Electrochemical performance of Mo-doped LiFePO4/C composites prepared by two-step solid-state reaction

To improve the performance of LiFePO₄, LiFe_1?x Mo _x PO₄/C (x?=?0, 0.005, 0.010, 0.015, 0.020, 0.025) cathode materials were synthesized via two-step ball milling solid-state reaction. The prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectra, and galvanostatic charge–discharge test. It is apparent from XRD analysis that Mo doping enlarges the interplanar distance of crystal plane parallel to [010] direction in LiFePO₄. In other words, it widens one-dimensional diffusion channels of Li⁺ along the [010] direction. The results of electrochemical test indicate that the LiFe_0.99Mo_0.01PO₄/C composite exhibits a discharge capacity of 144.8 mAh g^?1 at 1 C rate, a decreased charge transfer resistance of 162.4 Ω and better reversibility of electrode reactions. The present synthesis route is promising and practical for the preparation of LiFePO₄ materials.     

Effects of yttrium ion doping on electrochemical performance of LiFePO<Subscript>4</Subscript>/C cathodes for lithium-ion battery

The olivine-type LiFe_1-x Y _x PO₄/C (x?=?0, 0.01, 0.02, 0.03, 0.04, 0.05) products were prepared through liquid-phase precipitation reaction combined with the high-temperature solid-state method. The structure, morphology, and electrochemical performance of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), energy-dispersive spectroscopy (EDS), galvanostatic charge-discharge, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). We found that the small amount of Y³⁺ ion-doped can keep the microstructure of LiFePO₄, modify the particle morphology, decrease charge transfer resistance, and enhance exchange current density, thus enhance the electrochemical performance of the LiFePO₄/C. However, the large doping content of Y³⁺ ion cannot be completely doped into LiFePO₄ lattice, but existing partly in the form of YPO₄. The electrochemical performance of LiFePO₄/C was restricted owing to YPO₄. Among all the doped samples, LiFe_0.98Y_0.02PO₄/C showed the best electrochemical performance. The LiFe_0.98Y_0.02PO₄/C sample exhibited the initial discharge capacity of 166.7, 155.8, 148.2, 139.8, and 121.1 mAh g^?1 at a rate of 0.2, 0.5, 1, 2, and 5 C, respectively. And, the discharge capacity of the material was 119.6 mAh g^?1 after 100 cycles at 5 C rates.     

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.     

LiFexMn1-xPO4固溶体的密度泛函理论与电化学研究

本文用DFT计算方法研究了LiFe_xMn_1-xPO₄的热力学稳定性和嵌/脱锂电位. 结果表明,LiFe_xMn_1-xPO₄固溶体的自由能比相分离的LiFePO₄/LiMnPO₄混合物略高,这两种形式可能在实际LiFe_xMn_1-xPO₄材料中共存. 计算表明,LiFe_xMn_1-xPO₄固溶体的嵌/脱锂电位随锰/铁比以及过渡金属离子的空间排列而变化,并用计算结果解释了放电曲线的形状. 采用固相反应法合成了LiFe_xMn_1-xPO₄材料并研究了其电化学性质,实验中观察到附加的放电平台,其出现可能与LiFe_xMn_1-xPO₄固溶体的存在有关.     

Hydrothermal synthesis and properties of manganese-doped LiFePO4

A series of carbon-coated LiFe_1???x Mn _x PO₄ compounds are prepared by a hydrothermal method at 170 °C for 12 h. The structure and morphology of the prepared composites are characterized to examine the effects of Mn²⁺ substitution. All LiFe_1???x Mn _x PO₄ compositions are found to have an ordered olivine-type structure with homogeneous Fe²⁺ and Mn²⁺ distributions. The substitution leads to grain refinement from ~500 to ~150 nm, as well as to increased initial capacity and improved electronic conductivity. The amount of carbon coating varies with increased doping amount. The discharge curves of the LiFe_1???x Mn _x PO₄/C materials reveal a high discharge plateau corresponding to Fe^2+/3+ and no obvious plateau assigned to Mn^2+/3+, although a slight contribution of manganese is detected. However, the electrochemical performance, including the discharge capacity and cyclic performance, deteriorates with increased Mn content in the composite.     

Synthesis and lithium-ion storage performances of LiFe<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>PO<Subscript>4</Subscript>/C nanoplatelets and nanorods

Carbon-coated olivine-structured LiFe_0.5Co_0.5PO₄ solid solution was synthesized by a facile rheological phase method and applied as cathode materials of lithium-ion batteries. The nanostructure’s properties, such as morphology, component, and crystal structure for the samples, characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer, Emmett, and Teller (BET) determination, X-ray photoelectron spectroscopy (XPS), and the electrochemical performances were evaluated using constant current charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results indicate that nanoplatelet- and nanorod-structured LiFe_0.5Co_0.5PO₄/C composites were separately obtained using stearic acid or polyethylene glycol 400 (PEG400) as carbon source, and the surfaces of particles for the two samples are ideally covered by full and uniform carbon layer, which is beneficial to improving the electrochemical behaviors. Electrochemical tests verify that the nanoplatelet LiFe_0.5Co_0.5PO₄/C shows a better capacity capability, delivering a discharge specific capacity of 133.8, 112.1, 98.3, and 74.4 mAh g^?1 at 0.1, 0.5, 1, and 5 C rate (1 C?=?150 mA g^?1); the corresponding cycle number is 5th, 11th, 15th, 20th, and 30th, respectively, whereas the nanorod one possesses more excellent cycling ability, with a discharge capacity of 83.3 mAh g^?1 and capacity retention of 86.9% still maintained after cycling for 100 cycles at 0.5 C. Results from the present study demonstrate that the LiFe_0.5Co_0.5PO₄ solid solution nanomaterials with favorable carbon coating effect combine the characteristics and advantage of LiFePO₄ and LiCoPO₄, thus displaying a tremendous potential as cathode of lithium-ion battery.     

Synthesis of Cr-doped LiMnPO4/C cathode materials by sol–gel combined ball milling method and its electrochemical properties

LiMn_1-x Cr _x PO₄/C (x?=?0, 0.01, 0.03, and 0.05) compounds are synthesized by a sol–gel combined ball milling method. The effects of Cr doping on the structure, morphology, and electrochemical performance of LiMnPO₄ are investigated. XRD analysis results indicate that all the samples exhibit the single LiMnPO₄ phase and Cr ions substitute on Mn site (x?≤?0.03), with charge compensating vacancies on Li site. The vacancies are of benefit to improving the electronic conductivity of LiMnPO₄. SEM studies reveal that Cr doping can effectively inhibit the aggregation of LiMnPO₄ particles. Electrochemical tests show that the Cr-doped samples exhibit higher initial capacities and better cycling performance than the undoped one. LiMn_0.97Cr_0.03PO₄/C exhibit the best electrochemical performance that the first specific discharge capacity is 132.4 mAh g^?1 at 0.1 C rate, and the capacity retention is 94.8 % after 30 cycles.     

Study on LiFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript>/C used as cathode materials for lithium-ion batteries with low Sm component

LiFe_1???x Sm _x PO₄/C cathode materials were synthesized though a facile hydrothermal method. Compared with high-temperature solid-phase sintering, the method can allow for the fabrication of low Sm content (2 %), a scarce and expensive rare earth element, while the presence of an optimized carbon coating with large amount of sp²-type carbon sharply increases the material’s electrochemical performance. The high-rate dischargeability at 5 C, as well as the exchange current density, can be increased by 21 and 86 %, respectively, which were attributed to the fine size and the large cell parameter a/c as much. It should be pointed out that the a/c value will be increased for the LiFePO₄ Sm-doped papered by both of the two methods, while the mechanism is different: The value c is increased for the front and the value a is decreased for the latter, respectively.     

Electrochemical comparison of LiFe<Subscript>0.4</Subscript>Mn<Subscript>0.595</Subscript>Cr<Subscript>0.005</Subscript>PO<Subscript>4</Subscript>/C and LiMnPO<Subscript>4</Subscript>/C cathode materials

A comparison of electrochemical performance between LiFe_0.4Mn_0.595Cr_0.005PO₄/C and LiMnPO₄/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe_0.4Mn_0.595Cr_0.005PO₄/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 163.6 mAh g^?1 at 0.1C (1C = 160 mA g^?1), compared to 112.3 mAh g^?1 for LiMnPO₄/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO₄/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li⁺ diffusion in the structure. Furthermore, LiFe_0.4Mn_0.595Cr_0.005PO₄/C composite presented high energy density (606 Wh kg^?1) and high power density (574 W kg^?1), thus suggested great potential application in lithium ion batteries (LIBs).     

Synthesis and characterization of Li<Subscript>1-x</Subscript>Tb<Subscript>x</Subscript>NiPO<Subscript>4</Subscript> solid solution as cathode materials for lithium ion battery application

Modified Pechini-type polymerizable precursor method has been used to prepare nanosized Li_1-xTb_xNiPO₄ (x = 0, 0.03, 0.05, and 0.07) solid solutions to obtain homogeneous with controlled stoichiometry and smaller particle size. The reaction temperature was determined by thermogravimetric (TG/DTA) analysis. X-ray diffraction analysis reveals the formation of orthorhombic structure and the calculated crystallite sizes are found to be in the range of 75–89 nm. Morphological, compositional, and vibrational properties were performed by SEM, EDAX, and FTIR, respectively. Conductivity measurements were carried out at room temperature by AC impedance analysis. The Li_0.97Tb_0.03Ni_0.99PO₄ sample shows one order of higher conductivity than pure LiNiPO₄. Higher concentration of terbium samples such as Li_0.95Tb_0.05Ni_0.99PO₄ and Li_0.93Tb_0.07Ni_0.99PO₄ lead to decrease of conductivity. The frequency dependency of dielectric permittivity, dielectric loss, and electric modulus of Li_1-x Tb_xNiPO₄ solid solutions are studied. The frequency-dependent plot of modulus reveals that the conductivity relaxation is of non-Debye type.     

Synthesis and electrochemical characterization of graphene nanoflakes and LiFe<Subscript>0.97</Subscript>Ni<Subscript>0.03</Subscript>PO<Subscript>4</Subscript>/C for lithium-ion battery

The graphene nanoflakes and olivine-type LiFe_0.97Ni_0.03PO₄/C (LFNP3/C) samples have been synthesized as anode and cathode materials, respectively. Physicochemical characterization of the graphene nanoflakes and LFNP3/C material were studied using X-ray diffraction (XRD) and scanning electron microscope (SEM). The XRD patterns reveal the formation of the pure phase of both the synthesized samples. SEM micrographs disclose the formation of spherically shaped nanosized particles for LFNP3/C while graphene shows flake-type morphology. CR2032 half and full coin cells were assembled for electrochemical testing of the synthesized samples. Cyclic voltammetry (CV) results indicate that the graphene-based half-cells, i.e., GN1H and GN2H, possess reduction peak/plateau around 0.17 V while LFNP3/C cathode shows discharging voltage plateau at 3.4 V vs. Li/Li⁺. The discharge capacities were found to be 700, 900, and 153 mAhg^?1 for GN1H, GN2H, and LFNP3/C half-cells vs. Li/Li⁺, respectively. Among full cells, LFPGN1F with γ = 0.75 (mass/capacity balancing factor) shows better charging/discharging profile at each C-rate as compared to LFPGN2F with γ = 0.55. LFPGN1F delivered an initial discharge capacity of around 154 mAhg^?1 at 0.1C and even at a high discharge rate of 1C, it retained ~97% of the discharge capacity as compared to the initial cycle at the same rate.     

通过掺杂V和F提高碳包覆的磷酸铁锂锂离子电池的电化学性能

在原位聚合合成方法的基础上,结合两步烧结过程制得LiFe_1-xV_x(PO₄)_(3-y)/₃F_y/C.V和F掺杂对碳包覆的磷酸铁锂材料的结构、形貌和电化学性能有影响.通过XRD、FTIR、SEM、充/放电测试和电化学阻抗谱对材料的结构、形貌和电化学性能进行了表征.结果表明,V和F的掺杂并没有破坏橄榄石结构中的LiFePO₄/C,但可以提高晶体结构的稳定,降低电荷的转移阻抗,提高锂离子扩散速度,改善了LiFePO₄/C材料的循环性能和高倍率性能.     

Mn掺杂LiFePO4的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 计算了不同Mn掺杂浓度LiFe_1-xMn_xPO₄ (x=0,0.25,0.50,0.75) 的电子结构. 同时采用流变相辅助高温固相碳热还原法制备了LiFe_1-xMn_xPO₄ (x= 0,0.25,0.50,0.75) 材料. 理论计算表明: LiFePO₄具有E_g = 0.725 eV的带隙宽度, 为半导体材料. 通过Fe位掺杂25%的Mn离子可最大程度地 减小材料带隙宽度、降低Fe---O键及Li---O键键能, 进而提高材料的电子电导率及锂离子扩散速率. 实验结果亦表明, 当Mn掺杂量x=0.25时, 材料具有最优的电化学性能, 其具有约为158 mAh· g^-1的放电比容量以及551 Wh· kg^-1的能量密度. 理论计算与实验结果非常符合.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Electrochemical properties of LiFe0.9Mg0.1PO4 / carbon cathode materials prepared by ultrasonic spray pyrolysis

The LiFe_0.9Mg_0.1PO₄/C powder of pure olivine phase can be prepared with the duplex process of spray pyrolysis synthesis (at 450 ^°C) and subsequent heat treatment (at 700 ^°C for 2, 4 and 8 h). From scanning electron microscopy observation with corresponding elemental mapping images of iron, phosphorous and magnesium, it could be found that the LiFe_0.9Mg_0.1PO₄ powders are covered with fine pyrolyzed carbon. Raman spectra indicate that the phase of carbon with higher electronic conductive phase is predominant when prolonged subsequent heat treatment is carried out. The carbon coatings on the LiFe_0.9Mg_0.1PO₄ surface can improve the conductivity of the LiFe_0.9Mg_0.1PO₄ powder (3.8×10⁻⁵ S cm⁻¹) to about a factor of ∼10⁴ higher than the conductivity of LiFePO₄. The stability and cycle life of a charge/discharge cycle test of lithium ion secondary batteries are also enhanced. The results indicate that the LiFe_0.9Mg_0.1PO₄ powder, prepared at a pyrolysis temperature of 450 ^°C and with post-heat-treatment at 700 ^°C for 8 h, exhibits a specific initial discharge capacity of about 132 mA h g⁻¹ at C/10 rate, 105 mA h g⁻¹ at 1C, and 87 mA h g⁻¹ at 5C.     

Li3V2(PO4)3 modified LiFePO4/C cathode materials with improved high-rate and low-temperature properties

LiFePO₄/C surface modified with Li₃V₂(PO₄)₃ is prepared with a sol–gel combustion method. The structure and electrochemical behavior of the material are studied using a wide range of techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. It is found that LiFePO₄/C surface modified with Li₃V₂(PO₄)₃ has the better electrochemical performance. The discharge capacity of the as-prepared material can reach up to 153.1, 137.7, 113.6, and 93.3 mAh g^?1 at 1, 2, 5, and 10 C, respectively. The capacitance of the LiFePO₄/C modified by Li₃V₂(PO₄)₃ is higher under lower discharging rate at ?20 °C, and the initial discharge capacity of 0.2 C is 131.4 mAh g^?1. It is also demonstrated that the presence of Li₃V₂(PO₄)₃ in the sample can reduce the charge transfer resistance in the range of ?20 to 25 °C, resulting in the enhanced electrochemical catalytic activity.     

Modified carbothermal synthesis and electrochemical performance of LiFePO4/C composite as cathode materials for lithium-ion batteries

LiFePO₄/C active materials were synthesized via a modified carbothermal method, with a low raw material cost and comparatively simple synthesis process. Rheological phase technology was introduced to synthesize the precursor, which effectively decreased the calcination temperature and time. The LiFePO₄/C composite synthesized at 700 °C for 12 h exhibited an optimal performance, with a specific capacity about 130 mAh g^?1 at 0.2C, and 70 mAh g^?1 at 20C, respectively. It also showed an excellent capacity retention ratio of 96 % after 30 times charge–discharge cycles at 20C. EIS was applied to further analyze the effect of the synthesis process parameters. The as-synthesized LiFePO₄/C composite exhibited better high-rate performance as compared to the commercial LiFePO₄ product, which implied that the as-synthesized LiFePO₄/C composite was a promising candidate used in the batteries for applications in EVs and HEVs.     

NMR Investigations of the Protonic Transport Mechanism in Composed Materials on the Basis of Cesium Acid Sulfates and Phosphates

The composite materials Cs(HSO₄)_1?x (H₂PO₄) _x were investigated by X-ray phase analysis, differential scanning calorimetry, nuclear magnetic resonance (NMR) relaxation, pulsed field gradient NMR (PFG-NMR) and impedance spectroscopy. Three composite materials types x = 0.1 ÷ 0.3 mixture CsHSO₄, α-Cs₃(HSO₄)₂(H₂PO₄), β-Cs₃(HSO₄)_2.5(H₂PO₄)_0.5—compositions of area I; x = 0.4 ÷ 0.5 mixture α-Cs₃(HSO₄)₂(H₂PO₄) and Cs₂(HSO₄)(H₂PO₄)—compositions of area II; x = 0.6 ÷ 0.9 mixture Cs₂(HSO₄)(H₂PO₄) and CsH₂PO₄—compositions of area III, were synthesized. The phase transition temperature from the low-to-high conductive phase for obtained composite materials is notably below (about 100 °C) than that for the individual components. The proton self-diffusion coefficients measured by PFG-NMR are lower than the diffusion coefficients calculated from proton conductivities data. The correlation times τ _d controlling the ³¹P–¹H magnetic dipole–dipole interaction were calculated according to data of the spin–lattice relaxation on ³¹P nuclei. The self-diffusion coefficients estimated from the Einstein equation are in good agreement with the experimental self-diffusion coefficients measured by PFG-NMR. It confirms the fact that the proton mobility is caused by the rotation of PO₄ anion tetrahedra.     

Enhanced electrochemical performance of LiFePO4/C prepared by sol–gel synthesis with dry ball-milling

LiFePO₄/C was prepared by a modified aqueous sol–gel route developed by incorporating an additional ball-milling step where the dry gel was milled with the additives of synthetic graphite and carbon black. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), transmission electron microscopy (TEM), high resolution TEM (HRTEM) and elemental analysis. Results showed that the LiFePO₄/C synthesized by suitable ball-milling process had pure, fine and homogenous LiFePO₄ particles. Results of cyclic voltammetry and charge/discharge plateaus demonstrated that the LiFePO₄/C composite synthesized by milling for 2 h had much better electrochemical kinetics. High performances were achieved with its discharge capacities of 157 mA h g^?1 at 0.1?C and 133 mA h g^?1 at 1?C between 2.5 and 4.2 V (1?C?=?170 mA g^?1). And no obvious capacity fading was observed upon cycling. The simple and convenient synthesis route is promising for large-scale production of LiFePO₄/C.     

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.