Preparation and electrochemical performances of submicro-TiP2O7 cathode for lithium ion batteries

The TiP₂O₇ with a cubic 3?×?3?×?3 superstructure was synthesized by a liquid-assisted solid-state reaction, and characterized by x-ray diffraction, scanning electron microscopy, cyclic voltammogram, galvanostatic charge/discharge testing, and electrochemical impedance spectroscopy (EIS) technique. The results showed that there was only one step of intercalation into TiP₂O₇, corresponding to a pair redox (E _Li/Li ⁺?=?2.74/2.48 V). The initial discharge capacity of TiP₂O₇ was 110 mAh/g at a current density of 15 mA/g, and the capacity retention was 76.12 % of the initial discharge capacity after 100 cycles. The EIS of TiP₂O₇ electrode consisted of two semicircles in organic electrolyte, which was attributed to SEI resistance as well as the contact resistance, and charge transfer process, respectively. A suitable model was proposed to explain the impedance response of the insertion TiP₂O₇ material of lithium ion batteries.     

Synthesis and characterization of LiMnBO3 cathode material for lithium ion batteries

LiMnBO₃ with enhanced powder density was successfully synthesized by a commercially available spray-drying process. A monoclinic-LiMnBO₃ single phase was experimentally substantiated by an X-ray diffractometer with crystallinity investigated by Rietveld refinement method (Bragg R-factor and RF-factor <10). The dense LiMnBO₃ powder prepared by the spray drying process showed spherical morphology. The electrochemical property of LiMnBO₃ was extensively investigated, positively revealing that 0.27 Li⁺ (Li_0.27MnBO₃) was stoichiometrically extracted from the host LiMnBO₃ material at first cycle.     

Preparation of Li3V2 (PO4)3/LiFePO4 composite cathode material for lithium ion batteries

A novel process was attempted for synthesis of Li₃V₂ (PO₄)₃/LiFePO₄ composite cathode material via loading nano-LiFePO₄ (LFP) powders onto the outside of micrometer-size spherical Li₃V₂ (PO₄)₃ (LVP). The precursor of nano-LFP and LVP were synthesized via “controlled crystallization” and “spray drying” techniques, respectively. The X-ray diffraction characterization, scanning electron microscopy, and electrochemical performance measurements were studied. The results indicated that the prepared Li₃V₂(PO₄)₃/LiFePO₄ (LVP/LFP) composite material exhibited better discharging capacity at high C rate and at low temperature than that of LFP and bulk LVP/LFP. This can pave an effective way to improve the performance of LFP at high C rate and at low temperature.     

Synthesis of optimized LiNiO2 for lithium ion batteries

The synthesis of LiNiO₂, an attractive 4 V lithium ion battery cathode material, was investigated in view of identifying optimum preparation conditions by adopting various methods and comparing the structural, physical and electrochemical properties of the products. The conventional high temperature method (solid state annealing at 800 °C) and a novel low temperature method (self propagating high temperature method at 300 °C) allowed to synthesise crystalline LiNiO₂ with a composition close to the ideal stoichiometry. Optimisation of the preparation conditions which are responsible for forming high performance LiNiO₂ favoured LiNO₃ and Ni(NO₃)₂ as starting material along with an internal fuel (glycine) and a temperature of 300 °C for about three hours as most suitable heat treating condition. The electrochemical performance of LiNiO₂ synthesized via the various methods is reported.     

Improving electrochemical performance of spherical LiMn2O4 cathode materials for lithium ion batteries by Al-F codoping and AlF3 surface coating

Ionics - In this paper, combination of both codoping and coating with Al, F compounds on spherical LiMn2O4 is studied to obtain an improved charge/discharge cycling performance. Firstly, Al,...     

Mössbauer study on LiFePO4 cathode material for lithium ion batteries

Crystalline LiFePO₄ has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld’s refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.     

Influence of NiCl2 modification on the electrochemical performance of LiV3O8 cathode for lithium ion batteries

The 5.0, 8.0, and 10.0 wt% NiCl₂-modified LiV₃O₈ materials are successfully prepared and the effects of NiCl₂ modification on the electrochemical performance of LiV₃O₈ cathode have been investigated. The structural and surface morphologic properties of synthesized materials are characterized by X-ray diffraction and scanning electron microscopy. The electrochemical properties are investigated by charge–discharge testing and cyclic voltammetry. It is found that 8.0 wt% NiCl₂-modified LiV₃O₈ shows excellent electrochemical properties. The initial discharge capacity of 8.0 wt% NiCl₂-modified LiV₃O₈ is much higher than that of pristine LiV₃O₈, and can attain 336.7 mAh g^?1 at the current rate of 0.5 C (300 mA g^?1 is assumed to be 1 C rate). Additionally, NiCl₂ modification significantly improves the cyclability of LiV₃O₈. The NiCl₂ modification is shown to be able to suppress the capacity fade of LiV₃O₈ without specific capacity expense by suppressing the characteristic phase transitions during cycling.     

Time-domain simulations of transient response in LiFePO4 cathode lithium ion batteries

The time domain transients of batteries comprised of LiFePO₄ cathode material exhibit large nonlinearity with the increasing discharging rates. Hence, the calculated overpotential transients match the experimental determined well only when the discharging current is low enough. The results of electrochemical impedance spectra at different OCV level indicate that the change of the parameters of equivalent circuit or even the circuit architecture are probably responsible for the large discrepancy between the predicted and the measured transient profiles. By taking the change of equivalent circuit model at high discharging current into consideration, we successfully simulate the time domain transients of polarization within the entire discharging current range. Also with the help of circuit analysis, the contribution of the ohmic resistance, charge transfer impedance and solid-state diffusion impedance to total polarization has been differentiated as a function of discharging time.     

Enhanced electrochemical properties of ZnO-coated LiMnPO<Subscript>4</Subscript> cathode materials for lithium ion batteries

We demonstrated the effect of ZnO (different wt%)-coated LiMnPO₄-based cathode materials for electrochemical lithium ion batteries. ZnO-coated LiMnPO₄ cathode materials were prepared by the sol-gel method. X-ray diffraction (XRD) analysis indicates that there is no change in structure caused by ZnO coating, and field emission scanning electron microscopy (FESEM) images depict the closely packed particles. Galvanostatic charge-discharge tests show the ZnO-coated LiMnPO₄ sample has an enhanced electrochemical performance as compared to pristine LiMnPO₄. The 2 wt% of ZnO-based LiMnPO₄ exhibited maximum discharge capacity of 102.2 mAh g^?1 than pristine LiMnPO₄ (86.2 mAh g^?1) and 1 wt% of ZnO-based LiMnPO₄ (96.3 mAh g^?1). The maximum cyclic stability of 96.3 % was observed in 2 wt% of ZnO-based LiMnPO₄ up to 100 cycles. This work exhibited a promising way to develop a surface-modified LiMnPO₄ using ZnO for enhanced electrochemical performance in device application.     

Co-precipitation synthesis and performance of multi-doped LiCrxNixMn2-2xO4-zFz cathode materials for lithium ion batteries

Multiple ion-doped lithium manganese oxides LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z =  0.05, 0.1) with a spinel structure and space group Fd m were prepared by using the co-precipitation procedure carried out in water–alcohol solvent using adipic acid as the chelating agent. The electrochemical measurements indicated that the charge/discharge capacities of the samples prepared at 600 °C are higher than that of the treatment at 800 °C or microwave heating. The capacitance-voltage (CV) curves of LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z = 0.05, 0.1) showed that when x ≤ 0.1, the samples had two reduction–oxidation peaks at 4.0 to 4.2-V region, whereas when x > 0.1, the samples had only one reduction–oxidation peak at 4.0- to 4.2-V region in CV measurements and could offer more stable voltage plateau in a 4-V region and also had stable electrical conductivity after 20 cycles. Another reduction–oxidation peak appeared in 4.6-4.8-V region (Ni²⁺–Ni⁴⁺ reduction–oxidation peaks); this suggests that the LiCr_xNi_xMn_2-2xO_4-zF_z (0.1 < x≤ 0.25, z = 0.05, 0.1) cathode material could offer 4.6 to 4.8-V charge/discharge plateaus, and its specific capacity increases with increasing Ni²⁺. The impedance measurements of the cell proved that the F⁻ anion doped can not only prevent Mn³⁺ from disproportion but also can prevent the passivation film from forming and can help keep stable the cell’s electrical properties. The LiCr_0.05Ni_0.05Mn_1.9O_3.9F_0.1 sintered at 600 °C shows the best cycle performance and the largest capacity in all prepared samples; its first discharge capacity is 120 mAh/g, and the discharge capacity loses only 1.78% after 20 cycles. After 100 cycles, it still remains in the spinel structure.     

Improvement of electrochemical properties of MgO-coated LiNi0.4Co0.2Mn0.4O2 cathode materials for lithium ion batteries

The surface of LiNi_0.4Co_0.2Mn_0.4O₂ cathode is coated using MgO coating materials. The electrochemical properties of the coated materials are investigated as a function of the pH value of the coating solution and the composition of coating materials. Their microscopic structural features have been investigated using scanning electron microscopy and X-ray diffraction. The electrochemical properties of the samples were monitored using coin-cell by galvanostatic charge–discharge cycling test, EDS test, EIS test, and cyclic voltammetry. The coating solution with pH?=?10.5 is found to be favorable for the formation of stable coating layers, which enhances the electrochemical properties. In contrast, 2 % MgO-coated LiNi_0.4Co_0.2Mn_0.4O₂ shows better cycle performance and rate capability than the bare sample. Such enhancements are attributed to the presence of a stable MgO layer which acts as the interfacial stabilizer on the surface of LiNi_0.4Co_0.2Mn_0.4O₂.     

Synthesis of N-doped graphene/SnS composite and its electrochemical properties for lithium ion batteries

N-doped graphene/SnS composite as high-performance anode materials has been synthesized by a simultaneous solvothermal method using ethylene glycol as solvent. The morphology, structure, and electrochemical performance of N-doped graphene/SnS composite were investigated by transmission electron microscope (TEM), X-ray diffraction (XRD), Raman spectra, Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. The SnS nanoparticles with sizes of 3–5 nm uniformly distribute on the N-doped graphene matrix. The N-doped graphene/SnS composite exhibits a relatively high reversible capacity and good cycling stability as anode materials for lithium ion batteries. The good electrochemical performance can be due to that the N-doped graphene as electron conductor improves the electronic conductivity of composite and elastic matrix accommodates the large volume changes of SnS during the cycles.     

Structural and electrochemical study on Li(Li1/3Ti5/3)O4 anode material for lithium ion batteries

Chemical and electrochemical studies have shown that various titanium oxides can incorporate lithium in different ratios. Other compounds with a spinel-type structure and corresponding to the spinel oxides LiTi₂O₄ and Li₄Ti₅O₁₂ have been evaluated in rechargeable lithium cells with promising features. The spinel Li[Li_1/3Ti_5/3]O₄ [1–5] compound is a very appealing electrode material for lithium ion batteries. The lithium insertion-deinsertion process occurs with a minimal variation of the cubic unit cell and this assures high stability which may reflect into long cyclability. In addition, the diffusion coefficient of lithium is of the order of 10⁻⁸ cm²s⁻¹ [5] and this suggests fast kinetics which may reflect in high power capabilities. In this work we report a study on the kinetics and the structural properties of the Li[Li_1/3Ti_5/3]O₄ intercalation electrode carried out by: cyclic voltammetry, galvanostatic cycling and in-situ X-ray diffraction. The electrochemical characterization shows that the Li[Li_1/3Ti_5/3]O₄ electrode cycles around 1.56 V vs. Li with a capacity of the order of 130 mAhg⁻¹ which approaches the maximum value of 175 mAhg⁻¹ corresponding to the insertion of 1 equivalent per formula unit. The delivered capacity remains constant for hundred cycles confirming the stability of the host structure upon the repeated Li insertion-deinsertion process. This high structural stability has been confirmed by in situ Energy Dispersion X-ray analysis. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

表面效应对锂离子电池正极材料LiMn2O4性能的影响

应用基于自旋极化和广义梯度近似(generalized gradient approximation,GGA)的密度泛函理论计算,研究了锂离子电池正极材料LiMn₂O₄ (001)表面原子和电子结构.发现表面和亚表面附近的原子在垂直于(001)面的方向上具有非常大的弛豫,这对LiMn₂O₄材料在锂离子电池中应用时发现的表面Mn的溶解现象有很大关联.由于表面效应,在LiMn₂O₄ (001) 表面只有三价Mn³⁺离子存在,而这些三价锰离子非常活跃,在该材料电极/电解液界面很容易发生歧化反应,从而加速了Mn的溶解.其他计算结果也和实验观察相符合. 关键词： 锂二次电池 表面弛豫 从头算     

Preparation of TEMPO-contained pyrrole copolymer by in situ electrochemical polymerization and its electrochemical performances as cathode of lithium ion batteries

Composite electrodes based on the nitroxide free radical-contained pyrrole copolymer (PPy-co-PPy-C-TEMPO) as active material were one-step synthesized by in situ electrochemical polymerization, which was then directly applied as the cathode of lithium ion batteries. The structure, morphology, electrochemical property, and charge-discharge performances of prepared copolymers were characterized by FTIR, SEM, cyclic voltammogram, electrochemical impedance spectroscopy, and galvanostatic charge-discharge testing, respectively. The results demonstrated that PPy-co-PPy-C-TEMPO-based composite cathodes have been successfully prepared by in situ electrochemical method, and the introduction of the nitroxide free radical (TEMPO) could obviously affect the morphology and electrochemical characteristics of the obtained electroactive polymers. And the charge/discharge tests showed that with the introduction of the TEMPO, PPy-co-PPy-C-TEMPO-based composite cathodes exhibited an improved specific capacity of 70.9 mAh g^?1 for PPy-co-PPy-C-TEMPO (4:1) and 62.6 mAh g^?1 for PPy-co-PPy-C-TEMPO (8:1) as measured at 20 mA g^?1 between 2.5 and 4.2 V, which were remarkably higher than that of the pure PPy cathode of 41.0 mAh g^?1 under the same experimental conditions. Also, the obtained PPy-co-PPy-C-TEMPO copolymers demonstrated an acceptable cycling stability during the charge-discharge process. These obtained cell performances for the composite cathodes were attributed to the application of the in situ electrochemical polymerization technology, which enhanced the intimate integration between conductive polymer film and electrode. Furthermore, the introduction of TEMPO-contained pyrrole (Py-C-TEMPO) improved the morphology of the composite cathode, which was in favor of the utilization of active materials and the improved electrochemical performances.     

Lithium nickel oxide Li(Ni0.75Al0.17Co0.08)O2 as cathode material for lithium ion batteries

Al- and Co-substituted lithium nickel oxide of the nominal composition Li(Ni_0.75Al_0.17Co_0.08)O₂ was synthesised by a coprecipitation technique and by several solid state routes. Rietveld analysis of XRD profiles and galvanostatic cycling in glass cells were performed for structural and electrochemical characterisation. Depending on the reactivity of the respective precursor, there is in each case a minimal synthesis temperature, at which a single phase of the R layered structure could be obtained. The coprecipitation technique and solid state routes using pre-substituted nickel hydroxide are suitable for the synthesis of single phase Al- and Co-substituted lithium nickel oxide, even at rather low synthesis temperatures. The electrochemical performance of lithium nickel oxide Li(Ni_0.75Al_0.17Co_0.08)O₂ synthesised in air is poor due to an enhanced lithium nickel disorder. Synthesis in oxygen atmosphere seems to be required. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Brief overview of electrochemical potential in lithium ion batteries

The physical fundamentals and influences upon electrode materials' open-circuit voltage(OCV) and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries(LIBs), and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.     

Comparison of the electrochemical behaviour of SnO2 and PbO2 negative electrodes for lithium ion batteries

In this paper we report our structural and electrochemical investigations of tin dioxide and lead dioxide electrodes in order to highlight the difference observed between them. The electrochemical reactions of these two oxides are known: the reduction of the metal oxide and the reversible formation/decomposition of the lithium-metal alloys. The reversible capacity of these systems is based on the alloy formation. The first reaction is supposedly irreversible (formation of Li₂O), but the X-ray diffraction analysis and especially¹¹⁹Sn Mössbauer spectrometry show a possible re-oxidation of the metal particles in the case of tin dioxide electrodes. However, this reaction is not fully reversible and occurs at a high potential vs. Li. For lead dioxide electrodes, the re-oxidation of the metal particles seems more difficult in spite of the similar structure of both oxides.     

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Solid-state synthesis of graphite carbon-coated Li4Ti5O12 anode for lithium ion batteries

Graphites are widely used for their high electrical conductivity and good thermal and chemical stability. In this work, graphitic carbon-coated lithium titanium (Li₄Ti₅O₁₂/GC) was successfully synthesized by a simple one-step solid-state reaction process with the assistance of sucrose without elevating sintering temperature. The lattice fringe of 0.208 nm clearly seen from the high-resolution transmission electron microscopy (HRTEM) images was assigned to graphite (010). The average grain size of the as-prepared Li₄Ti₅O₁₂/GC was about 100–200 nm, 1 order smaller than that of pure Li₄Ti₅O₁₂ prepared similarly. The rate performance and cycle ability were significantly improved by the hybrid conducting network formed by graphitic carbon on the grains and amorphous carbon between them. The specific capacity retention rate was 66.7 % when discharged at a rate of 12C compared with the capacity obtained at 0.5C. After 300 cycles, the capacity retention was more than 90 % at a high rate of 15C.