A review of recent developments in the surface modification of LiMn2O4 as cathode material of power lithium-ion battery

LiMn₂O₄ (LMO) is a very attractive choice as cathode material for power lithium-ion batteries due to its economical and environmental advantages. However, LiMn₂O₄ in the 4-V region suffers from a poor cycling behavior. Recent research results confirm that modification by coating is an important method to achieve improved electrochemical performance of LMO, and the latest progress was reviewed in the paper. The surface treatment of LMO by coating oxides and nonoxide systems could decrease the surface area to retard the side reactions between the electrode and electrolyte and to further diminish the Mn dissolution during cycling test. At present, LiMn₂O₄ is the mainstreaming cathode material of power lithium-ion battery, and, especially the modified LMO, is the trend of development of power lithium-ion battery cathode material in the long term.     

Recent developments in the doping and surface modification of LiFePO4 as cathode material for power lithium ion battery

Lithium ion batteries have become attractive for portable devices due to their higher energy density compared to other systems. With a growing interest to develop rechargeable batteries for electric vehicles, lithium iron phosphate (LiFePO₄) is considered to replace the currently used LiCoO₂ cathodes in lithium ion cells. LiFePO₄ is a technically important cathode material for new-generation power lithium ion battery applications because of its abundance in raw materials, environmental friendliness, perfect cycling performance, and safety characteristics. However, the commercial use of LiFePO₄ cathode material has been hindered to date by their low electronic conductivity. This review highlights the recent progress in improving and understanding the electrochemical performance like the rate ability and cycling performance of LiFePO₄ cathode. This review sums up some important researches related to LiFePO₄ cathode material, including doping and coating on surface. Doping elements with coating conductive film is an effective way to improve its rate ability.     

Compatibility study of oxide and olivine cathode materials with lithium aluminum titanium phosphate

The compatibility of the solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) with the cathode materials LiCoO₂, LiMn₂O₄, LiCoPO₄, LiFePO₄, and LiMn_0.5Fe_0.5PO₄ was investigated in a co-sintering study. Mixtures of LATP and the different cathode materials were sintered at various temperatures and subsequently analyzed by thermal analysis, X-ray diffraction, and electron microscopy. Oxide cathode materials display a rapid decomposition reaction with the electrolyte material even at temperatures as low as 500 °C, while olivine cathode materials are much more stable. The oxide cathode materials tend to decompose to lithium-free compounds, leaving lithium to form Li₃PO₄ and other metal phosphates. In contrast, the olivine cathode materials decompose to mixed phosphates, which can, in part, still be electrochemically active. Among the olivine cathode materials, LiFePO₄ demonstrated the most promising results. No secondary phases were detected by X-ray diffraction after sintering a LATP/LiFePO₄ mixture at temperatures as high as 700 °C. Electron microscopy revealed a small secondary phase probably consisting of Li₂FeTi(PO₄)₃, which is ionically conductive and should be electrochemically active as well.     

Ex situ FTIR spectroscopy study of LiVPO4F as cathode material for lithium-ion batteries

The LiVPO₄F as cathode material for lithium-ion batteries was synthesized through two steps of solid-state reactions and investigated by ex situ Fourier transform infrared (FTIR) spectroscopy for the initial charge and discharge cycle. The characterization of the effect on the structure of the LiVPO₄F in the process of lithium-ion insertion/extraction at a molecular level by ex situ FTIR spectroscopy is helpful for the mechanism research for lithium-ion insertion/extraction and the improvement of the performance of lithium-ion batteries. In the process of the initial cycle, new bands of VPO₄F appear in the charge and the featured bands of LiVPO₄F reappear in the discharge. In this paper, ex situ FTIR spectra indicates that the structure of the LiVPO₄F in the process of lithium-ion insertion/extraction is almost not affected, which clearly states that the LiVPO₄F possesses stable structure as cathode material. Consequently, the LiVPO₄F might be expected as a potential cathode replacement for commercial lithium-ion batteries.     

Effects of sintering temperature on the structure and electrochemical performance of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> cathode materials

The objective of the present study was to investigate the effects of sintering temperature on the structure and electrochemical performance of Mg₂SiO₄ cathode materials using sol-gel method. X-ray diffraction and Fourier-transform infrared analysis were used to study the structural properties of the materials. The temperatures applied in the sintering process influenced the structure, morphology, as well as particle size distribution of the Mg₂SiO₄. All samples sintered at temperatures of 900, 1000, and 1100 °C yielded pure Mg₂SiO₄ compounds consisting of orthorhombic crystalline phase with a space group of Pbnm. Particle size and lattice parameters of Mg₂SiO₄ samples increased with the increases of sintering temperature due to an increase of the nucleation and crystal growth rates. The cyclic voltammetry analysis showed the presence of redox reaction. This result shows that the Mg₂SiO₄ material has potential to be used as cathode materials in magnesium rechargeable batteries.     

Structural and electrochemical investigation of Zn-doped LiCoO2 powders

A commercial cathode material (LiCoO₂) was modified by doping with Zn to improve its performance in lithium battery. The structure and morphology of the doped cathode material were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). The synthesized samples were characterized using X-ray photoelectron spectra (XPS), used to investigate the elementary states on the system. The electrical conductivity variations of doped powders were measured in the temperature range between 30 and 150?°C. The 3?mol% Zn-doped LiCoO₂ sample shows the highest reversibility capacity (178?mA?h g^?1) after 30 cycles in the voltage window 3.0?C4.5?V.     

Electrochemical properties of carbon-coated LiFePO4 synthesized by a modified mechanical activation process

Carbon-coated lithium iron phosphate (LiFePO₄/C) composites were synthesized by conventional mechanical activation (MA) process and also by a modified MA process. Phase-pure particles were obtained of ∼100 nm size with a nano-meter thick web of carbon surrounding the particles. The composite prepared by the modified MA process shows good performance as cathode material in lithium cells at room temperature. A high performance was achieved at 0.1 C-rate with >96% utilization of the active material. A stable cycle performance even at higher C-rates was achieved with a cathode that has a total carbon content of only 12 wt%. The use of the modified MA process to synthesize LiFePO₄/C has promise to be an efficient process to decrease the total carbon content of the cathode, resulting in the enhanced energy density.     

Effect of fluorine in Li1.27Cr0.2Mn0.53O2 cathode for secondary lithium batteries

Fluorine substituted Li_1.27Cr_0.2Mn_0.53O₂ electrode, prepared by sol–gel method, was investigated in the present work. Thermal analysis was done on this cathode material and found to be thermally stable with a loss of weight near 300 °C. Influence of fluorine substitution on the structural and electrochemical properties of the Li_1.27Cr_0.2Mn_0.53O₂ electrode was studied by X-ray diffraction (XRD) and field emission scanning electron microscope. XRD pattern of the fluorine-doped Li_1.27Cr_0.2Mn_0.53O₂ cathode material quenched at 900 °C indicates a phase pure material. The charge–discharge profile of the prepared cathode material showed that the fluorine substitution for oxygen in the cathode material resulted in improved capacity retention. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006.     

Physicochemical properties of NaxCoO2 as a cathode for solid state sodium battery

An intercalation compound with composition Na_0.7CoO₂ has been synthesized through different preparative techniques such as solid state reaction, ball milling and sol gel techniques. The investigation reveals that the cathode material with an average particle size of about 500 nm of uniform morphology can be synthesized through sol gel technique. Further, this synthesis technique improves the stoichiometry of the sodium content significantly. The electrical resistivity of these cathode materials is found to be in the range of 4 to 12 mΩ-cm at 300 K. It has been observed that, the resistivity of the cathode material increases with increase in sodium content. The electrochemical cells with the configuration Na | [wt.% 0.3 PEO-0.7 PEG]₆:NaPO₃ |composite cathode material, have shown an open circuit voltage (OCV) value of 2.7 V. The (OCV) of the cells with the cathode prepared by sol-gel and ball milling route has shown a plateau region of about 40 h, when compared to the plateau region of 10 h for the battery with the cathode prepared by solid state reaction. The reduction in the particle size of the cathode material has improved the stability of the electrode electrolyte interface and thereby discharges characteristics.     

Structural and electrochemical properties of LiFe1 − 3x/2Bi x PO4/C synthesized by sol–gel

In this study, LiFe_1???3x/2Bi _x PO₄/C cathode material was synthesized by sol–gel method. From XRD patterns, it was found that the Bi-doped LiFePO₄/C cathode material had the same olivine structure with LiFePO₄/C. SEM studies revealed that Bi doping can effectively decrease the particle sizes. It shortened Li⁺ diffusion distance between LiFePO₄ phase and FePO₄ phase. The LiFe_0.94Bi_0.04PO₄/C powder exhibited a specific initial discharge capacity of about 149.6 mAh g^?1 at 0.1 rate as compared to 123.5 mAh g^?1 of LiFePO₄/C. EIS results indicated that the charge-transfer resistance of LiFePO₄/C decreased greatly after Bi doping.     

Investigation of the synergetic effects of LiBF<Subscript>4</Subscript> and LiODFB as wide-temperature electrolyte salts in lithium-ion batteries

Herein, we present the use of lithium tetrafluoroborate (LiBF₄) as an electrolyte salt for wide-temperature electrolytes in lithium-ion batteries. The research focused on the application of blend salts to exhibit their synergistic effect especially in a wide temperature range. In the study, LiCoO₂ was employed as the cathode material; LiBF₄ and lithium difluoro(oxalate)borate (LiODFB) were added to an electrolyte consisting of ethylene carbonate (EC), propylene carbonate (PC), and ethyl methyl carbonate (EMC). The electrochemical performance of the resulting electrolyte was evaluated through various analytical techniques. Analysis of the electrical conductivity showed the relationship among solution conductivity, the electrolyte composition, and temperature. Cyclic voltammetry (CV), charge-discharge cycling, and AC impedance measurements were used to investigate the capacity and cycling stability of the LiCoO₂ cathode in different electrolyte systems and at different temperatures. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were applied to analyze the surface properties of the LiCoO₂ cathode after cycling. The results indicated that the addition of a small amount of LiODFB into the LiBF₄-based electrolyte system (LiBF₄/LiODFB of 8:2) may enhance the electrochemical performance of the LiCoO₂ cell over a relatively wide temperature range and improve the cyclability of the LiCoO₂ cell at 60 °C.     

Structure and electrochemical performance of LiV x Mn2 − x O4 (0 ≤ x ≤ 0.20) cathode materials for rechargeable lithium ion batteries

LiMn₂O₄ and vanadium-substituted LiV _x Mn_2???x O₄ (x?=?0.05, 0.10 0.15 and 0.20) cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using X-ray diffraction, SEM, TEM and charge–discharge studies. X-ray powder diffraction analysis was changed in lattice parameters with increasing vanadium content suggesting the occupation of the substituent within LiMn₂O₄ interlayer spacing. TEM and SEM analyses show that LiV_0.15Mn_1.85O₄ has a smaller particle size and more regular morphological structure with narrow size distribution than LiMn₂O₄. It is concluded that the structural stability and cycle life improvement were due to many factors like better crystallinity, smaller particle size and uniform distribution compared to the LiMn₂O₄ cathode material. The LiV_0.15Mn_1.85O₄ cathode material has improved the structural stability and excellent electrochemical performances of the rechargeable lithium ion batteries.     

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Nano-structured LiVPO₄F/Ag composite cathode material has been successfully synthesized via a sol–gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO₄F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO₄F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO₄F material exhibits high discharge capacity, good cycle performance (108.5 mAh g⁻¹ after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g⁻¹ for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (R_ct) of LiVPO₄F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO₄F for lithium-ion batteries cathode material.     

Hydrothermal synthesis of FeS2 for lithium batteries

Nanocrystalline FeS₂ cathode material of lithium cell was synthesized from cheap materials of FeSO₄, Na₂S₂O₃, and sulfur by a hydrothermal process. The scanning electron microscopy analysis showed the obtained material was nano-sized, about 500 nm. The X-ray powder diffraction analysis showed that the synthetic FeS₂ material had two phases of the crystalline structure, pyrite and marcasite. The phase of marcasite seems to have no negative effect on the electrochemical performance of the material. The synthetic FeS₂ showed a significant improvement of electrochemical performance for Li/FeS₂ cells.     

Hydrothermal synthesis of spinel Li1+x Mn2O4 as cathode material for rechargeable lithium battery

Abstract

The hydrothermal synthesis of Li-Mn spinel oxide (Li_1+xMn₂O₄) was undertaken in order to develop high quality, low cost cathode material for a rechargeable lithium battery. In our experiments, γ-MnOOH, LiOH · H₂O and H₂O₂ were used as starting materials to synthesize Li-Mn spinel oxide under hydrothermal conditions of 180-230°C and about 1.0-2.8 MPa. The chemical composition and particle size of the Li_1+xMn₂O₄ is easily controlled in the hydrothermal reaction. The Li_1+xMn₂O₄ produced was characterized by X-ray diffraction, with the spinel phase having a Li/Mn ratio of 0.50-0.60. There is convincing evidence, as a result of this work, that our synthesis process is most suitable for producing high quality cathode material that can be used in a rechargeable lithium battery.     

Phenomenon of enhanced diffusion of lithium-ion in LiMn2O4 induced by electrochemical cycling

Lithium-ion diffusion in insertion-host materials is of significant interest because of its importance in improving the power density of lithium-ion batteries. In this study, the dependence of the chemical diffusion coefficient (D) of lithium-ion in spinel LiMn₂O₄ cathode material on electrochemical cycling has been investigated by the capacity intermittent titration technique (CITT). Results show that there are two minimum peaks in the curves of D∼E respectively at ∼3.95 and ∼4.12 V in the voltage range from 3.85 to 4.30 V. The curves of D∼E at different cycles show an interesting phenomenon that the values of D tend to increase with the cycling numbers. This phenomenon indicates an enhanced diffusion of lithium-ion in LiMn₂O₄ cathode material induced by the electrochemical cycling.     

Research status in preparation of FePO4: a review

The cathode is the most important component of a lithium-ion battery. The olivine structure lithium iron phosphate (LiFePO₄) with its numerous appealing features, such as high theoretical capacity, acceptable operating voltage, increased safety, environmental benignity, and low cost, has attracted extensive interest as a potential cathode material for Li-ion batteries. As a precursor, FePO₄ can be used to produce LiFePO₄ on a large scale with high bulk density, discharge rate, and capacity. This can be realized by controlling the crystal size and morphology of FePO₄. The characteristics, structure, and synthesis methods of FePO₄ are discussed in this review. The relative merits of these synthetic methods, as well as some suggestions on how to improve them, are also presented.     

A carbothermal reduction method for enhancing the electrochemical performance of LiFePO4/C composite cathode materials

LiFePO₄/C composite cathode material has been synthesized by a carbothermal reduction method using β-FeOOH nanorods as raw materials and glucose as both reducing agent and carbon source. The results indicate that the content of carbon and the morphology of raw material have effect on the electrochemical performance of the final LiFePO₄/C material. Sample LFP14 with a carbon content of 2.79 wt.% can deliver discharge capacities of 158.8, 144.3, 111.0, and 92.9 mAh g^?1 at 0.1, 1, 10, and 15 C, respectively. When decreasing the current from 15 C back to 0.1 C, a discharge capacity of 157.5 mAh g^?1 is recovered, which is 99.2 % of its initial capacity. Therefore, as a kind of cathode material for lithium ion batteries, this LiFePO₄/C material synthesized via a carbothermal reduction method is promising in large-scale production, and has potential application in upcoming hybrid electric vehicles or electric vehicles.     

Surface modification by silver coating for improving electrochemical properties of LiFePO4

LiFePO₄ is a potential candidate for the cathode material of the lithium secondary battery. Fine particle LiFePO₄ was synthesized by the simple co-precipitation method, and aqueous coating on the LiFePO₄ was tried using silver nitrate solution in order to increase electronic conductivity. Highly dispersed silver on the particles enhances the electronic conductivity and increases the capacity. The electrochemical properties of the silver coated LiFePO₄ with the various current densities are analogous to those of highly conductive LiFePO₄. The silver coating can be a promising tool to preserve the capacity even at the high current densities.     

Effect of mesoporous carbon containing binary conductive additives in lithium ion batteries on the electrochemical performance of the LiCoO2 composite cathodes

Binary conductive additives (BCA), formed by sonication of mesoporous carbon (MC) and acetylene black (AB), were used as conductive additives to improve the electrochemical performance of a LiCoO₂ composite cathode. The electrochemical performance of the LiCoO₂ composite cathode dispersed with BCA was investigated. The results showed that the electrochemical performance (including the discharge capacity, the discharge voltage and the total internal resistance) of a BCA loaded LiCoO₂ composite cathode was better than that of a cathode loaded with AB. The possible mechanism is that the MC in BCA can adsorb and retain electrolyte solution, which allows an intimate contact between the lithium ions and the cathode active material LiCoO₂ due to its large mesopore specific surface area. A simplified model was also proposed.