The Surface Coating of Commercial LiFePO_4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

The requirement of energy-storage equipment needs to develop the lithium ion battery(LIB) with high electrochemical performance. The surface modification of commercial LiFePO_4(LFP) by utilizing zeolitic imidazolate frameworks-8(ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances.In this work, the carbonized ZIF-8(C_(ZIF-8)) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/C_(ZIF-8) sample. The N_2 adsorption and desorptionisotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/C_(ZIF-8) cathode-active material delivers a discharge specific capacity of 159.3 m Ah g^(-1) at 0.1 C and a discharge specific energy of 141.7 m Wh g^(-1) after 200 cycles at 5.0 C(the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity,the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/C_(ZIF-8) cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.

Controllable synthesis of high loading LiFePO_4/C nanocomposites using bimodal mesoporous carbon as support for high power Li-ion battery cathodes

Mesoporous LiFePO4/C composites containing 80 wt% of highly dispersed LiFePO4 nanoparticles(4-6 nm) were fabricated using bimodal mesoporous carbon(BMC) as continuous conductive networks. The unique pore structure of BMC not only promises good particle connectivity for LiFePO4, but also acts as a rigid nano-confinement support that controls the particle size. Furthermore, the capacities were investigated respectively based on the weight of LiFePO4 and the whole composite. When calculated based on the weight of the whole composite, it is 120 mAh·g-1at 0.1 C of the high loading electrode and 42 mAh·g-1at 10 C of the low loading electrode. The electrochemical performance shows that high LiFePO4 loading benefits large tap density and contributes to the energy storage at low rates, while the electrode with low content of LiFePO4 displays superior high rate performance, which can mainly be due to the small particle size, good dispersion and high utilization of the active material, thus leading to a fast ion and electron diffusion.

Regeneration of spent LiFePO4 as a high-performance cathode material by a simultaneous coating and doping strategy

With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal salts are economically inefficient and polluting.Meanwhile,the recycled material obtained by lithium remediation alone has limited performance in cycling stability.Herein,a short method of solid-phase reduction is developed to recover spent LiFePO4 by simultaneously introducing Mg2+ions for hetero-atom doping.Issues of particle agglomeration,carbon layer breakage,lithium loss,and Fe3+defects in spent LiFePO4 are also addressed.Results show that Mg2+addition during regeneration can remarkably enhance the crystal structure stability and improve the Li+diffusion coefficient.The regenerated LiFePO4 exhibits significantly improved electrochemical performance with a specific discharge capacity of 143.2 mAh·g^(−1)at 0.2 C,and its capacity retention is extremely increased from 37.9%to 98.5%over 200 cycles at 1 C.Especially,its discharge capacity can reach 95.5 mAh·g^(−1)at 10 C,which is higher than that of spent LiFePO4(55.9 mAh·g^(−1)).All these results show that the proposed regeneration strategy of simultaneous carbon coating and Mg2+doping is suitable for the efficient treatment of spent LiFePO4.

Electrochemical performance of LiFePO_4 cathode material for Li-ion battery

In the search for improved materials for rechargeable lithium batteries, LiFePO4 offers interesting possibilities because of its low raw materials cost, environmental friendliness and safety. The main drawback with using the material is its poor electronic conductivity and this limitation has to be overcome. Here Al-doped LiFePO4/C composite cathode materials were prepared by a polymer-network synthesis technique. Testing of X-ray diffraction, charge-discharge, and cyclic voltammetry were carried out for its performance. Results show that Al-doped LiFePO4/C composite cathode materials have a high initial capacity, good cycle stability and excellent low temperature performance. The electrical conductivity of LiFePO4 material can be obviously improved by doping Al. The better electrochemical performances of Al-doped LiFePO4/C composite cathode materials have a connection with its conductivity.

A Novel Real-Time State-of-Health and State-of-Charge Co-Estimation Method for LiFePO_4 Battery

The state of charge （SOC） and state of health （SOH） are two of the most important parameters of Li-ion batteries in industrial production and in practical applications. The real-time estimation for these two parameters is crucial to realize a safe and reliable battery application. However, this is a great problem for LiFePO4 batteries due to the large constant potential plateau in the charge/discharge process. Here we propose a combined SOC and SOH co-estimation method based on the experimental test under the simulating electric vehicle working condition. A first-order resistance-capacitance equivalent circuit is used to model the battery cell, and three parameter values, ohmic resistance （Rs）, parallel resistance （Rp） and parallel capacity （Cp）, are identified from a real-time experimental test. Finally we find that Rp and Cp could be utilized to make a judgement on the SOIl. More importantly, the linear relationship between Cp and the SOC is established to make the estimation of the SOC for the first time.

Synthesis and electrochemical performances of spherical LiFePO_4 cathode materials for Li-ion batteries

Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g-1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g-1. The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.

Electrochemical performance of carbon nanotube-modified LiFePO_4 cathodes for Li-ion batteries

Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and electrochemical performances of as-prepared LiFePO4 were evaluated by means of transmission electron microscopy (TEM), charge-discharge test, electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV). CNTs contribute to the interconnection of the isolated LiFePO4 or carbon particles. For the CNTs-modified LiFePO4, it exhibits excellent performance in terms of both specific capacity and cycle life. The initial discharge capacity is 147.9 mA·h/g at 0.2C rate and 134.2 mA·h/g at 1C rate, keeping a capacity retention ratio of 97% after 50 cycles. The results from EIS indicate that the impedance value of the solid electrolyte interface decreases. The cyclic voltammetric peak profiles is more symmetric and spiculate and there are fewer peaks. CNTs are promising conductive additives candidate for high-power Li-ion batteries.

Research Progress in Improving the Rate Performance of LiFePO_4 Cathode Materials

Olivine lithium iron phosphate(Li Fe PO4) is considered as a promising cathode material for high power density lithium ion battery due to its high capacity, long cycle life, environmental friendly, low cost, and safety consideration. The theoretical capacity of Li Fe PO4 based on one electron reaction is 170 m Ah g-1at the stable voltage plateau of 3.5 V vs. Li/Li+. However, the instinct drawbacks of olivine structure induce a poor rate performance, resulting from the low lithium ion diffusion rate and low electronic conductivity.In this review, we summarize the methods for enhancing the rate performance of Li Fe PO4 cathode materials,including carbon coating, elements doping, preparation of nanosized materials, porous materials and composites,etc. Meanwhile, the advantages and disadvantages of above methods are also discussed.

A novel synthetic route for LiFePO_4/C cathode materials by addition of starch for lithium-ion batteries

LiFePO4/Carbon composite cathode material was prepared using starch as carbon source by spray-pelleting and subsequent pyrolysis in N2. The samples were characterized by XRD, SEM, Raman, and their electrochemical performance was investigated in terms of cycling behavior. There has a special micro-morphology via the process, which is favorable to electrochemical properties. The discharge capacity of the LiFePO4.C composite was 170 mAh g-1, equal to the theoretical specific capacity at 0.1 C rate. At 4 C current density, the specific capacity was about 80 mAh g-1, which can satisfy for transportation applications if having a more flat discharge flat.

粒径可控纳米LiFePO4/C的制备及其电化学性能研究

LiFePO4电极的倍率特性与材料的粒度和电子导电性有很大关系.采用共沉淀方法,调控预处理温度,将3种不同尺寸的FePO4前驱体通过表面修饰对-羟基苯甲酸的聚合物,可合成不同尺度的LiFePO4/C材料,分别为80 nm、200nm和1μm.纳米尺度LiFePO4-a/C电极,30C放电比容量达到了100 mAh·g-1,而微米级LiFePO4-c/C电极放电比容量仅为54mAh·g-1.均一碳包覆的LiFePO4/C电极表现出强抗氧化性,不仅提高其导电性,还可防止材料氧化.

Review on Li-insertion/extraction Mechanisms of LiFePO4 Cathode Materials

The work distills the main mechanisms during the lithium insertion/extraction of LiFePOcathode materials. The "diffusion-controlled" and "phase-boundary controlled" mechanism are especially illustrated. Meanwhile, some recent observation and analyses by in-situ or in operando on the Li-insertion/extraction of LiFePOare summarized and prospected.

Synthesis of LiFePO_4 using FeSO_4·7H_2O byproduct from TiO_2 production as raw material

As the byproduct of TiO2 industrial production, impure FeSO4.7H2O was used for the synthesis of LiFePO4. With the purified solution of FeSO4-7H2O, FePO4.xH2O was prepared by a normal titration method and a controlled crystallization method, respectively. Then LiFePO4 materials were synthesized by calcining the mixture of FePO4,xH2O, LizCO3, and glucose at 700℃ for 10 h in flowing Ar. The results indicate that the elimination of FeSO4.TH2O impurities reached over 95%, and using FePO4-xH2O prepared by the controlled crystallization method, the obtained LiFePO4 material has fine and sphere-like particles. The material delivers a higher initial discharge specific capacity of 149 mAh.g^-1 at a current density of 0.1C rate （1C = 170 mA.g^-0）; the discharge specific capacity also maintains above 120 rnAh.g^-1 after 100 cycles even at 2C rate. Thus, the employed processing is promising for easy control, low cost of raw material, and high electrochemical performance of the prepared material.

锂离子电池正极材料LiFePO4制备技术研究进展

磷酸铁锂材料具有良好的循环性、热稳定性、环保性,在锂离子电池正极材料中已得到广泛研究。由于该材料电导率低、锂离子扩散速率慢等缺点影响其在电池领域的发展。介绍了锂离子电池正极材料磷酸铁锂的基本结构、制备方法以及针对其材料的不足而进行的材料改性方法,同时对目前磷酸铁锂材料存在的问题及前景进行了综述,分析了改善磷酸铁锂材料性能的途径,并展望了磷酸铁锂正极材料未来的发展趋势。

Physical and Electrochemical Properties of Doped LiFePO4 as Cathode Material for Lithium-Ion Batteries

LiFePO4 cathode material was synthesized by a solid-state reaction using doping several elements (Nb5 + ,Zr4 + ). The starting materials were mixed with a high-efficient sander and treated thermally under flowing N2. The samples were characterized by X-ray diffraction (XRD), field-emission gun electron microscopy (FEG), and their electrochemical performance was investigated in the term of cycling behavior. Room temperature discharge capacity about 140.6 mA·h·g-1 was obtained at C/5 rate.

Synthesis and performance of carbon-modified LiFePO_4 using an in situ PVA pyrolysis procedure

LiFePOa/carbon composite cathode material was prepared by granulating and subsequent pyrolysis processing in N2 atmosphere with polyvinyl alcohol （PVA） as the carbon source. The influences of carbon content on the microstructure and battery performance were investigated. Single LiFePO4 phase and amorphous carbon can be found in the products. A special micro-morphology of the optimum sample was observed. The discharge capacity of the cell with the optimum cathode was 135 mAh.g^-1, close to the charge capacity of 153 mAh.g^-1 at 17 mA.g^-1. The influence of ambient temperature on the cell capacity was investigated. The temperature dependence of its electrochemical characteristic was evaluated by using AC impedance spectroscopy. A new equivalent circuit based on the charge and mass transfer control process in an electrode was proposed to fit the obtained AC impedance spectra. The tendency of every element in the equivalent circuit was used to interpret the temperature dependence of the capacity of the optimum cathode.

Pure LiFePO4 with high energy density prepared by water quenching treatment

A compound ＂vacuum firing and water quenching＂ technique was presented in the synthesis of LiFeP04 cathode powder. The sample was prepared by heating the we-decomposed precursor mixtures sealed in vacuum quartz-tube, followed by water quenching at the sintering temperature. The results indicate that using the ＂fast quenching＂ treatment can succeed in controlling overgrowth of the grain size of final product and improving its utilization ratio of active material. The sample synthesized by this technique has the high reversible discharge specific capacity and good cyclic electrochemical performance.

Synthesis of Low-cost LiFePO_4 from Li_2CO_3 by a Novel Hydrothermal Method and Investigation on the Reaction Mechanism

Phspho-olivine Li Fe PO4 was synthesized from the relatively insoluble lithium source Li2CO3, proper iron and phosphorus sources（n（Li）：n（Fe）：n（P）=1：1：1） by a novel hydrothermal method. Afterwards, the optimal sample was mixed with glucose and two-step calcinated（500 ℃ and 750 ℃） under high-purity N2 to obtain the Li Fe PO4/C composite. The resultant samples were characterized by X-ray diffraction（XRD）, atomic absorption spectrometry（AAS）, scanning electron microscops（SEM）, transmission electron microscopy（TEM）, energy dispersive spectrometry（EDS）, elementary analysis（EA） and electrochemical tests. The results show that the optimal reaction condition is to set the reactant concentration at 0.5 mol·L^-1, the reaction temperature at 180 ℃ for 16 h duration. During the reaction course, an intermediate product NH4 Fe PO4·H2O was first synthesized, and then it reacted with Li＋ to form Li Fe PO4. The optimized Li Fe PO4 sample with an average particle size（300 to 500 nm） and regular morphology exhibits a relatively high discharge capacity of 84.95 m Ah· g^-1 at the first charge-discharge cycle（0.1C, 1C=170 m A·g^-1）. Moreover, the prepared Li Fe PO4/C composite shows a high discharge capacity of 154.3 m Ah·g^-1 at 0.1C and 128.2 m Ah·g^-1 even at 5C. Besides it has good reversibility and stability in CV test.

An Improved Method to Prepare FePO4 by Introduction of Na3PO4 and Its Usage for Fabricating LiFePO4

A LiFePO4/C composite was synthesized by a simple solid-state reaction method using glucose as reductive agent and carbon source and FePO4 as precursor, which was prepared by introduction of Na3PO4 as phosphorus source and pH regulator in order to pursue lower cost and environmental protection. The structure and morphology of FePO4 and LiFePO4/C were investigated by X-ray diffraction(XRD) and scanning electron microscopy(SEM). Furthermore, electrochemical performance of LiFePO4/C was investigated by galvanostatic charge–discharge tests and cyclicvoltammogram(CV). The results indicate that FePO4 obtained has a small particle size and uniform particle distribution, which is demonstrated to be applicable as the iron source to synthesize LiFePO4/C. Prepared LiFePO4/C shows an excellent rate capability and cycle performance. At rates of 0.1 C, 0.2 C, 1 C and 2 C, the initial discharge capacities of 161, 158, 145 and 120 mAh/g were achieved, respectively and the discharge capacity is 154, 153, 140 and 116 mAh/g after 400 cycles. The employed method of preparing FePO4 by introduction of Na3PO4 has advantages such as low cost, safe raw material, environmental benign and recyclable products, which is suitable for industrial production.