Laser‐induced phase changes in olivine FePO4: a warning on characterizing LiFePO4‐based cathodes with Raman spectroscopy

Raman spectroscopy is an excellent technique for probing lithium intercalation reactions of many diverse lithium ion battery electrode materials. The technique is especially useful for probing LiFePO₄‐based cathodes because the intramolecular vibrational modes of the PO₄³⁻ anions yield intense bands in the Raman spectrum, which are sensitive to the presence of Li⁺ ions. However, the high power lasers typically used in Raman spectroscopy can induce phase transitions in solid‐state materials. These phase transitions may appear as changes in the spectroscopic data and could lead to erroneous conclusions concerning the delithiation mechanism of LiFePO₄. Therefore, we examine the effect of exposing olivine FePO₄ to a range of power settings of a 532‐nm laser. Laser power settings higher than 1.3 W/mm² are sufficient to destroy the FePO₄ crystal structure and result in the formation of disordered FePO₄. After the laser is turned off, the amorphous FePO₄ compound crystallizes in the electrochemically inactive α‐FePO₄ phase. The present experimental results strongly suggest that the power setting of the excitation laser should be carefully controlled when using Raman spectroscopy to characterize fundamental lithium ion intercalation processes of olivine materials. In addition, Raman spectra of the amorphous intermediate might provide insight into the α‐FePO₄ to olivine FePO₄ phase transition that is known to occur at temperatures higher than 450 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

纳米颗粒的表面效应和电极颗粒间挤压作用对锂离子电池电压迟滞的影响

硅作为锂离子电池电极材料之一,其应力效应尤为突出,进而将影响电池性能.本文建立了电化学反应-扩散-应力全耦合模型,并研究了恒压充放电条件下扩散诱导应力、表面效应和颗粒间挤压作用对电压迟滞的影响.结果发现,应力及其导致的电压迟滞程度与颗粒尺寸相关.在大颗粒(颗粒半径r 100 nm)中,扩散诱导应力是导致电势迟滞效应的主要因素,这将导致电池能量耗散.对于纳米级小颗粒(r 100 nm)而言,表面效应占据主导,表面效应虽然能缓解电压迟滞,同时却会使驱动电化学反应部分的过电势回线下移,造成锂化容量衰减.本文综合考虑了扩散诱导应力和表面效应,得出:半径为10 nm的颗粒将会使电极具备较好的综合性能.此外,对于硅电极而言,颗粒间挤压作用会使应力回线向压应力状态演化,进而导致锂化容量的衰减.计算结果表明,在电极设计中,对孔隙率设定下限值有助于提升电极性能.     

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.     

Nanostructured transition metal phosphide as negative electrode for lithium-ion batteries

In the Li-ion technology, the diffusion of Li in the electrode is often limited by the quality of interfaces. Two synthetic approaches are proposed to develop the transition metal phosphides (TMP)/electrolyte interface. The first route consists in the preparation of nickel nanopowder by solution phase synthesis, and the second is based on the electrochemical synthesis of nickel nanorods in a template followed by vaporization of phosphorous. In the former, the nanosized metallic particles are foreseen to be used as starting nanomaterial to directly react with phosphorous agents (P or Li₃P) during the cycling of the lithium battery. A preliminary electrochemical test of the NiP _x nanorods/Li half-cell shows the feasibility of the use of such nanostructured TMP electrode in a Li battery. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Influence of the geometry of a porous network on the phase transition in a ferroelectric embedded in a porous matrix

A ferroelectric phase transition in a system of electrically interacting small particles is considered. The size effects in a single particle are described in terms of the Landau phenomenological model. The interaction between particles is reduced to a dipole-dipole interaction. It is shown that the interparticle interaction can lead to a substantial increase in the phase transition temperature as compared to the temperature of the ferroelectric transition in a single small particle.     

Numerical modeling of lithium ion battery for predicting thermal behavior in a cylindrical cell

The thermal behavior of lithium ion battery during charge and discharge is investigated by a numerical simulation. The commercially available cylindrical 18650 battery is modeled in this study. Two different models are used. The porous electrode model is simulated to obtain the Li content inside the particles. The transient thermo-electric model is used to predict the temperature distribution inside the cell. The results suggest that the increase in temperature during discharge is higher than that during charge. The temperature difference between charge and discharge is decreased with increasing C-rates. At a rate of 1C, the discharge temperature increases with a waving region at the beginning, whereas the charge temperature increases until certain point and then decreases. The thermal behavior is closely related to the change in entropy and applied current.     

A new insight into the LiFePO4 delithiation process

Raman and Fourier transform infrared measurements for Li_xM_0.03Fe_0.97PO₄, M = Cr, Cu, Al, Ti were performed. The spectra for delithiated samples to a low content of lithium extraction are practically the same as those of LiFePO₄. For a high content of lithium extraction, the spectra repeat that of FePO₄. In the case of the Li_0.11FePO₄ oxide the spectra cannot be reproduced just by the superposition of the end member profiles. An additional broad band contribution is found in both Raman and infrared spectra probably due to a disordered structure present in the mixture. This suggests that the well accepted two-phase model for the delithiation process in LiFePO₄ is incorrect. The model should be revised to include the new phase as detected here for a particular level of lithium extraction close to that of complete oxidation of the Fe²⁺ ions to Fe³⁺.     

Square model for charge and discharge behavior of cathode electrode materials

The shape of cathode electrode affects severely the potential curves of charge/discharge process of lithium ion cells. In this paper, we take LiFePO₄ for an example. The square model is presented to predict the concentration of lithium on the cathode electrode under some simplified conditions. With the square model as a tool, effects of shape and position are determined and analyzed. Meanwhile, the lithium transportation, Gibbs free energy, and battery potential are proved to be different from that of sphere models. It shows that asymmetry of electrode materials makes a great impact on the performance of charge or discharge process.     

Dynamic aspect of solid solution cathodes by method of integral transform

A mathematical model is presented for a thin film, spherical and cylindrical particles electrodes under galvanostatic discharge. The model available to simulate the electrochemical behavior is discussed considering not only their electrochemical representation (transport phenomena), but also the mathematical techniques, i.e. Integral transform that have been used for solving the equations. We examine the non-homogeneous material balance equation in the rectangular, spherical and cylindrical coordinate system; determine the elementary solutions, the norms and the eigenvalues of the problems for galvanostatic boundary conditions and systematically tabulate the resulting expressions. Expressions are developed for plane, cylindrical and spherical particles giving the relation between battery load and the amount of cathode material utilized. The particle shape and a single parameter Q is used to describe cathode performance.     

A dynamic capacity fading model with thermal evolution considering variable electrode thickness for lithium-ion batteries

Capacity is one of the key parameters to characterize the performances of lithium-ion batteries. Heat generation analysis is essential to evaluate the safety of batteries. To figure out the effects of electrode thickness on capacity fade and thermal behaviors, a capacity fading model is proposed considering reaction kinetics and mass transfer processes on solid electrolyte interface (SEI) layers coupled with thermal evolution. Simulations are conducted on seven LiFePO₄ batteries with variable electrode thicknesses. Results show that, with the increase of electrode thickness, the capacity losses of batteries deteriorate, and the total heat generation aggravates. For the battery with thick electrode, both the polarization overpotential and the gradient of lithium ion concentrations on particle surfaces of active materials increase on the edges, and then decrease perpendicularly to the cathodes. Under the adiabatic conditions, the temperature of battery (with anode 68 μm and cathode 140 μm) is increased to over 130 °C at the sixth cycle. The temperature of batteries declines when discharging in the beginning and then rises, which is noticeable for the batteries with thin electrodes. The proposed model and the simulation results would provide deep insights into both design and operation of batteries.     

Filling dependence of correlation exponents and metal-Mott insulator transition in strongly correlated electron systems

Using a universal relation between electron filling factor and ground state energy,this paper studies the dependence of correlation exponents on the electron filling factor of one-dimensional extended Hubbard model in a strong coupling regime,and demonstrates that in contrast to the usual Hubbard model(gc = 1/2),the dimensionless coupling strength parameter g c heavily depends on the electron filling,and it has a "particle-hole" symmetry about electron quarter filling point.As increasing the nearest neighbouring repulsive interaction,the single particle spectral weight is transferred from low energy to high energy regimes.Moreover,at electron quarter filling,there is a metal-Mott insulator transition at the strong coupling point gc = 1/4,and this transition is a continuous phase transition.     

Lanthanide Luminescence as a Probe of Nanocrystalline Materials

The sharp lines in the optical spectra of lanthanide ions in solids are sensitive to the local environment surrounding the ion and, therefore, provide a local probe to study new materials. This paper reports the laser spectroscopic characterization of a series of Eu₂O₃ nanocrystals, which serve as a model compound for understanding the spectroscopy of lanthanides in nanocrystalline materials. The optical spectra of Eu₂O₃ particles with diameters of approximately 18 to 4 nm show an increase in inhomogeneous broadening and a transition to a very disordered phase as the particle size decreases. The ⁵D₀ fluorescence transients of the nanocrystals are shorter than in bulk material show no clear trend as a function of particle size but do become single exponential for 6- and 4-nm particles.     

锂离子电池多尺度数值模型的应用现状及发展前景

锂离子电池是一种较为复杂的电化学系统, 其涵盖质量传递、电荷传递、热量传递以及多种电化学反应等物理化学过程. 其不仅物理尺度跨越大, 从微观活性颗粒、极片、电芯跨越到电池模组, 还面临着成组配对以及均衡性的问题, 这些问题加剧了电池设计和性能综合评估的难度. 通过计算机数值仿真技术, 建立数学模型, 全面和系统地捕捉电池工作过程各物理场的相互作用机理, 分析其演化规律, 能够为优化电池系统设计提供理论支撑. 本文对锂离子电池的数值模型研究进展和发展趋势进行了综述. 同时对主要理论模型进行了分类整理, 总结了它们的特点、适用范围和局限性, 指出了将来进一步研究的方向和难点所在, 这些对锂离子电池多尺度数值模型的理论研究和工程应用都具有指导性的意义.     

锂离子动力电池高倍率充放电过程中弛豫行为的仿真

基于电化学热耦合模型研究了动力锂离子电池高倍率充放电过程中的弛豫行为, 分析对比了不同充放电机制对电池弛豫行为的影响. 研究发现: 充放电过程中, 欧姆极化是造成电压骤变的主要原因; 而恒流-恒压的充电模式能够缓慢消除欧姆极化, 避免电池电压的骤变; 利用恒流恒压对电池进行充电能够充进更多的电量, 有利于电池性能的完全发挥; 固相锂离子浓度的弛豫时间比液相锂离子浓度的弛豫时间长, 并且在放电后期, 固相扩散的特征时间与液相扩散特征时间的比值不断增大, 固相扩散造成的极化在整个放电过程不可忽略.     

Apparent viscosity and particle pressure of a concentrated suspension of non-Brownian hard spheres near the jamming transition

We consider the steady shear flow of a homogeneous and dense assembly of hard spheres suspended in a Newtonian viscous fluid. In a first part, a mean-field approach based on geometric arguments is used to determine the viscous dissipation in a dense isotropic suspension of smooth hard spheres and the hydrodynamic contribution to the suspension viscosity. In a second part, we consider the coexistence of transient solid clusters coupled to regions with free flowing particles near the jamming transition. The fraction of particles in transient clusters is derived through the Landau-Ginzburg concepts for first-order phase transition with an order parameter corresponding to the proportion of “solid” contacts. A state equation for the fraction of particle-accessible volume is introduced to derive the average normal stresses and a constitutive law that relates the total shear stress to the shear rate. The analytical expression of the average normal stresses well accounts for numerical or experimental evaluation of the particle pressure and non-equilibrium osmotic pressure in a dense sheared suspension. Both the friction level between particles and the suspension dilatancy are shown to determine the singularity of the apparent shear viscosity and the flow stability near the jamming transition. The model further predicts a Newtonian behavior for a concentrated suspension of neutrally buoyant particles and no shear thinning behavior in relation with the shear liquefaction of transient solid clusters.     

First-principles study on electronic structure of LiFePO4

The electronic structure and band structure of olivine LiFePO₄ and its virtually delithiated product FePO₄ are compared based on first-principles calculations. It is found that Li intercalation mainly impacts the electronic and band structures of the Fe atom. Total static energy calculations indicate that it is more difficult for lithium to transfer in LiFePO₄ than in FePO₄.     

Electrochemical performance of surfactant-processed LiFePO4 as a cathode material for lithium-ion rechargeable batteries

This study focuses on the effect of addition of surfactant as a dispersing agent during vibratory ball milling of LiFePO₄ (LFP) precursor materials on the electrochemical performance of solid-state reaction synthesized LFP for lithium-ion battery cathode material. LFP particles formed after calcinations of ball milled LFP precursors (Li₂CO₃, FeC₂O₄, and NH₄H₂PO₄) showed better size uniformity, morphology control, and reduced particle size when anionic surfactant (Avanel S-150) was used. The specific surface area of LFP particles increased by approximately twofold on addition of surfactant during milling. These particles showed significantly enhanced cyclic performance during charge/discharge due to a reduced polarization of electrode material. Electrodes fabricated from LFP particles by conventional milling process showed a 22 % decrease in capacity after 50 cycles, whereas the performance of electrode prepared by surfactant processed LFP showed only 3 % loss in capacity. The LFP particles were characterized using XRD, FE-SEM, particle size distribution, density measurement, and BET-specific surface area measurement. Electrochemical impedance spectra and galvanostatic charge/discharge test were performed for the electrochemical performance using coin-type cell.     

LixFePO4(x=0.0, 0.75, 1.0)电子结构与弹性性质的第一性原理研究

采用基于密度泛函理论的第一性原理研究方法,计算了不同嵌锂态Li_xFePO₄(x=0,0.75,1.0)的电子结构. 对于橄榄石型Li_xFePO₄正极材料,虽然Fe3d电子在费米能级附近相互交错,但由于受晶体场作用的限制,并不能真正成为自由电子,Fe3d电子对体系的导电性没有很大贡献,而Fe—O键在低能成键区形成p-d杂化的局域态共价键对稳定合金骨架具有重要作用. 随着锂离子的脱 关键词： 锂离子电池 4')" href="#">LiFePO₄ 电子结构 弹性性质