Nitrogen-doped carbon nanofiber decorated LiFePO<Subscript>4</Subscript> composites with superior performance for lithium-ion batteries

Nitrogen-doped carbon nanofiber (NCNF) decorated LiFePO₄ (LFP) composites are synthesized via an in situ hydrothermal growth method. Electrochemical performance results show that the embedded NCNF can improve electron and ion transfer, thereby resulting in excellent cycling performance. The as-prepared LFP and NCNF composites exhibit excellent electrochemical properties with discharge capacities of 188.9 mAh g^?1 (at 0.2 C) maintained at 167.9 mAh g^?1 even after 200 charge/discharge cycles. The electrode also presents a good rate capability of 10 C and a reversible specific capacity as high as 95.7 mAh g^?1. LFP composites are a potential alternative high-performing anode material for lithium ion batteries.     

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 high-energy milling on the solid-state synthesis of pure nano-sized Li4Ti5O12 for high power lithium battery applications

Li₄Ti₅O₁₂ was synthesized from Li₂CO₃ and anatase TiO₂ using different degree of milling to test the hypothesis that finer starting materials can result in a smaller Li₄Ti₅O₁₂ particle size and better high-rate discharging capacities. The degree of milling was controlled using three different ZrO₂ media sizes for 3 hours of high-energy milling, whereas 5 mm balls were used for 24 hours ball milling. High-energy milling produced significantly finer starting materials and Li₄Ti₅O₁₂ particles compared to those produced by ball milling. Among the three different balls used in high-energy milling, the 0.10 mm media showed the most favorable results. Pure Li₄Ti₅O₁₂ with a mean particle size of 146 and 175 nm were synthesized by an economic solid-state reaction combined with high-energy milling using 0.05 and 0.10 mm beads, respectively. These pure nano-sized Li₄Ti₅O₁₂ exhibited a much higher specific capacity and superior rate capability than those of coarse rutile TiO₂-contained Li₄Ti₅O₁₂ particles.     

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.     

Synthesis and electrochemical performance of LiNi0.6Co0.2Mn0.2O2/reduced graphene oxide cathode materials for lithium-ion batteries

A LiNi_0.6Co_0.2Mn_0.2O₂/reduced graphene oxide (RGO) composite with RGO content of 1.2 % was prepared by a simple spray-drying method instead of high-energy ball milling method. The composite has been characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy, energy dispersive spectroscopy, and charge/discharge test. The X-ray diffractometry result showed that composite possessed a typical hexagonal structure. The RGO sheets served as efficient electronically conductive frameworks benefitting from its 2D structure and outstanding electronic conductivity. The scanning electron microscope and transmission electron microscopy verified that LiNi_0.6Co_0.2Mn_0.2O₂ particles were wrapped with RGO sheets, which facilitated electronic conductivity between particles. The electrochemical results indicated that composite delivered a higher discharge capacity at various discharge rates. The cycling performance was also evaluated. The composite exhibited better cycling performance than pristine sample. Electrochemical impedance spectroscopy showed that the RGO can greatly reduce the charge transfer resistance. The results here gave clear evidence of RGO to improve electrochemical performance.     

Synthesis and characterization of Li4Ti5O12/graphene composite as anode material with enhanced electrochemical performance

The use of graphene as a conductive additive to enhance the rate capability and cycle stability of Li₄Ti₅O₁₂ electrode material has been demonstrated. Li₄Ti₅O₁₂ and its composite with graphene (1.86 wt%) are prepared by ball milling and simple chemical method, respectively. Among the as-synthesized composites, Li₄Ti₅O₁₂ particles uniformly clung to the graphene sheets. When used as an electrode material for lithium ion battery, the composite presents excellent rate performance and high cyclic stability. It is found that the composite displayed high-rate capacity of 118.7 mAh?g^?1 at 20 C. Furthermore, the composite exhibits good cycle stability, retaining over 96 % of its initial capacity after 50 cycles at 10 C. The excellent electrochemical performance is attributed to a decrease in the charge-transfer resistance.     

An improved solid-state reaction route to Mg2+-doped LiFePO4/C cathode material for Li-ion battery

An improved solid-state reaction route has been employed to synthesize Mg²⁺-doped LiFePO₄/C nanocomposite cathode by calcining the precursor obtained via evaporating the mixture of ascorbic acid, LiCH₃COO·2H₂O, Mg(CH₃COO)₂·4H₂O, and amorphous FePO₄ nanoparticles in anhydrous ethanol under continuous stirring. Ascorbic acid used here acted as both reducing agent and carbon source. The amorphous FePO₄ was pre-prepared via a simple and fast oxidic precipitation method. Electrochemical tests showed that the final product exhibited good rate and cycling performance, with discharge capacities of 145.2 mAh g^?1 at 0.2 C, 129.8 mAh g^?1 at 1 C, 107.6mAh g^?1 at 5 C, and 81.4 mAh g^?1 at 20 C, respectively. The Mg²⁺-doped LiFePO₄/C showed enhanced charge–discharge performance compared with undoped LiFePO₄/C, especially at high rates. The enhanced electrochemical performance of the composite could be attributed to a combination result of the fine particle size with narrow particle size distribution, homogeneous carbon coating on the surface of the particles, and magnesium ion doping.     

ZnO-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material for lithium-ion batteries synthesized by a combustion method

ZnO-coated LiMn₂O₄ cathode materials were prepared by a combustion method using glucose as fuel. The phase structures, size of particles, morphology, and electrochemical performance of pristine and ZnO-coated LiMn₂O₄ powders are studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge test, and X-ray photoelectron spectroscopy (XPS). XRD patterns indicated that surface-modified ZnO have no obvious effect on the bulk structure of the LiMn₂O₄. TEM and XPS proved ZnO formation on the surface of the LiMn₂O₄ particles. Galvanostatic charge/discharge test and rate performance showed that the ZnO coating could improve the capacity and cycling performance of LiMn₂O₄. The 2 wt% ZnO-coated LiMn₂O₄ sample exhibited an initial discharge capacity of 112.8 mAh g^?1 with a capacity retention of 84.1 % after 500 cycles at 0.5 C. Besides, a good rate capability at different current densities from 0.5 to 5.0 C can be acquired. CV and EIS measurements showed that the ZnO coating effectively reduced the impacts of polarization and charge transfer resistance upon cycling.     

Pickering emulsion polymerization of polyaniline/LiCoO2 nanoparticles used as cathode materials for lithium batteries

The oil in water (o/w) emulsions were prepared using aniline dissolved in toluene and LiCoO₂ particles as stabilizers (Pickering emulsions). Pickering emulsions are stabilized by adsorbed solid particles instead of emulsifier molecules. The mean droplet diameter of emulsions was controlled by the mass ratio M (oil)/M (solid particles). The emulsions showed great stability during 3 days. The composite materials containing LiCoO₂ and the conductive polymer polyaniline (PANI) have been prepared by means of polymerization of aniline emulsion stabilized by LiCoO₂ particles. The composite materials were characterized by nanosphere and nanofiber-like structures. The nanofiber-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The electrochemical reactivity of PANI/LiCoO₂ composites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ (1:4) composite materials exhibited the best electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The first discharge capacity of PANI/LiCoO₂ (1:4) was 167 mAh/g, while that of LiCoO₂ was136 mAh/g.     

Enhanced high-rate performance of sub-micro Li4Ti4.95Zn0.05O12 as anode material for lithium-ion batteries

Zn-doped Li₄Ti₅O₁₂ was prepared by a ball milling-assisted solid-state method, and the characters were determined by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, cyclic voltammetry, and galvanostatic charge–discharge testing. The results show that Li₄Ti_5?x Zn _x O₁₂ (x?=?0, 0.05) exhibits the pure phase structure, and Zn doping does not change the electrochemical reaction process and basic spinel structure of Li₄Ti₅O₁₂. The particle size of both samples is about 300–500 nm. The prepared Li₄Ti_4.95Zn_0.05O₁₂ presents an excellent rate capability and capacity retention. At the charge–discharge rate of 1C, the initial discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is 268 mAh g^?1. After 90 cycles at 5C, the discharge capacity of Li₄Ti_4.95Zn_0.05O₁₂ is obviously higher than that of Li₄Ti₅O₁₂. The excellent electrochemical performance of the Li₄Ti_4.95Zn_0.05O₁₂ electrode could be attributed to the improvement of reversibility by doping zinc and the sub-micro particle size.     

One-step solid-state synthesis of nanosized LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material with power properties

A simple one-step solid state reaction way of preparing nanosized LiMn₂O₄ powders with high-rate properties is investigated. Oxalic acid is used as a functional material to lose volatile gases during the process of calcining in order to control the morphology and change the particle size of materials. The results of X-ray diffraction and scanning electron microscopy show that particle size of materials decreases with the increase of the oxalic acid content. The electrochemical test results indicate that optimal LiMn₂O₄ particles (S_0.5) is synthesized when the molar ratios of oxalic acid and total Mn source are 0.5:1. It also manifests that LiMn₂O₄ sample with middle size has the optimal electrochemical performance among five samples instead of the smallest LiMn₂O₄ sample. The obtained sample S_0.5 with middle size exhibits a high initial discharge capacity of 125.8 mAh g^?1 at 0.2C and 91.4% capacity retention over 100 cycles at 0.5C, superior to any one of other samples. In addition, when cycling at the high rate of 10C, the optimal S_0.5 in this work could still reach a discharge capacity of 80.8 mAh g^?1. This observation can be addressed to the fact that the middle size particles balance the contradictory of diffusion length in solid phase and particle agglomeration, which leads to perfect contacts with the conductive additive, considerable apparent Li-ion diffusion rate, and the optimal performance of S_0.5.     

Influence of cooling mode on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials for lithium-ion batteries

Li₄Ti₅O₁₂ (LTO) was synthesized with two different cooling methods by solid-state method, namely fast cooling and air cooling. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), galvanostatic charge–discharge test, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), respectively. XRD revealed that the basic LTO structure was not changed. FESEM images showed that fast cooling effectively reduced the particle sizes and the agglomeration of particles. Galvanostatic charge–discharge test showed that the air cooling sample exhibited a mediocre performance, having an initial discharge capacity of 136.3mAh?·?g^?1 at 0.5 C; however, the fast cooling sample demonstrated noticeable improvement in both of its discharge capacity and rate capability, with a high initial capacity value of 142.7 mAh?·?g^?1 at 0.5 C. CV measurements also revealed that fast cooling enhanced the reversibility of the LTO. EIS confirmed that fast cooling resulted in lower electrochemical polarization and a higher lithium-ion diffusion coefficient. Therefore, fast cooling have a great impact on discharge capacity, rate capability, and cycling performance of LTO anode materials for lithium-ion batteries.     

Ultrasound assisted wet media milling synthesis of nanofiber-cage LiFePO4/C

To meet the objectives of the Intergovernmental Panel on Climate Change nations are adopting policies to encourage consumers to purchase electric vehicles. Electrification of the automobile industry reduces greenhouse gases but active metals for the cathode—LiCoO₂ and LiNiO₂—are toxic and represent an environmental challenge at the end of their lifetime. LiFePO₄ (LFP) is an attractive alternative that is non-toxic, thermally stable, and durable but with a moderate theoretical capacity and a low electrical conductivity. Commercial technologies to synthesize LFP are energy-intensive, produce waste that incurs cost, and involve multiple process steps. Here we synthesize LFP precursor with lignin and cellulose in a sonicated grinding chamber of a wet media mill. This approach represents a paradigm shift that introduces mechanochemistry as a motive force to react iron oxalate and lithium hydrogen phosphate at ambient temperature. Ultrasound-assisted wet media milling increases carbon dispersion and reduces the particle size simultaneously. The ultrasound is generated by a 20 kHz,500 W automatic tuning ultrasound probe. The maximum discharge rate of the LFP synthesized this way was achieved with cellulose as a carbon source, after 9 h milling, at 70% ultrasound amplitude. After 2.5 h of milling, the particle size remained constant but the crystal size continued to drop and reached 29 nm. Glucose created plate-like particles, and cellulose and lignin produced spindle-shaped particles. Long mill times and high ultrasound amplitude generate smoother particle surfaces and the powder densifies after a spray drying step.     

Surfactant-assisted synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> particles as high-rate and long-life cathode materials for lithium-ion batteries

Herein, we reported the synthesis of uniform LiMn₂O₄ submicroparticles by surfactant-assisted preparation of spherical MnCO₃ precursor followed by solid-state reaction. Polyethylene glycol (Mw = 1000) was used as surfactant to control the morphology and size of the MnCO₃ precursor as well as the MnO₂ intermediate and LiMn₂O₄ product. The influence of particle size, homogeneity, and crystallinity on the electrochemical performance of LiMn₂O₄ was intensively investigated. The test results indicate that the LiMn₂O₄ sample using polyethylene glycol with weight as 10% of reactants shows the best rate capability and long-term cyclability. Due to the homogeneous particles with the average size of ca. 250 nm and high crystallinity, the discharge capacities are as high as 125, 118, 114, and 100 mAh g^?1 at 1, 10, 20, and 50 C rates, respectively, along with high capacity retention of 74% after 1000 cycles at 20 C.     

Synthesis of Li3V2(PO4)3/reduced graphene oxide cathode material with high-rate capability

The Li₃V₂(PO₄)₃/reduced graphene oxide (LVP/rGO) composite is successfully synthesized by a conventional solid-state reaction with a high yield of 10 g, which is suitable for large-scale production. Its structure and physicochemical properties are investigated using X-ray diffraction, Raman spectra, field-emission scanning electron microscopy, transmission electron microscopy, and electrochemical methods. The rGO content is as low as ~3 wt%, and LVP particles are strongly adhered to the surface of the rGO layer and/or enwrapped into the rGO sheets, which can facilitate the fast charge transfer within the whole electrode and to the current collector. The galvanostatic charge–discharge tests show that the LVP/rGO electrode delivers an initial discharge capacity of 177 mAh g^?1 at 0.5 C with capacity retention of 88 % during the 50th cycle in a wide voltage range of 3.0–4.8 V. A superior rate capability is also achieved, e.g., exhibiting discharge capacities of 137 and 117 mAh g^?1 during the 50th cycle at high C rates of 2 and 5 C, respectively.     

Effect of milling time on the performance of bowl-like LiFePO4/C prepared by wet milling-assisted spray drying

LiFePO₄/C was prepared by wet milling-assisted spray drying. The effects of ball-milling time on the characteristics of LiFePO₄/C were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, cyclic voltammograms, electrochemical impedance spectra, and galvanostatic charge–discharge testing. Bowl-like material was obtained, surrounded by a network of carbon, which display larger specific surface area. The specific surface area of particle first increased and then decreased, as the increasing of ball-milling time; when ball-milling time reach 2.5 h, it showed the largest specific surface area of 29.350 m² g^?1, primary particles with size of ～50 nm, delivered a discharge capacity of 162 mAh g^?1 at 0.5 C and 123 mAh g^?1 at 10 C, and with no capacity loss.     

Studies of the electrochemical properties and thermal stability of LiNi1/3Co1/3Mn1/3O2/LiFePO4 composite cathodes for lithium ion batteries

A series of LiNi_1/3Co_1/3Mn_1/3O₂/LiFePO₄ composite cathodes with the LiFePO₄ mass content ranging from 10 to 30 wt% were prepared by ball milling in order to combine the merits of layered LiNi_1/3Co_1/3Mn_1/3O₂ and olivine LiFePO₄. The structure and morphology of the samples were characterized by X-ray diffraction and scanning electron microscope. The composite cathodes exhibited improved electrochemical performance compared with pristine LiNi_1/3Co_1/3Mn_1/3O₂. Among all the composite cathodes, the one with 20 wt% of LiFePO₄ showed the best electrochemical performance in terms of discharge capacity, cycle stability, and rate capability. Electrochemical impedance spectroscopy showed that mixing of LiFePO₄ in LiNi_1/3Co_1/3Mn_1/3O₂ decreased the internal resistance of the electrode, retarded the formation of SEI film, and facilitated the charge transfer reaction. Differential scanning calorimetry showed that the composite cathode had better thermal stability than pristine LiNi_1/3Co_1/3Mn_1/3O₂.     

Electrochemical impedance spectroscopic studies on aging-dependent electrochemical degradation of p-toluene sulfonic acid-doped polypyrrole thin film

The conducting polymer polypyrrole thin film was galvanostatically polymerized on stainless steel substrate for the supercapacitor electrode. The electrochemical stability of the electrode was monitored each 30 days of aging up to 90 days. The FTIR analysis showed an increase in intensity of the absorption peaks, especially high growth of the carbonyl peaks after 90 days of aging. The electrochemical capacitance degradation of the electrode was studied using cyclic voltammetric and galvanostatic charge/discharge analysis in 1 M Na₂SO₄ electrolyte, which showed ~?53% of fading in the initial specific capacitance value after 90 days. Further, the electrochemical degradation of polypyrrole electrodes was analyzed in detail using electrochemical impedance spectroscopy. The analysis showed a large increase in the internal resistance and low-power deliverability of the electrode with respect to aging as the main reasons for the degradation of specific capacitance of the polypyrrole electrode.     

Enhanced electrochemical performance of Cu<Subscript>2</Subscript>O-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium-ion batteries

Li₄Ti₅O₁₂/Cu₂O composite was prepared by ball milling Li₄Ti₅O₁₂ and Cu₂O with further heat treatment. The structure and electrochemical performance of the composite were investigated via X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. Li₄Ti₅O₁₂/Cu₂O composite exhibited much better rate capability and capacity performance than pristine Li₄Ti₅O₁₂. The discharge capacity of the composite at 2 C rate reached up to 122.4 mAh g^?1 after 300 cycles with capacity retention of 91.3 %, which was significantly higher than that of the pristine Li₄Ti₅O₁₂ (89.6 mAh g^?1). The improvement can be ascribed to the Cu₂O modification. In addition, Cu₂O modification plays an important role in reducing the total resistance of the cell, which has been demonstrated by the electrochemical impedance spectroscopy analysis.     

Electrochemical behavior of carbonic precursor with Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>nanostructured material in hybrid battery system

The nanostructured Na₃V₂(PO₄)₃ (NVP) cathode material has been synthesized using the sol-gel route for different molar fractions of citric acid as a carbon source during the synthesis. The nanostructured NVP as cores with carbonic shell structures are fabricated with two different citric acid molar ratios. The thermal treatment has been optimized to convert the amorphous carbon shell into graphitic carbon to realize the better electrical conductivity and thus effective electron transfer during the electrochemical charge transfer process. The X-ray diffraction measurements confirmed the rhombohedral crystallographic phase (space group R-3c) with average crystallite size ~28 ± 5 nm. The coin cells are assembled in a hybrid rechargeable electrochemical cell configuration with lithium as a counter electrode and LiPF₆-EC:DEC:DMC (1:1:1 ratio) as the electrolyte. The electrochemical charge/discharge measurements are carried out at C/10 and C/20 rates and the measured specific capacities are 80 and 120 mAhg^?1 for samples with lower and higher citric acid molar ratios, respectively. The studies suggest that NVP can be used as an effective cathode material in hybrid electrochemical cells, and a higher concentration of citric acid may result in the effective carbonic shell for optimal electron transfer and thus enhanced electrochemical performance.