Synthesis of porous nano/micro structured LiFePO_4/C cathode materials for lithium-ion batteries by spray-drying method

In order to enhance electrochemical properties of LiFePO4 （LFP） cathode materials, spherical porous nano/micro structured LFP/C cathode materials were synthesized by spray drying, followed by calcination. The results show that the spherical precursors with the sizes of 0.5-5 μm can be completely converted to LFP/C when the calcination temperature is higher than 500 ℃. The LFP/C microspheres obtained at calcination temperature of 700 ℃ are composed of numerous particles with sizes of -20 nm, and have well-developed interconnected pore structure and large specific surface area of 28.77 mE/g. The specific discharge capacities of the LFP/C obtained at 700 ℃ are 162.43, 154.35 and 144.03 mA.h/g at 0.5C, 1C and 2C, respectively. Meanwhile, the capacity retentions can reach up to 100% after 50 cycles. The improved electrochemical properties of the materials are ascribed to a small Li＋ diffusion resistance and special structure of LFP/C microspheres.

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.

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.

One Step Ball-Milling Synthesis of LiFePO_ 4 Nanoparticles as the Cathode Material of Li-Ion Batteries

A one-step synthetic method was used to synthesize Olivline LiFePO4 powders by direct ball milling the stoichiometric mixture of Fe, Li3PO4 , and FePO4 powders. XRD and TEM measurements revealed that the as-prepared LiFePO4 powder have a homogeneous Olivine structure and a uniform size distribution of ca. 50 nm. Based on this material, a LiFePO4/C composite was prepared and used for the cathode material of Li-ion batteries. The charge-discharge experiments demonstrated that the LiFePO4/C composite material has a high capacity of 132 mAh/g at 0.1 C and a quite highrate capability of 95 mAh/g at 1 C. This new ball-milling method may provide a completely green synthetic route for preparing the materials of this type cost-effectively and in large volume.

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.

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.

Characterization and Electrochemical Performance of ZnO Modified LiFePO_4/C Cathode Materials for Lithium-ion Batteries

To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. The structures and compositions of ZnO modified LiFePO4/C cathode materials are characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy, which indicates that the existence of ZnOhas little or no effect on the crystal structure, particles size and morphology of LiFePO4. The electrochemical performances are also characterized and analyzed with charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the existence of ZnO improves the specific capability and lithium ion diffusion rate of LiFePO4 cathode materials and reduces the charge transfer resistance of cell, and the one with 3 wt% ZnO exhibits the best electrochemical performance.

Synthesis and electrochemical properties of Li_(1-x)V_xCr_yFe_(1-x)PO_4/C as a cathode material

Composites Li1-xVxCryFe1-yPO4/C（x=0.01, 0.02; y = 0.01, 0.02） were synthesized by solid-state reaction method. The influence of the content of doping vanadium and chromium on the structure of Li1-xVxCryFe1-yPO4/C was investigated by XRD, while the morphology of powders was observed by SEM. The investigation of the electrochemical performances showed that the Li0.99V0.01Cr0.02Fe0.98PO4/C material has a higher capacity. At 0.1 C discharging rate, it is capable of delivering reversible specific capacity of 163.8 mAh/g with fairly stable cycleability.

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.

Synthesis of nanostructured Li_2FeSiO_4/C cathode for lithium-ion battery by solution method

Nanosphere-like Li2FeSiO4/C was synthesized via a solution method using sucrose as carbon sources under a mild condition of time-saving and energy-saving, followed by sintering at high temperatures for crystallization. The amount of carbon in the composite is less than 10% （mass fraction）, and the X-ray diffraction result confirms that the sample is of pure single phase indexed with the orthorhombic Pmn21 space group. The particle size of the Li2FeSiO4/C synthesized at 700 °C for 9 h is very fine and spherical-like with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, were tested. The cell of this sample can deliver a discharge capacity of 166 mA-h/g at C/20 rate in the first three cycles. After 30 cycles, the capacity decreases to 158 mA-h/g, and the capacity retention is up to 95%. The results show that this method can prepare nanosphere-like Li2FeSiO4/C composite with good electrochemical performance.

Synthesis of LiMnPO_4/C composite material for lithium ion batteries by sol-gel method

The LiMnPO4/C composite material was synthesized via a sol-gel method based on the citric acid. The X-ray diffraction （XRD）, scanning electron microscopy （SEM） and electrochemical performance tests were adopted to characterize the properties of LiMnPO4/C. The XRD studies show that the pure olivine phase LiMnPO4 can be obtained at a low temperature of 500 °C. The SEM analyses illustrate that the citric acid used as the chelating reagent and carbon source can restrain the particle size of LiMnPO4/C well. The LiMnPO4/C sample synthesized at 500 °C for 10 h performs the highest initial discharge capacity of 122.6 mA-h/g, retaining 112.4 mA-h/g over 30 cycles at 0.05C rate. The citric acid based sol-gel method is favor to obtain the high electrochemical performance of LiMnPO4/C.

喷雾干燥条件对合成纳/微结构LiFePO_4/C形貌及性能的影响

采用湿法球磨-喷雾干燥-碳热还原制备纳/微结构LiFePO4/C复合材料。通过XRD、SEM表征材料结构形貌,利用充放电测试循环伏安、交流阻抗测试等表征电化学性能,分别考察不同喷雾干燥条件对其形貌及性能的影响。结果表明:浆料浓度、进风温度、进料速率对材料形貌及性能影响较大,喷嘴口径对性能影响较小,随着浆料浓度的减小,所得样品由碗状结构转变为球形。最佳喷雾干燥条件为浆料浓度200g/L,进风温度200℃,进料速率1.3L/h,喷嘴口径0.5mm。此条件下制备的材料表现出最佳的放电比容量,常温下材料在0.5C倍率下的放电比容量为160mAh·g-1,10C放电比容量为123mAh·g-1,循环100次后容量几乎无衰减。

Synthesis and characterization of LiFePO_4 coating with aluminum doped zinc oxide

Aluminum doped zinc oxide （AZO）, as an electrically conductive material, was applied to coating on the surface of olivine-type LiFePO4 synthesized by solid-state method. The charge-discharge test results show that the rate performance and low-temperature performance of LiFePO4 are greatly improved by the surface treatment. Even at 20C rate, the discharge specific capacity of 100.9 mA.h/g was obtained by the AZO-coated LiFePO4 at room temperature. At -20 ℃, the discharge specific capacity at 0.2C for un-coated LiFePO4 and the coated one are 50.3 mA.h/g and 119.4 mA.h/g, respectively. It should be attributed to the electrically conductive AZO-coating which increases the electronic conductivity of LiFePO4. Furthermore, the surface-coating increases the tap-density of LiFePO4. The results indicate that the AZO-coated LiFePO4 is a good candidate of cathode material for applying in lithium power batteries.

采用两步固相法配合表面活性剂制备LiMn_(0.7)Fe_(0.3)PO_(4)/C正极材料的研究

磷酸锰铁锂复合材料能够兼具磷酸铁锂和磷酸锰锂优点,得到较高的能量密度,但锰铁比过高反而会降低材料的离子电导率和电子电导率。为了提高电导率并降低材料阻抗,采用表面活性剂油酸辅助的两步固相方法,制备了粒径较小、孔隙分布均匀且碳包覆薄厚均匀适中的LiMn_(0.7)Fe_(0.3)PO_(4)/C正极材料(LFMP/C-3)。循环充放电测试表明,该材料在1C下放电比容量为119.6 mA·h/g,循环100次后为102.8 mA·h/g,循环效率为88.87%。经倍率测试得出,在0.1C、0.5C、1C、2C、5C和10C倍率下的平均放电比容量分别为141.08、132.70、128.44、105.86、89.10、83.40 mA·h/g,在之后的0.1C倍率下仍能恢复到开始5次的平均水平。循环伏安(CV)和交流阻抗(EIS)测试表明,LFMP/C-3样品具备较小的极化程度、最低的电荷转移阻抗(139.75Ω/s^(1/2))和较高的锂离子扩散系数(1.46×10^(-14)cm^(2)/s)。结果表明,油酸的加入可获得良好的形貌特征,从而促进锂离子的脱嵌,提高材料的离子电导率和电子电导率,提高磷酸锰铁锂正极材料的电化学性能。

Electrochemical performance of Ti^(4+)-doped LiFePO_4 synthesized by co-precipitation and post-sintering method

Ti4+-mixed FePO4·xH2O precursor was prepared by co-precipitation method,with which Ti4+ cations were added in the process of preparing FePO4·xH2O to pursue an effective and homogenous doping way.Ti4+-doped LiFePO4 was prepared by an ambient-reduction and post-sintering method using the as-prepared precursor,Li2CO3 and oxalic acid as raw materials.The samples were characterized by scanning electron microscopy (SEM),X-ray diffractometry (XRD),electrochemical impedance spectroscopy (EIS),and electrochemical charge/discharge test.Effects of Ti4+-doping and sintering temperature on the physical and electrochemical performance of LiFePO4 powders were investigated.It is noted that Ti4+-doping can improve the electrochemical performance of LiFePO4 remarkably.The Ti4+-doped sample sintered at 600 ℃ delivers an initial discharge capacity of 150,130 and 125 mA·h/g with 0.1C,1C and 2C rates,respectively,without fading after 40 cycles.

Synthetic LiFePO4/C without using inert gas

LiFePO4/C was synthesized by high temperature solid-state method with cheap Fe2O3, LiH2PO4 and glucose as raw materials in absence of inert gas. The sample had ordered olivine-type structure other impurities characterized by the test of X-ray diffraction （XRD）. The charge-discharge test showed the sample could demonstrate 120.5 mAh/g at 0.2C rate with good cyclic capability. The powder microeleetrode cyclic voltammetry test indicated that the redox process of the sample had good reversibility.

Preparation and Characterization of Novel Ti-doped M-site Deficient Olivine LiFePO_4

A novel Ti-doped M-site deficient olivine LiFePO4, i.e. Li0.95Fe0.95Ti0.05PO4, was synthesized by a solid-state reaction method. XRD and VTR were used to characterize the as-prepared samples. As a cathode material for lithium-ion batteries, Li0.95Fe0.95Ti0.05PO4 exhibited improved rate capability.

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.

LiFePO_4/C via fluoride doping

Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping cannot change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were detected. Charge-discharge curves show that fluoride-doped samples have higher capacity at low rates compared with undoped LiFePO4/C. AlF3-doped samples have highest capacity at high discharge current. Both doped samples have larger polarization voltage than undoped samples. All samples exhibit good cycle stability.

Effects of Co^(2+)Doping on the Crystal Structure and Electrochemical Performance of LiFePO_4

Co2＋-doped LiFePO4/C composite material was prepared by solid-state synthesis method using Fe2O3,Li2CO3 and NH4H2PO4 as the starting materials.The structures and elec-trochemical performance of samples were studied by XRD,SEM and constant current charge-discharge method.The results showed that the Co2＋ doping did not change the crystal structure of LiFePO4.The unit cell volume changed with the increase of Co2＋,and reached the maximum at x = 0.04.The LiFe0.96Co0.04PO4/C sample proved the best electrochemical properties.Its initial discharge capacity was 138.5 mA·h /g at 1 C rate.After 30 cycles,the capacity remained 127.7 mA·h /g,and the capacity retention rate was 92.2%.