite-coke hybrid negative electrode after 2350 cycles still have sufficient ability discharge capacity of 86 and 92% of their initial capacity, respectively. Accompanied by the result for a composition analysis of the positive electrode material by inductively coupled plasma (ICP) spectroscopy and atomic absorption spectrometry (AAS), electrochemical active lithium decreased and the Li_xNi_0.7Co_0.3O₂ positive electrode could be charged-discharged in a narrow range of between x=0.41 and 0.66 in the battery, although it had enough ability discharge capacity that can use between x=0.36 and 0.87. It is predicted that solid electrolyte interface formation by electrolyte decomposition on the carbon negative electrode during the charge-discharge cycle test is a main factor of the decrease of electrochemical active lithium.     

Preparation and performance of a core-shell carbon/sulfur material for lithium/sulfur battery

The core-shell carbon/sulfur material with high performance is prepared by a facile and fast deposit method in an aqueous solution. As sulfur ratio is 85% (w/w) in the composite, scanning electron microscope (SEM) and transmission electron microscope (TEM) observation show that the moniliform particles with 10 nm sulfur shells preserve the morphology of carbon cores. Tested as the cathode material in a lithium cell with binary organic electrolyte at room temperature, the composite shows excellent electrochemical performance. It exhibits a specific capacity up to 1232.5 mAh g⁻¹ at the initial discharge and its specific capacity remained above 800 mAh g⁻¹ after 50 cycles. Meanwhile, the composite also exhibits the high-rate behavior at 800 mA g⁻¹ of current density. Assuming a complete reaction to the final product, Li₂S, the utilization of the electrochemically active sulfur is about 85% at the initial cycle. Electrochemical impedance spectroscopy (EIS) is introduced to understand the impact of the microstructure of composite on electrochemistry. According to our study, a novel core-shell structural carbon/sulfur material is proposed and the key factors of the preparation are discussed.     

Morphological and crystallite size impact on electrochemical performance of electrospun rutile and rutile/multiwall carbon nanotube nanofibers for lithium ion batteries

A sol–gel based route was used to produce TiO₂ based nanocomposites. Sols were electrospun into continuous nanofibers and calcined to get rutile phase. Fibers with diameter around 100 nm and crystallites size between 10 and 50 nm were obtained. The morphological impact and crystallites size dependence of the electrochemical performance for as-synthesized materials are reported. Enhancements using inert calcination atmosphere and incorporation of multi-wall carbon nanotubes (MWCNT) into the system are also presented.     

Doping effects on structure and electrode performance of K-birnessite-type manganese dioxides for rechargeable lithium battery

The potassium birnessites doped with Al, Ni, and Co were prepared by calcination and aqueous treatment, which showed that single phase products were obtained with Ni and Al up to 5 at.% and Co up to 25 at.% addition to strating KMnO₄. The discharge-recharge capacities and capacity retentions in an aprotic Li cell were not improved by the Ni and Al dopings, but those of the cobalt doped birnessite were improved. The initial discharge capacities of the undoped and cobalt doped birnessites were 170 and 200 mAh g⁻¹ with capacity retentions of 56 and 80% during the initial 20 cycles, respectively. The reasons for the improvement of the battery performance by Co doping were considered as follows: (i) a change in the stacking structure, (ii) a decrease in the charge transfer resistance, and (iii) improved structural stability of the oxide. Their micro structures were evaluated by X-ray diffraction, photoelectron and Raman spectroscopies, and electron microscopy. Also, potassium birnessite synthesized by adding about 3 times excess potassium indicated that the stacking structure was similar to the 30 at.% cobalt doping sample, furthermore, the better capacity retention was achieved as cathode in a Li cell.     

Electrochemical properties of porous bismuth electrodes

The properties of Bi surfaces with different roughnesses were characterized by electron microscopy, cyclic voltammetry, and impedance spectroscopy. Two different strategies were used for preparation of porous bismuth layers onto Bi microelectrode surface in aqueous 0.1 M LiClO₄ solution. Firstly, treatment at potential E < −2 V (vs. Ag|AgCl in sat. KCl) has been applied, resulting in bismuth hydride formation and decomposition into Bi nanoparticles which deposit at the electrode surface. Secondly, porous Bi layer was prepared by anodic dissolution (E = 1 V) of bismuth electrode followed by fast electroreduction of formed Bi³⁺ ions at cathodic potentials E = −2 V. The nanostructured porous bismuth electrode, with surface roughness factor up to 220, has negligible frequency dispersion of capacitance and higher hydrogen evolution overvoltage than observed for smooth Bi electrodes.     

Preparation of controlled porosity carbon aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO₂ atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O₂ cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O₂ cell using the carbon with the largest pore volume (2.195 cm³/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290 mA h g⁻¹.     

Permeable porous 1–3 nm thick overoxidized polypyrrole films on nanostructured carbon fiber microdisk electrodes

Ionically conducting 1–3 nm thick porous films of overoxidized polypyrrole (OPPY) were electrodeposited on nanostructured 7 μm diameter carbon fiber microdisk electrodes. The microdisk electrodes were fabricated from two types of polyacrylonitrile (PAN) carbon fibers, PAN T650 and PAN HCB. The electrodes were nanostructured by electrochemical etching of the microdisk electrode surface. Ultrathin porous polypyrrole (PPY) films were electrodeposited by the electropolymerization of pyrrole (PY) to PPY by a short (10 ms) single potential pulse. During the electropolymerization, the polymer “precipitated” on the nanostructured surface producing ultrathin porous film. OPPY films were fabricated by constant potential overoxidation of PPY.In steady-state voltammetry of ferricyanide, the nanostructured electrodes behave as a random array of microscopic nodules and pores. At potential scan rates of 0.050 V s⁻¹ diffusion fields at the 300–600 nm nodules on the 7 μm diameter microdisk electrode overlap. The surface area of the electroactive nanofeatures decreases after deposition of insulating OPPY. Kinetics of ferricyanide at bare and OPPY-coated nanostructured electrodes reflect the electrode surface area, as predicted by the model for charge transfer at a partially blocked surface. A model reflecting the 58–94% coverage of the nanostructured electrodes by OPPY was developed to address the high permeability of the porous OPPY-coated microdisk electrodes.     

Electrochemical characterization of screen-printed and conventional carbon paste electrodes

This work compares the electroactivity of a conventional carbon paste electrode and non-pretreated commercially available screen-printed carbon electrodes (from Alderon Biosciences, University of Florence and DropSens) towards some benchmark redox couples like hexaammineruthenium (III), ferricyanide, p-aminophenol and hydroquinone. While cyclic voltammograms of Ru³⁺ did not show significative electron transfer reactivity differences between the electrodes tested, the other redox systems exhibited higher reversible behaviours on DropSens electrodes. Scanning electron microscopy and roughness analysis with a profilometer were applied to detect the surface morphology of the working electrodes. The roughness evaluated of the screen-printed carbon working electrodes increased in this order Alderon < University of Florence < DropSens. Finally, the most electrochemically active and rough unpretreated electrode (DropSens commercial screen-printed electrode) was used to study the electrochemical-chemical reaction mechanism of indigo carmine oxidation in 0.1 M sulphuric acid. This study showed that the adsorption of the oxidation product of indigo carmine is stabilized when it is adsorbed on the surface of the electrode.     

锂在负极材料中的扩散行为对其大倍率充放电性能的影响

采用恒电位阶跃的方法,对锂在锂离子电池负极材料中的扩散系数进行测量,对天然石墨和中间相炭微球两种负极材料进行了大倍率充放电性能测试。结果表明,锂在两种负极材料中的扩散系数是不同的,锂在天然石墨中的扩散系数较小,只有1.90×10-11cm2/s,而锂中间相炭微球中的扩散系数较大,达4.25×10-9cm2/s,扩散系数大,电极的大电流充放电性能好,天然石墨在5 C放电下放电平台升高到0.3 V,放电容量急剧减小,而中间相炭微球在5 C放电下仍能保持0.2 V左右的放电平台,放电容量保持在234 mA.h/g。     

水性胶粘剂在锂离子电池电极中的应用

胶粘剂是锂离子电池中的重要辅助材料之一,它的合理选择和应用,直接影响着电池的电化学综合性能。由于良好的环保效应及性质,水性胶粘剂在电池中的应用及发展,已成为人们当前关注的一个技术热点。本文对不同类型水性胶粘剂,如水性天然高分子、水性半合成天然高分子及水性合成高分子等的应用及研究进展进行了简要综述。     

Rational design of electrochemically active polymorphic MnOx/rGO composites for Li+-rechargeable battery electrodes

Electrochemical behavior of different MnO_x @reduced graphene oxide (rGO) composites derived from a MnO₂/GO template are thoroughly investigated. As-prepared MnO₂/GO mixture is gradually converted to MnO₂/rGO and finally to Mn₃O₄/rGO composites under controlled post annealing conditions. The semispherical Mn₃O₄ crystalline compound anchored composite exhibits stable electrode performances, including both the Li⁺ anode and the Li⁺-air cathode catalyst, induced by the electrochemically favorable composite with an effective large contact area between the active materials and the electronic conductive rGO. It is such a meaningful to suggest the facile and controllable synthetic procedures for obtaining Li-rechargeable electrodes with a MnO_x nanoparticle-incorporated composites for the highly reactive lithiation/delithiation electrochemical reactions.     

Sc3+-doping effects on porous Li3V2(PO4)3/C cathode with superior rate performance and cyclic stability

An enhanced sol-gel combustion method was used to synthesize different porous Sc³⁺-doped Li₃V_2-xSc_x(PO₄)₃/C (x = 0.00, 0.05, 0.10 and 0.15) compounds. The substitution of Sc³⁺ into the V³⁺ sites of Li₃V_2-xSc_x(PO₄)₃/C expands the lattice volume along with the enlargement of Li⁺ diffusion channel, which is beneficial for Li⁺ transportation and ionic conductivity improvement. Besides, the Sc³⁺ doping content exhibits a great impact on the morphology of Li₃V_2-xSc_x(PO₄)₃/C composite. The pristine Li₃V₂(PO₄)₃/C are constituted of porous particles and nanorods, and the ratio of nanorods to particles can be controlled by adjusting the amount of Sc³⁺ doping since the ratio of nanorods to particles decreases with increasing Sc³⁺ doping content. When Sc³⁺ doping content increases to a certain level (x = 0.15, Li₃V_1.85Sc_0.15(PO₄)₃/C), the nanorods are hardly seen. Li₃V_1.90Sc_0.10(PO₄)₃/C with higher tapped density, better reversibility, smaller resistance and larger Li⁺ diffusion coefficient demonstrates outstanding rate performance and cyclic stability, together with high specific discharge capacities of 130.2 and 92.9 mAh g⁻¹ at 0.5 and 20 C, respectively. Furthermore, a superior specific discharge capacity of 85.8 mAh g⁻¹ was retained at 20 C following 1000 cycles. Overall, a novel approach for the preparation of high-performance Li₃V_2-xSc_x(PO₄)₃/C cathodes with different morphologies for lithium-ion batteries is provided.