Synthesis and electrochemical characteristics of isostructural LiMTiO4 (M = Mn,Fe, Co)

Isostructural LiMTiO₄ (M = Mn, Fe, Co) have been successfully synthesized by a facile sol-gel route and evaluated their possibility as an anode materials for lithium ion batteries (LIBs). All the samples exhibit high operating potential plateaus (>1.7 V vs. Li⁺/Li), which can prevent the formation of the solid electrolyte interphase (SEI) film on the electrode surface effectively. In addition, electrochemical investigations show that LiCoTiO₄ has a superior cycling performance, better rate capability, lower charge transfer resistance and higher lithium-ion diffusion coefficient than those of LiMnTiO₄ and LiFeTiO₄. These electrochemical results indicate that LiCoTiO₄ is the most promising lithium storage material among all the examined spinel-type LiMTiO₄ samples.     

Preparation and characterization of partially substituted LiMyMn2−yO4 (M=Ni, Co, Fe) spinel cathodes for Li-ion batteries

The electrochemical and thermal behaviors of the spinels-LiMn₂O₄, LiCo_1/6Mn_11/6O₄, LiFe_1/6Mn_11/6O₄, and LiNi_1/6Mn_11/6O₄ were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge-discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention was observed for the substituted spinels (0.11% loss per cycle for LiCo_1/6Mn_11/6O₄; 0.3% loss per cycle for LiFe_1/6Mn_11/6O₄; and 0.2% loss per cycle for LiNi_1/6Mn_11/6O₄) than for the lithium manganese dioxide spinel (1.6% loss per cycle for first ten cycles, 0.9% loss per cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels.     

Sol-gel synthesis,characterization, and supercapacitor applications of MCo2O4 (M = Ni,Mn, Cu,Zn) cobaltite spinels

High performance MCo₂O₄spinels (M = Ni, Mn, Cu, Zn) were synthesized by the sol gel method (citrate) and their capacitive behavior was investigated in alkaline electrolyte. Their structural, morphological, functional groups and textural properties were characterized by TG/DSC, XRD, SEM, FTIR, EDS and BET. The capacitive properties of spinel MCo₂O₄ samples were thoroughly investigated in 1?M KOH aqueous electrolyte using cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results revealed high stability of the samples and excellent electrochemical reversibility, and exhibited specific capacity depending on the nature of the transition metal ion M. A high specific capacitance of 285?F?g^?1 was measured for CuCo₂O₄ and a low capacitance of 158?F?g^?1 for ZnCo₂O₄.In addition, MCo₂O₄ spinels displayed good stability during long-term cycles with a cycling efficiency which exceeds75% after 1000 cycles. The obtained results classified MCo₂O₄ cobaltite spinels as most promising materials for their application in super capacitors.     

Magnetic phase transition and magneto-dielectric analysis of spinel chromites: MCr2O4 (M = Fe,Co and Ni)

In this work, we present magnetic phase transition temperatures and magneto-dielectric coupling in MCr₂O₄ (M = Fe, Co and Ni) ceramics, synthesized using sol–gel auto-combustion route. In order to develop their respective crystalline textures, all these chromites were calcined at 650?°C for 2?h. X-ray diffraction patterns confirmed that FeCr₂O₄ had a rhombohedral structure while NiCr₂O₄ and CoCr₂O₄ exhibited a spinel-type cubic structure. The presence of relevant elements in the specific stoichiometric ratios was confirmed using energy dispersive X-ray spectroscopy. The shapes and sizes of the grains for all the samples were determined using the images obtained from a field emission scanning electron microscope. Temperature dependent magnetic analysis have shown that FeCr₂O₄, CoCr₂O₄ and NiCr₂O₄ are ferromagnetic at 5?K and their magnetic phase transition temperatures were measured as 80, 83 and 90?K, respectively. Spin-orbit interference was also studied through magneto-dielectric coupling for these chromites using a modified impedance analyzer set-up.     

Effect of calcination temperature on morphology and electrochemical performance of PbLi2Ti6O14

As a promising anode material, PbLi₂Ti₆O₁₄ has attracted the attention of many researchers. In this work, a series of PbLi₂Ti₆O₁₄ are prepared by solid state method at five different calcination temperatures and used as anode materials in lithium ion batteries. Through a series of tests, the results show that the phase purity, morphology and electrochemical performance of PbLi₂Ti₆O₁₄ can be seriously influenced by calcination temperature. When the calcination temperature is 900?°C, the phase-pure PbLi₂Ti₆O₁₄ can be obtained with relatively small particle size, excellent cycle performance and outstanding lithium ion diffusion behavior. It provides an initial charge capacity of 151.3?mA?h?g^?1 at 100?mA?g^?1. After 100 cycles, it shows a reversible capacity of 142.0?mA?h?g^?1 with superior capacity retention of 93.85%. In contrast, PbLi₂Ti₆O₁₄ formed at 800?°C displays an unsatisfactory performance due to the presence of impurity, even though it has the smallest particle size and the largest lithium ion diffusion coefficient among the five samples. The reversible capacity is only 82.6?mA?h?g^?1 after 100 cycles with capacity retention of 53.9%. In order to further study the lithium ion diffusion behavior of PbLi₂Ti₆O₁₄, the in-situ X-ray diffraction technique is also implemented. It is found that during the lithiation/delithiation process, the stable framework can effectively inhibit the volume change and ensures the excellent electrochemical performance of PbLi₂Ti₆O₁₄.     

In-situ grown hierarchical ZnCo2O4 nanosheets on nickel foam as binder-free anode for lithium ion batteries

Nickle foam-supported hierarchical ZnCo₂O₄ nanosheets was prepared via a facile solution-based method. Porous ZnCo₂O₄ nanosheets were in-situ grown on current collector, forming a binder-free electrode. When evaluated as anode for Lithium ion batteries (LIB_S), the binder-free electrode showed an attractive electrochemical performance. A reversible capacity of 773?mAh?g^?1 could be stably delivered after a 500-cycle test at a current density of 0.25?A?g^?1, with a high capacity retention of 87%. The electrode could maintain a high reversible capacity of 245?mA?h?g^?1 even at an elevated current density of 8.0?A?g^?1. Integrated structure and rich porosity of the binder-free electrode were believed to contribute to the superior performance. Thus, the Nickle foam-supported ZnCo₂O₄ electrode is a promising anode for high performance LIBs in the coming future.     

Effects of Al substitution for Ni and Mn on the electrochemical properties of LiNi0.5Mn1.5O4

The effects of Al substitution for Ni or (and) Mn in LiNi_0.5Mn_1.5O₄ spinel on the structures and electrochemical properties are investigated. Powders of LiNi_0.5Mn_1.5O₄, Li_0.95Ni_0.45Mn_1.5Al_0.05O₄, LiNi_0.475Mn_1.475Al_0.05O₄ and Li_1.05Ni_0.5Mn_1.45Al_0.05O₄ are synthesized by a thermopolymerization method. Their structures and electrochemical properties are studied by X-ray powder diffraction, scanning electron microscopy, infrared spectroscopy, cyclic voltammetry and galvanostatic charge–discharge testing. The introduction of Al in these LiNi_0.5Mn_1.5O₄ samples has resulted in structure variation, and greatly improved their cyclic performance and rate capability. The effects of Al substitutions for Ni and Mn in the LiNi_0.5Mn_1.5O₄ are different. Compared with LiNi_0.5Mn_1.5O₄, Li_0.95Ni_0.45Mn_1.5Al_0.05O₄ demonstrates higher specific capacity at room temperature but faster capacity fading at elevated temperatures. Li_1.05Ni_0.5Mn_1.45Al_0.05O₄ displays a lower discharge capacity but better capacity retention at 55 °C. Moreover, the cyclic performance and rate capability of the Ni-substituted Li_0.95Ni_0.45Mn_1.5Al_0.05O₄, Ni/Mn co-substituted LiNi_0.475Mn_1.475Al_0.05O₄ and Mn-substituted Li_1.05Ni_0.5Mn_1.45Al_0.05O₄ at room temperature are similar, and have improved substantially compared with the Al-free LiNi_0.5Mn_1.5O₄ sample.     

Study of the potentiometric response of the doped spinel Li1.05Al0.02Mn1.98O4 for the optimization of a selective lithium ion sensor

In this paper, we studied the development of a selective lithium ion sensor constituted of a carbon paste electrode modified (CPEM) with an aluminum-doped spinel-type manganese oxide (Li_1.05Al_0.02Mn_1.98O₄) for investigating the influence of a doping ion in the sensor response. Experimental parameters, such as influence of the lithium concentration in the activation of the sensor by cyclic voltammetry, pH of the carrier solution and selectivity for Li⁺ against other alkali and alkaline-earth ions were investigated. The sensor response to lithium ions was linear in the concentration range 5.62 × 10⁻⁵ to 1.62 × 10⁻³ mol L⁻¹ with a slope 100.1 mV/decade over a wide pH 10 (Tris buffer) and detection limit of 2.75 × 10⁻⁵ mol L⁻¹, without interference of other alkali and alkaline-earth metals, demonstrating that the Al³⁺ doping increases the structure stability and improves the potentiometric response and sensitivity of the sensor. The super-Nernstian response of the sensor in pH 10 can be explained by mixed potential arising from two equilibria (redox and ion-exchange) in the spinel-type manganese oxide.     

Preparation and electrochemical properties of LiCoO2-LiNi0.5Mn0.5O2-Li2MnO3 solid solutions with high Mn contents

The solid solutions LiCoO₂-LiNi_1/2Mn_1/2O₂-Li₂MnO₃ with higher Mn content have been prepared by a spray drying method between 750 and 950 °C and their electrochemical performances have also been characterized. The effects of the Li content on the structure and electrochemical performance of the samples have been studied. It was found that their lattice parameters a, c and V increase with the increase in Ni content and the decrease in Co content. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18, 0.27 and y = 0.2 have the largest discharge capacity, which is more than 200 mAh/g in the voltages of 3.0-4.6 V. It is believed that the optimum Co content x in xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ is between 0.2 and 0.3 in the charge-discharge voltage range of 3.0-4.6 V. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18-0.36 and y = 0.2 have the excellent cycling performance and the capacity retention attains to almost 100% after 50 cycles. Moreover, it is found that the discharge capacity gradually increases with the increment of cycle number especially in the initial 10 cycles. XRD showed that the layered structure has been kept all the time in 20 cycles, which is perhaps the reason why the sample has the excellent cycling performance.     

锂离子二次电池新型正极材料LiMPO4(M=Fe、Co、Ni等)的研究进展

综述了锂离子二次电池新型正极材料LIMPO4(M=Fe、Co、Ni、Mn等)的研究进展。重点对该材料的结构、结构与电化学性能的关系、多种阳离子掺杂对材料性能的影响以及多种合成方法进行了较详细的评述,并对该材料的应用前景进行了展望。     

Synthesis and characterization of abundant Ni-doped LiNixMn2−xO4 (x = 0.1-0.5) powders by spray-drying method

The structure and electrochemical properties of LiNi_xMn_2−xO₄ cathode materials for lithium ion batteries were studied by the means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), cyclic voltammetry, and galvanostatic charge-discharge tests. The cathodes with different Ni contents (LiNi_xMn_2−xO₄, x = 0.1, 0.2, 0.3, 0.4, and 0.5) were synthesized by a spray-drying method and showed a single-phase spinel structure without any impurity. The amount of Ni has a large effect on the electrochemical characteristics. Capacity values of different voltage ranges (4- and 5-V ranges) change obviously with amount of Ni-doped. Also, the total discharge capacities increase with the Ni content, and all of them have good cycle stability.     

Structural,electronic, elastic,optical and vibrational properties of MAl2O4 (M = Co and Mn) aluminate spinels

First principles density functional theory calculations were performed to study structural, electronic, elastic, optical and vibrational properties of CoAl₂O₄ and MnAl₂O₄ aluminate spinels. Computed ground state properties such as unit-cell parameter and oxygen positional parameter differ by less than 1% from previously available theoretical and experimental results. However, the bulk modulus differs by less than 4% difference from available theoretical and experimental values for CoAl₂O₄ and less than 10% for MnAl₂O₄. Zone-center phonon frequencies and the phonon spectrum along high symmetry direction together with the phonon density of states were calculated using supercell method. Bandgaps of CoAl₂O₄ and MnAl₂O₄ were obtained as 1.78 and 2.21 eV respectively. CoAl₂O₄ was found to be more ionic than the MnAl₂O₄ spinel. And quasi harmonic method was used to calculate the Debye temperature for the studied compounds.     

The role of in situ generated nano-sized metal particles on the coulombic efficiency of MGeO3 (M = Cu, Fe, and Co) electrodes

To improve the coulombic efficiency of GeO₂ electrode, a Cu-containing ternary metal oxide (CuGeO₃) was prepared and the electrochemical behavior of Cu component was studied. The GeO₂ electrode shows a low coulombic efficiency in the first cycle (43%), which is mainly caused by a poor Ge oxidation kinetics (Ge + 2Li₂O → GeO₂ + 2Li⁺ + 2e⁻). The X-ray absorption spectroscopy (XAS) data illustrate that the Cu component in CuGeO₃ is converted to nano-sized metallic Cu in the earlier stage of lithiation but idles thereafter. In contrast, the Ge component in CuGeO₃ behaves like the GeO₂ electrode. It is converted to nano-sized Ge by a conversion reaction and further lithiated by alloying reaction. The de-lithiation proceeds in the reverse order. The CuGeO₃ electrode shows a much improved coulombic efficiency (74%) in the first cycle, which is indebted to a facilitated Ge oxidation with a much reduced electrode polarization. This feature has been explained by the favorable roles provided by the in situ generated nano-sized metallic Cu particles that make such an intimate contact with the nano-sized Ge and Li₂O that they can catalyze Li₂O decomposition and provide an electronic conductive network for Ge oxidation. A similar favorable effect was observed with the other ternary oxides (FeGeO₃ and CoGeO₃), wherein the formation of nano-sized metallic Fe and Co can be assumed.     

Synthesis and characterization of carbon-coated Li3V2(PO4)3 cathode materials with different carbon sources

The carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP) cathode materials were synthesized by a solid-state reaction process under the same conditions using citric acid, glucose, PVDF and starch, respectively, as both reduction agents and carbon coating sources. The carbon coating can enhance the conductivity of the composite materials and hinder the growth of Li₃V₂(PO₄)₃ particles. Their structures and physicochemical properties were investigated using X-ray diffraction (XRD), thermogravimetric (TG), scanning electron microscopy (SEM) and electrochemical methods. In the voltage region of 3.0-4.3 V, the electrochemical cycling of these LVP/C electrodes all presents good rate capability and excellent cycle stability. It is found that the citric acid-derived LVP owns the largest reversible capacity of 118 mAh g⁻¹ with no capacity fading during 100 cycles at the rate of 0.2C, and the PVDF-derived LVP possesses a capacity of 95 mAh g⁻¹ even at the rate of 5C. While in the voltage region of 3.0-4.8 V, all samples exhibit a slightly poorer cycle performance with the capacity retention of about 86% after 50 cycles at the rate of 0.2C. The reasons for electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ composites are also discussed. The solid-state reaction is feasible for the preparation of the carbon coated Li₃V₂(PO₄)₃ composites which can offer favorable properties for commercial applications.     

Effect of Sn doping on the electrochemical performance of NaTi2(PO4)3/C composite

In this paper, NaTi_2-xSn_x(PO₄)₃/C (x?=?0.0, 0.2, 0.3, and 0.4) composites were fabricated via facile sol-gel method, and employed as anodes for aqueous lithium ion batteries. Effect of Sn doping with various content on electrochemical properties of NaTi₂(PO₄)₃/C was investigated systematically. Sn doping on Ti site has no obvious effect on the lattice structure and morphology of NaTi₂(PO₄)₃/C. Among all samples, NaTi_1.7Sn_0.3(PO₄)₃/C (NC-Sn-3) demonstrates the best electrochemical properties. NC-Sn-3 exhibits the outstanding rate performance, delivering a discharge capacity of 103.3, 95.2, and 87.4?mAh?g^?1 at 0.5, 7, and 20?°C, respectively, 1.7, 30.5, and 56.2?mAh?g^?1 larger than those of pristine NaTi₂(PO₄)₃/C. In addition, NC-Sn-3 shows excellent cycling performance with the capacity retention of 80.6% after 1000 cycles at 5?°C. This work reveals that Sn doped NaTi₂(PO₄)₃/C with outstanding electrochemical properties are potential anode for aqueous lithium ion batteries.     

Facile synthesis of MTaO4 (M = Al,Cr and Fe) metal oxides and their application as anodes for lithium-ion batteries

Ternary metal oxides have attracted much attention in energy storage fields. Herein, tantalum-based oxides MTaO₄ (M = Al, Cr and Fe) are synthesized by a facile co-precipitation method, and their performance as lithium-ion battery anodes are evaluated. Among them, the FeTaO₄ electrode presents superior electrochemical performance compared to the MTaO₄ (M = Al and Cr) and a reversible capacity of more than 200?mAh?g^?1 can be maintained after 100 cycles, while a capacity of 53.6 and 128.9?mAh?g^?1 can be obtained at the same condition for AlTaO₄ and CrTaO₄, respectively. The explanation that FeTaO₄ exhibits the excellent electrochemical performance in MTaO₄ (M = Al, Cr and Fe) are further discussed.     

Electrochemical properties of carbon-coated LiFePO4 cathode using graphite, carbon black, and acetylene black

Electrochemical properties of LiFePO₄ were investigated by incorporating conductive carbon from three different carbon sources (graphite, carbon black, acetylene black). SEM observations revealed that the carbon-coated LiFePO₄ were smaller than the bare LiFePO₄ particles. The carbon-coated LiFePO₄ showed much better performance in terms of the discharge capacity and cycling stability than the bare LiFePO₄. Among carbon-coated LiFePO₄, the particles coated with graphite exhibited better electrochemical properties than others coated with carbon black or acetylene black.     

Electrochemical properties of bare and Ta-substituted Nb2O5 nanostructures

In this work, bare and Ta-substituted Nb₂O₅ nanofibers are prepared by electrospinning followed by sintering at temperatures in the 800–1100 °C range for 1 h in air. Obtained bare and Ta-substituted Nb₂O₅ polymorphs are characterized by X-ray diffraction, scanning electron microscopy, density measurement, and Brunauer, Emmett and Teller surface area. Electrochemical properties are evaluated by cyclic voltammetry and galvanostatic techniques. Cycling performance of Nb₂O₅ structures prepared at temperature 800 °C, 900 °C, and 1100 °C shows following discharge capacity at the end of 10th cycle: 123, 140, and 164 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹ (1.5 C rate). Heat treated composite electrode based on M-Nb₂O₅ (1100 °C) in argon atmosphere at 220 °C, shows an improved discharge capacity of 192 (±3) mAh g⁻¹ at the end of 10th cycle. The discharge capacity of Ta-substituted Nb₂O₅ prepared at 900 °C and 1100 °C showed a reversible capacity of 150, 202 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹. Anodic electrochemical properties of M-Nb₂O₅ deliver a reversible capacity of 382 (±5) mAh g⁻¹ at the end of 25th cycle and Ta-substituted Nb₂O₅ prepared at 900 °C, 1000 °C and 1100 °C shows a reversible capacity of 205, 130 and 200 (±3) mAh g⁻¹ (at 25th cycle) in the range, 0.005–2.6 V, at current rate of 100 mA g⁻¹.     

Behavior of the monophosphate tungsten bronzes (PO2)4(WO3)2m (m = 7 and 8) in the course of electrochemical lithium insertion

The electrochemical lithium insertion process has been studied in the family of monophosphate tungsten bronzes (PO₂)₄(WO₃)_2m, where m = 7 and 8. Structural changes in the pristine oxides were followed as lithium insertion proceeded. Through potentiostatic intermittent technique the different processes which take place in the cathode during the discharge of the cell were analyzed. The nature of the bronzes Li_x(PO₂)₄(WO₃)_2m formed was determined by in situ X-ray diffraction experiments. These results have allowed establishing a correlation with the reversible/irreversible processes detected during the electrochemical lithium insertion.     

ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu)上二氯甲烷的催化燃烧:A位阳离子的影响

采用溶胶-凝胶法制备4种不同ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu),考察A位阳离子对ACr_2O_4尖晶石氧化物的性质以及对二氯甲烷催化燃烧性能的影响,并对催化剂进行SEM、HRTEM、H_2-TPR、NH_3-TPD以及XPS等表征。结果表明,A位离子显著影响催化剂的可还原性和表面酸性,催化剂催化活性顺序为CoCr_2O_4Zn Cr_2O_4Mn Cr_2O_4CuCr_2O_4。结合表征结果,认为催化剂活性与其可还原性能和表面酸性存在密切关系。CoCr_2O_4由于具有最佳的可还原性和较高的表面酸性,具有最高的催化活性;而CuCr_2O_4由于具有最低的表面酸性导致其催化活性最低。