Synthesis and electrochemical performance of LiFePO<Subscript>4</Subscript>/C cathode materials from Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> for high-power lithium-ion batteries

Carbon-coated olivine-structured LiFePO₄/C composites are synthesized via an efficient and low-cost carbothermal reduction method using Fe₂O₃ as iron source at a relative low temperature (600 °C). The effects of two kinds of carbon sources, inorganic (acetylene black) and organic (sucrose), on the structures, morphologies, and lithium storage properties of LiFePO₄/C are evaluated in details. The particle size and distribution of the carbon-coated LiFePO₄ from sucrose (LiFePO₄/SUC) are more uniform than that obtained from acetylene black (LiFePO₄/AB). Moreover, the LiFePO₄/SUC nanocomposite shows superior electrochemical properties such as high discharge capacity of 156 mAh g^?1 at 0.1 C, excellent cyclic stability, and rate capability (78 mAh g^?1 at 20 C), as compared to LiFePO₄/AB. Cyclic voltammetric test discloses that the Li-ion diffusion, the reversibility of lithium extraction/insertion, and electrical conductivity are significantly improved in LiFePO₄/SUC composite. It is believed that olivine-structured LiFePO₄ decorated with carbon from organic carbon source (sucrose) using Fe₂O₃ is a promising cathode for high-power lithium-ion batteries.     

A novel carbon source coated on C-LiFePO<Subscript>4</Subscript> as a cathode material for lithium-ion batteries

The poor electronic conductivity and low lithium-ion diffusion are the two major obstacles to the largely commercial application of LiFePO₄ cathode material in power batteries. In order to improve the defects of LiFePO₄, a novel carbon source polyacrylonitrile (PAN), which would form the hierarchical porous structure after carbonization, is fabricated and used. This work comes up with a simple and facile carbothermal reduction method to prepare porous-carbon-coated LiFePO₄ (C-LiFePO₄-PC) composite and to study the effect of carbon-coated temperature on ameliorating the electrochemical performance. The obtained C-LiFePO₄-PC composite shows a high initial discharge capacity of 164.1 mA h g^?1 at 0.1 C and good cycling stability as well as excellent rate capacity (49.0 mA h g^?1 at 50 C). The most possible factors that improve the electrochemical performance could be related to the enhancement of electronic conductivity and the existence of porous carbon layers. In a word, the C-LiFePO₄-PC material would become an excellent candidate for application in the fields of lithium-ion batteries.     

Highly enhanced low-temperature performances of LiFePO<Subscript>4</Subscript>/C cathode materials prepared by polyol route for lithium-ion batteries

Although LiFePO₄/C has been successfully put into practical use in lithium-ion batteries equipped on new energy vehicles, its unsatisfactory low temperature results in poor low performance of lithium-ion batteries, leading to a much smaller continue voyage course at extreme environments with low temperature for electric vehicles. In this paper, the electrochemical performance of the LiFePO₄/C prepared by polyol route was investigated at a temperature range from 25 to ?20 °C. Compared to commercial ones, as-prepared LiFePO₄/C shows a much better low-temperature performance with a reversible capacity of 30 mA h g^?1 even at 5 C under ?20 °C and a capacity retention of 91.1 % after 100 cycles at 0.1 C under 0 °C. Moreover, high-resolution transmission electron microscopy (HRTEM) revealed that this outstanding performance at low temperatures could be assigned to uniform carbon coating and the nano-sized particles with a highly crystalline structure.     

The formation and electrochemical property of lithium-excess cathode material Li<Subscript>1.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>O<Subscript>2</Subscript> with petal-like nanoplate microstructure

Lithium-excess oxide shows great potential for its high specific capacity of exceeding 280 mAh g^?1. However, the poor rate capability caused by the poor electrochemical kinetics condition as well as the structure instability block the way of its application. Here, we aimed to improve the kinetics circumstance for lithium ion transference through the material bulk by synthesizing lithium-excess oxide with high specific surface area. Petal-like nanoplates and nanoparticles with excellent electrochemical performance were obtained at different sintering temperatures and times by the electrospinning-sintering method, which facilitates the sufficient contact of electrode and electrolyte and helps to reduce the polarization during the electrochemical reaction process. Cyclic voltammetry tests verify that a portion of oxidized oxygen is reduced reversibly at 3.0 V and the reduction of oxygen contributes to the discharge capacity. Electrochemical impedance spectroscopy plots illustrate the ameliorative electrochemical kinetics is conductive to the oxidation of oxygen at 4.5 V.     

Synthesis of carbon microtubules core structure LiFePO4 via a template-assisted method

The carbon microtubules core structure LiFePO₄ is synthesized using a cotton fiber template-assisted method. The crystalline structure and morphology of the product is characterized by X-ray diffraction and field emission scanning electron microscopy. The charge–discharge kinetics of the LiFePO₄ electrode is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The result shows that the well-crystallized carbon microtubules core structure LiFePO₄ is successfully synthesized. The as-synthesized material exhibits a high initial discharge capacity of 167 mAh g^?1 at 0.2 C rate. The material also shows good high-rate discharge performance and cycling stability, about 127 mAh g^?1 and 94.7 % capacity retention after 100 cycles even at 5.0 C rate.     

Vertical aligned V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoneedle arrays grown on Ti substrate as binder-free cathode for lithium-ion batteries

V₂O₅ nanoneedle arrays were grown directly on titanium (Ti) substrate by a facile solvothermal route followed with calcination at 350 °C for 2 h. The as-prepared V₂O₅ nanoneedles are about 50 nm in diameter and 800 nm in length. The electrochemical behavior of V₂O₅ nanoarrays as binder-free cathode for lithium-ion batteries (LIBs) was evaluated by cyclic voltammetry and galvanostatic discharge/charge tests. Compared with V₂O₅ powder electrode, V₂O₅ nanoneedle arrays electrode exhibited improved electrochemical performance in terms of high discharge capacity of 262.5 mA h g^?1 between 2.0 and 4.0 V at 0.2 C, and high capacity retention up to 77.1% after 100 cycles. Under a high current rate of 2 C, a discharge capacity of about 175.6 mA h g^?1 can be maintained. The enhanced performance are mainly due to the intimate contact between V₂O₅ nanoneedle active material and current collector, which enable shortened electron transfer pathway and improved charge transfer kinetics, demonstrating their potential applications in high rate electrochemical storage devices.     

A piperidinium-based ester-functionalized ionic liquid as electrolytes in Li/LiFePO<Subscript>4</Subscript> batteries

A new functionalized ionic liquid (IL) based on cyclic quaternary ammonium cations with ester group and bis(trifluoromethanesulfonyl)imide ([TFSI]^?) anion, namely, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized and characterized. Physical and electrochemical properties, including Li-ion transference number, ionic conductivity, and electrochemical stability, were investigated. The electrochemical window of [MMOCPip][TFSI] was 6 V, which was wide enough to be used as a common electrolyte material. The Li-ion transference number of this IL electrolyte containing 0.1 M LiTFSI was 0.56. The half-cell tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of a Li/LiFePO₄ cell. For the Li/LiFePO₄ half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh g^?1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte for lithium-ion batteries.     

An efficient process to fabricate spherical hierarchical LiFePO<Subscript>4</Subscript>/C cathode composites with controllable coating thickness

Hierarchical lithium iron phosphate/carbon (LiFePO₄/C) microspheres were fabricated successfully using a facile spray drying-assisted coprecipitation method. A relatively short calcination time and a relatively low calcination temperature were adopted to prepare the hierarchical LiFePO₄/C microspheres. The hierarchical microspheres consisted of nanoparticles with a uniform coating of amorphous carbon. The thickness of the carbon layer was controlled by the addition of glucose. The hierarchical LiFePO₄/C microspheres exhibited a high tap density and a large specific surface area. The electrochemical properties of the sample were investigated. The sample exhibited a better rate capability and a better cyclability than the coral-like LiFePO₄/C cathode material, and these were ascribed to the highly uniform carbon coating and the self-assembled nanoparticles.     

Effect of slurry preparation and dispersion on electrochemical performances of LiFePO<Subscript>4</Subscript> composite electrode

A study is attempted on how the dispersion of solid ingredients in solvent affects the electrochemical performance of LiFePO₄ composite electrode. The slurries comprising LiFePO₄ powder, carbon black and polymeric binder in solvent NMP (N-methyl-2-pyrrolidone) are prepared by two different processes, and results in different dispersion qualities. With better dispersion, the surfactant (Triton-100) is added into slurry as dispersing agent, whereas no dispersing agent in the other sample. The former process leads to more uniform dispersion of solid ingredients as compared to the latter. In the composite electrode prepared from the former process, the LiFePO₄ and carbon black particles are homogeneously distributed without obviously reunion. Indebted to this favourable feature, this electrode exhibits a better high C-rate electrochemical performance for cycling and capacity than those without the surfactant.     

Hexagonal-like NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanostructure based high-performance supercapacitor electrodes

A novel approach of double hydroxide-mediated synthesis of nickel cobaltite (NiCo₂O₄) electro-active material by the hydrothermal method is reported. The obtained NiCo₂O₄ electro-active material displays the spinel cubic phase and hexagonal-like morphology. Thermogravimetry analysis confirms the thermal stability of the electrode material. The functional groups and phase formation of NiCo₂O₄ have been confirmed by FT-IR and Raman spectral analysis. The modified NiCo₂O₄ electrode exhibits the highest specific capacitance of 767.5 F g^?1 at a current density of 0.5 A g^?1 in 3 M KOH electrolyte and excellent cyclic stability (94 % capacitance retention after 1000 cycles at a high current density of 5 A g^?1). The excellent electrochemical performance of the electrode is attributed to the hexagonal-like morphology, which contributes to the rich surface electro-active sites and easy transport pathway for the ions during the electrochemical reaction. The attractive Faradic behavior of NiCo₂O₄ electrode has been ascribed to the redox contribution of Ni²⁺/Ni³⁺ and Co²⁺/Co³⁺ metal species in the alkaline medium. The symmetrical two-electrode cell has been fabricated using the NiCo₂O₄ electro-active material with excellent electrochemical properties for supercapacitor applications.     

Charge storage performance of lithiated iron phosphate/activated carbon composite as symmetrical electrode for electrochemical capacitor

In this study, a symmetric electrochemical capacitor was fabricated by adopting a lithium iron phosphate (LiFePO₄)-activated carbon (AC) composite as the core electrode material in 1.0 M Na₂SO₃ and 1.0 M Li₂SO₄ aqueous electrolyte solutions. The composite electrodes were prepared via a facile mechanical mixing process. The structural properties of the nanocomposite electrodes were characterised by scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) analysis. The electrochemical performances of the prepared composite electrode were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that a maximum specific capacitance of 112.41 F/g was obtained a 40 wt% LiFePO₄ loading on an AC electrode compared with that of a pure AC electrode (76.24 F/g) in 1 M Na₂SO₃. The improvement in the capacitive performance of the 40 wt% LiFePO₄–AC composite electrode is believed to be attributed to the contribution of the synergistic effect of the electric double layer capacitance (EDLC) of the AC electrode and pseudocapacitance via the intercalation/extraction of H⁺, OH⁻, Na⁺ and SO₃²⁻ and Li⁺ ions in LiFePO₄ lattices. In contrast, it appears that the incorporation of LiFePO₄ into AC electrodes does not increase the charge storage capability when Li₂SO₄ is used as the electrolyte. This behaviour can be explained by the fact that the electrolyte system containing SO₄²⁻ only exhibits EDLC in the Fe-based electrodes. Additionally, Li⁺ ions that have lower conductivity and mobility may lead to poorer charge storage capability compared to Na⁺ ions. Overall, the results reveal that the AC composite electrodes with 40 wt% LiFePO₄ loading on a Na₂SO₃ neutral electrolyte exhibit high cycling stability and reversibility and thus display great potential for electrochemical capacitor applications.     

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.     

Pseudo-capacitive properties of LiCoO<Subscript>2</Subscript>/AC electrochemical capacitor in various aqueous electrolytes

LiCoO₂ particles were synthesized by a sol-gel process. X-ray diffraction analysis reveals that the prepared sample is a single phase with layered structure. A hybrid electrochemical capacitor was fabricated with LiCoO₂ as a positive electrode and activated carbon (AC) as a negative electrode in various aqueous electrolytes. Pseudo-capacitive properties of the LiCoO₂/AC electrochemical capacitor were determined by cyclic voltammetry, charge–discharge test, and electrochemical impedance measurement. The charge storage mechanism of the LiCoO₂-positive electrode in aqueous electrolyte was discussed, too. The results showed that the potential range, scan rate, species of aqueous electrolyte, and current density had great effect on capacitive properties of the hybrid capacitor. In the potential range of 0–1.4 V, it delivered a discharge specific capacitance of 45.9 Fg^–1 (based on the active mass of the two electrodes) at a current density of 100 mAg^–1 in 1 molL^–1 Li₂SO₄ aqueous electrolyte. The specific capacitance remained 41.7 Fg^–1 after 600 cycles.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

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.     

Improved of cathode performance of LiFePO<Subscript>4</Subscript>/C composite using different carboxylic acids as carbon sources for lithium-ion batteries

Among the several materials under development for use as a cathodes in lithium-ion batteries olivine-type LiFePO₄ is one of the most promising cathode material. However, its poor conductivity and low lithium-ion diffusion limits its practical application. In this study, we report seven different carboxylic acids used to synthesize LiFePO₄/C composite, and influences of carbon sources on electrochemical performance were intensively studied. The structure and electrochemical properties of the LiFePO₄/C were characterized by X-ray diffraction, scanning electron microscopy, electrical conductivity, and galvanostatic charge–discharge measurements. Among the materials studied, the sample E with tartaric acid as carbon source exhibited the best cell performance with a maximum discharge capacity of 160 mAh g⁻¹ at a 0.1 C-rate. The improved electrochemical properties were attributed to the reduced particle size and enhanced electrical contacts by carbon.     

Thermoeletrochemical study on LiNi<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>O<Subscript>2</Subscript> with in situ modification of Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript>

To improve the electrochemical performance of Nickel-rich cathode material LiNi_0.8Co_0.1Mn_0.1O₂, an in situ coating technique with Li₂ZrO₃ is successfully applied through wet chemical method, and the thermoelectrochemical properties of the coated material at different ambient temperatures and charge-discharge rates are investigated by electrochemical-calorimetric method. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests demonstrate that the Li₂ZrO₃ coating decreases the electrode polarizatoin and reduces the charge transfer resistance of the material during cycling. Moreover, it is found that with the ambient temperatures and charge-discharge rates increase, the specific capacity decreases, the amount of heat increases, and the enthalpy change (ΔH) increases. The specific capacity of the cells at 30 °C are 203.8, 197.4, 184.0, and 174.5 mAh g^?1 at 0.2, 0.5, 1.0, and 2.0 C, respectively. Under the same rate (2.0 C), the amounts of heat of the cells are 381.64, 645.32, and 710.34 mJ at 30, 40, and 50 °C. These results indicate that Li₂ZrO₃ coating plays an important role to enhance the electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ and reveal that choosing suitable temperature and current is critical for solving battery safety problem.     

Polyol technique synthesis of Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> coated on LiFePO<Subscript>4</Subscript> cathode materials for Li-ion storage

A novel approach has been made to tailor Niobium pentoxide (Nb₂O₅) as a coating material on the surface of lithium iron phosphate (LiFePO₄) via a facile polyol technique. The coating content was optimized at 1 wt%. The superficial coating demonstrated superior discharge capacity than the pristine LiFePO₄. However, increasing the coating content further would result in a capacity loss. This may be due to the electrochemical inactiveness that increases with the content of the coating material, and 1 wt% of Nb₂O₅-coated LiFePO₄ sample exhibits initial discharge capacity of 163 mAh g^?1 at a current of 0.1 C and retains a stable discharge capacity of 143 mAh g^?1 up to 400 cycles at 1 C rate with a coulombic efficiency of 98%.

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LiFePO<Subscript>4</Subscript> composites decorated with nitrogen-doped carbon as superior cathode materials for lithium-ion batteries

The development of methods to synthesize electrode materials can improve the performance of lithium ion storage. In this study, a facile and low-cost approach is employed to synthesize LiFePO₄ (LFP/NC) hybrid materials decorated with nitrogen-doped carbon nanomaterials (NC). Melamine was used as nitrogen and carbon source with an NC to LFP ratio of 3.19%. As electrode materials for lithium ion batteries (LIBs), the LFP/NC composites exhibit an optimum performance with a high rate capacity of 144.6 mAh·g^?1 at 1 C after 500 cycles without apparent loss. The outstanding cycling stability may be attributed to the synergetic effects of well-crystallized particles and NC layers.     

Preparation of V-LiFePO4 cathode material for Li-ion batteries

The preparation of vanadium-modified olivine LiFePO₄ was attempted using vanadium-modified FePO₄ precursor which was synthesized by controlled crystallization. The structure and electrochemical behavior of V-LiFePO₄ with different vanadium contents were investigated. The electrochemical behavior of V-LiFePO₄ materials at high rate and low temperature was compared with that of the LiFePO₄ material. Incorporation of vanadium improved the electrochemical performance of LiFePO₄. The investigation showed that the 3%V-modified LiFePO₄ presented the best electrochemical performance.