Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method
© Yang et al; licensee Springer. 2012
Received: 19 September 2011
Accepted: 5 January 2012
Published: 5 January 2012
LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method.
Keywordslithium-ion batteries cathode material lithium iron phosphate sol-gel method complexing agent
LiCoO2, LiNiO2, and LiMn2O4 have been widely used as cathode materials in lithium-ion batteries currently. More recently, LiFePO4 has become one of the most promising candidates due to its relative lack of toxicity, inexpensiveness, and its ability to provide a long cycle life and high rate at high temperatures [1, 2]. LiFePO4 has a high lithium intercalation voltage of 3.4 V vs. lithium and a high theoretical capacity of 170 mAh g-1. However, it is difficult to make practical use of the full theoretical capacity at a high rate because the separation of the chain of FeO6 edge-shared octahedral contributes an extremely low electronic conductivity . There are two drawbacks in using LiFePO4 as a commercial cathode material: one problem is its poor electronic conductivity, and the other one is the difficulty of synthesizing LiFePO4 because of iron oxidation state.
It is an effective method to improve the electrochemical property of LiFePO4 by supervalent ion doping [4, 5], carbon coating [6, 7], and synthesizing particles with well-defined morphology . Olivine-type LiFePO4 can be synthesized by a solid-state reaction, sol-gel method, mechanical activation, or microwave heating, etc. The solid-state reaction has been widely adopted for synthesis of pure crystalline olivine-phase LiFePO4, resulting in the formation of large particles. Because the reaction occurred on a molecular level, sol-gel method is one of the effective means to prepare ultrafine particles [9–11]. Until now, most researchers have placed much more emphasis on the processing of the sol-gel method and its effect on the structures and electrochemical performances of cathode materials, but the mechanism is hardly studied to explain the effect of complexing agents in the process of preparation.
In this study, LiFePO4/C composites were prepared with different complexing agents by sol-gel method, and the analysis of the experimental data based on the ligand field theory was carried out. Tap density and charge-discharge experiments to evaluate the electrochemical performance of LiFePO4/C as a cathode material were also investigated.
Various LiFePO4/C cathode materials were synthesized by sol-gel method with acetic acid, ethanediol, oxalic acid, and ethylenediamine as complexing agents, and they were named as SGAc, SGEg, SGOc, and SGEn, respectively. The ingredient chemicals LiNO3 (A.R, Shanghai Chemical Reagents Co. Ltd., China), iron (III) nitrate Fe(NO3)3·9H2O (A.R, Shanghai Chemical Reagents Co. Ltd., China), and NH4H2PO4 (A.R, Shanghai Chemical Reagents Co. Ltd., China) were dissolved stoichiometrically in the saturated solution of complexing agent in water, and then, ascorbic acid was added to form a homogeneous solution after continuous stirring for 1 h at 55°C. The reaction mixture was adjusted to a pH of 6.5 with ammonia water and stirred at 75°C, and then, the solution was evaporated to dryness. The residue was formed into gel, which was dried in a vacuum drying oven at 80°C for 12 h. The mixture was pelletized and heated in a nitrogen atmosphere at 600°C for 4 h, and then cooled slowly to room temperature.
LiFePO4/C was characterized by scanning electron microscopy [SEM] and X-ray diffraction [XRD]. The SEM observation was performed on a JSM-5610 scanning electron microscope (JEOL Ltd., Akishima, Tokyo, Japan). X-ray diffraction was carried out by a Rigaku-D/MAX-2400 diffractometer (Rigaku Corporation, Tokyo, Japan) with CuKα radiation (λ = 0.15406 nm).
The testing electrodes were made by dispersing 80 wt.% active material, 15 wt.% acetylene black, and 5 wt.% poly(vinylidene fluoride) binder in a dimethyl phthalate solvent to form a slurry. The slurry was coated onto an Al foil and dried in a vacuum oven at 80°C. The separator was a Celgard 2400 microporous membrane (Celgard, LLC, Charlotte, NC, USA). 1 M LiPF6 solution in ethylene carbonate-dimethyl carbonate mixture (1:1 in volume) was used as an electrolyte, and lithium foil was used as an anode. The prototype cell was assembled in a dry glove box under argon. Cyclic voltammetry [CV] was performed at a scanning rate of 0.05 mV·s-1 from 2.0 V to 4.5 V. The charge-discharge cycle performance was examined by an Arbin instrument BT-2000 (Arbin Instruments, College Station, TX, USA) between 2.5 and 4.3 V vs. Li+/Li at room temperature.
Results and discussion
From the above analysis, we can conclude that the electrochemical performance of LiFePO4/C prepared by sol-gel method was affected by the complexing agents. Therefore, we also explored the possible effect mechanism of a complexing agent on the synthesis of LiFePO4/C by sol-gel method.
In the process of the sol-gel method, gel was formed by a reaction between the Fe2+ and complexing agent. There were three states which were sol, gel, and sintering products in the whole process. Because the electrochemical properties of LiFePO4/C depended on the particle size and its homogeneity, it was important that the gel was formed. The difference among gels was formed by using different complexing agents, so the effect mechanism of complexing agents on the synthesis of LiFePO4/C would be explained by coordinate chemistry theory.
Effects of complexing agents on Fe2+ and the characteristics of LiFePO4/C synthesized by sol-gel method
Discharge specific capacity (mAh g-1)
According to Table 1, we can see that the discharge specific capacity of the material that was formed by the acetic acid monodentate ligand was 161.1 mAh g-1, which was the highest. The discharge capacity of the material that was formed by different complexing agents had a reverse relationship between the stability constant of Fe2+ and various complexing agents. That is, the higher the stability constant, the lower the discharge capacity. Based on coordinate chemistry theory, complexes with a larger stability constant are more stable, and those complexes are difficult to decompose when sintering. The final product preserved the multi-ring interleaving structure, to a great extent, that lead to the poor crystallinity and low discharge capacity of the product. However, complexes with a low stability constant were unstable, and those complexes were easy to decompose when sintering at the same temperature. The average particle size of the final product was small, which was beneficial in reducing the diffusion length of the lithium ion inside, resulting in fast reaction and diffusion kinetics, which can increase the electrochemical properties of material.
where n1 was electron number in t2g orbit, n2 was electron number in eg orbit.
Acetic acid was a monodentate ligand; Fe2+ coordinated with three acetic acid molecules and one water molecule at the same time; so, Fe2+ was in a tetrahedral field composed of three oxygen atoms provided by acetic acid and one oxygen atom provided by water. The d electron configuration of the high-spin Fe2+ in a tetrahedral field was eg3t2g3, whose pairing electron number was one.
The CFSE that high-spin Fe2+ gained from the tetrahedral field was lower than that from the octahedral field. It is said that the stability Fe2+ in the tetrahedral field was poorer than that in the octahedral field, so the discharge capacity of the material formed with acetic acid was higher than that formed with oxalic acid.
In the process of complex decomposition, the carbon would partially produce residues in the product. The carbon content of LiFePO4/C had a direct ratio to the stability constant of Fe2+ with various complexing agents. The trend was consistent with the rule that the lower the stability constant was, the easier the product decomposed.
In short, complexing agents with a small stability constant would be chosen to format the precursor of LiFePO4/C, which would decompose easily due to poor stability when heating. Such method would beneficial in improving the electrochemical properties of the material.
The LiFePO4/C was synthesized via sol-gel method by using Fe3+ as iron sources, ascorbic acid as reducing reagent, and acetic acid, ethanediol, oxalic acid, and ethylenediamine as complexing agents. The LiFePO4/C synthesized with acetic acid as complexing agent has better electrochemical performance, having a discharge capacity of 161.1 mAh g-1 at the first cycle, and the capacity decreases to 157.5 mAh g-1 after 30 cycles. The capacity fading rate is 2.2%. According to the crystal field theory, a complexing agent with a small stability constant would be decomposed easily due to poor stability when heating. However, we found that the discharge capacity of LiFePO4/C synthesized with acetic acid as complexing agent was not consistent with the principle. The problem was solved by computing the CFSE of Fe2+ in a crystal field.
This work was co-supported by the Ministry of Education Key Laboratory of Synthetic and Natural Functional Molecular Chemistry, Education Department of Shaanxi Province (2010JK765) and a fellowship from the NRF of Korea.
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