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.     

Electrochemical properties of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode materials synthesized via ethylene glycol-assisted solvothermal method

The Li₃V₂(PO₄)₃/C (LVP/C) cathode materials for lithium-ion batteries were synthesized via ethylene glycol-assisted solvothermal method. The phase composition, phase transition temperature, morphology, and fined microstructure were studied using X-ray diffraction (XRD), differential thermal analyzer (DTA), scanning electron microscope (SEM), and transmission electron microscope (TEM), respectively. The electrochemical properties, impedance, and electrical conductivity of LVP/C cathode materials were tested by channel battery analyzer, the electrochemical workstation, and the Hall test system, respectively. The results shown that the appropriate amount of water added to ethylene glycol solvent contributes to the synthesis of pure phase LVP. The LVP₁₀/C cathode material can exhibit discharge capacities of 128, 126, 126, 123, 124, and 114 mAh g^?1 at 0.1, 0.5, 2, 5, 10, and 20 C in the voltage range of 3.0–4.3 V, respectively. Meanwhile, it shows also a stable cycling performance with the capacity retention of 89.6% after 180 cycles at 20 C.     

Synthesis of flower-like Li3V2(PO4)3/C cathode with mixed morphology for advanced lithium-ion batteries

A rheological phase-assisted ball milling method was developed to synthesize of flower-like Li₃V₂(PO₄)₃/C composites consisting of nanofibers and nanoplate porous microstructure. The flower-like Li₃V₂(PO₄)₃/C composite delivered specific capacities of 120 and 108 mAh g^?1 at 0.5 and 10 C rates, respectively. A capacity retention of 99.5 % was sustained after 100 cycles at a 10-C cycling rate. The remarkable performance was attributed to the porous nanostructures that provide short electron/ion diffusion distance and large electrode/electrolyte contact area.     

Preparation and characterization of Li3V2(PO4)3/MWCNTs cathode material for lithium-ion batteries

The Li₃V₂(PO₄)₃/multiwalled carbon nanotubes (LVP/MWCNTs) composite is successfully synthesized by a sol?Cgel route using oxalic acid as the chelating reagent. Its structure and physicochemical properties are investigated using X-ray diffraction, field-emission scanning electron microscopy, and electrochemical methods. LVP particles are well mixed with MWCNTs, and most of them are around 100?nm. The galvanostatic charge?Cdischarge tests show that LVP/MWCNTs electrode owns an initial discharge capacity of 126?mAh?g^?1 at 0.5 C with capacity retention of 94% during the 100th cycle in the voltage range of 3.0?C4.3?V. A superior rate capability is also achieved, e.g., exhibiting discharge capacities of 75 and 58?mAh?g^?1 at high C rates of 10 and 15 C, respectively.     

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.     

The preparation and electrochemical properties of the Li-excess cathode material Li1 + x (Mn0.7Fe0.3)1 − x O2 by coprecipitation method

The Fe-substituted Li₂MnO₃ cathode materials were synthesized by the coprecipitation method. The effects of the different precipitants of Na₂CO₃ and NaOH on the structure, morphology, and electrochemical performance were investigated by X-ray diffractometry, scanning electron microscopy, dQ/dV plots, and charge–discharge tests. The results indicate that the materials prepared using both precipitants possess layered α-NaFeO₂ structure with R-3m space group. However, the material prepared using Na₂CO₃ shows smaller primary particle size as well as higher discharge capacity. The cycling test shows that the initial discharge capacity is 206 mAh g^?1 in the voltage range of 2.5–4.8 V under current density of 30 mA g^?1 at 30 °C and 231 mAh g^?1 in the voltage range of 2.0–4.8 V. Meanwhile, the discharge capacity fades to 191 mAh g^?1 after 20 cycles. The activated Mn⁴⁺ was confirmed to contribute to the high reversible capacities.     

Enhanced electrochemical performance of lithium ion battery cathode Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C

Li-ion battery cathode material lithium-vanadium-phosphate Li₃V₂(PO₄)₃ was synthesized by a carbon-thermal reduction method, using stearic acid, LiH₂PO₄, and V₂O₅ as raw materials. And stearic acid acted as reductant, carbon source, and surface active agent. The effect of its content on the crystal structure and electrochemical performance of Li₃V₂(PO₄)₃/C were characterized by XRD and electrochemical performance testing, respectively. The results showed that the content of carbon source has no significant effect on the crystal structure of lithium vanadium phosphate. Lihtium vanadium phosphate obtained with 12.3% stearic acid demonstrated the best electrochemical properties with a typical discharge capacity of 119.4 mAh/g at 0.1 C and capacity retention behavior of 98.5% after 50 cycles. And it has high reversible discharge capacity of 83 mAh/g at 5 C with the voltage window of 3 to 4.3 V.     

Li2MnSiO4/carbon nanofiber cathodes for Li-ion batteries

Pure single-phase Li₂MnSiO₄ nanoparticle-embedded carbon nanofibers have been prepared for the first time via a simple sol-gel and electrospinning technique. They exhibit an improved electrochemical performance over conventional carbon-coated Li₂MnSiO₄ nanoparticle electrodes, including a high discharge capacity of ～200 mAh g^?1, at a C/20 rate, with the retention of 77 % over 20 cycles and a 1.6-fold higher discharge capacity at a 1 C rate.     

Influence of coated MnO2 content on the electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathodes

Layered cathode material Li_1.2Ni_0.2Mn_0.6O₂ has been synthesized using a coprecipitation method and coated by MnO₂ with varying amounts (1, 3, 5, and 9 wt%). The physical properties and electrochemical performances of the materials are characterized by XRD, SEM, charge/discharge tests, cycle life, and rate capability tests. XRD patterns show that the pristine and coated Li_1.2Ni_0.2Mn_0.6O₂ powders exhibit layered structure. The discharge capacities and coulombic efficiencies of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved and increase with the increasing content of coated MnO₂. The 9 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ delivers 287 mAhg^?1 for the first discharge capacity and 86.7 % for the first coulombic efficiency compared with 228 mAhg^?1 and 65.9 % for pristine Li_1.2Ni_0.2Mn_0.6O₂. However, the 5 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best capacity retention (99.9 % for 50 cycles) and rate capability (88.6 mAhg^?1 at 10 C), while the pristine Li_1.2Ni_0.2Mn_0.6O₂ only shows 91.5 % for 50 cycles and 25.3 mAhg^?1 at 10 C. The charge/discharge curves and differential capacity vs. voltage (dQ/dV) curves show that the coated MnO₂ reacts with Li⁺ during the charge and discharge process, which is responsible for higher discharge capacity after coating. Electrochemical impedance spectroscopy results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after coating, which is responsible for superior rate capability.     

Synthesis and characterization of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>·LiMn<Subscript>0.33</Subscript>Fe<Subscript>0.67</Subscript>PO<Subscript>4</Subscript>/C cathode materials

A new polyanionic cathode material, Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C for lithium-ion batteries, was synthesized using a sol-gel method and with N,N-dimethyl formamide as a dispersion agent. The analysis of electron transmission spectroscopy and X-ray diffraction revealed that the composite contained two phases. The material has high crystallinity with a grain size of 20–50 nm. The valence states of Mn, V, and Fe in the composite were analyzed by X-ray photoelectron spectroscopy. The electrochemical kinetics in Li₃V₂(PO₄)₃ is effectively enhanced by the incorporation of LiMnPO₄ and LiFePO₄, via structure modification and reduced Li diffusion length. The Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C materials displayed high rate capacity and steady cycle performance with discharge capacity remained 148 mAh g^?1 after 50 cycles at the rate of 0.2C. In particular, the composite exhibited excellent reversible capacities, with the values of 157, 134, 120, 102, and 94 mAh g^?1 at charge/discharge 0.2, 0.5, 1, 2, and 5C rates, respectively.     

Preparation of carbon encapsulated Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium ion battery through pre-coating method

Carbon encapsulated Li₄Ti₅O₁₂ (C/Li₄Ti₅O₁₂) anode material for lithium ion battery was prepared by using the pre-coat method of two steps, and the TiO₂ was pre coated before the reaction with Li₂CO₃. The structure and morphology of the resultant C/Li₄Ti₅O₁₂ materials were characterized by X-ray diffraction (XRD) and scanning microscopy (SEM). Electrochemical tests showed that at 0.1 C, the initial discharge capacity was 169.9 mAh g^?1, and the discharge capacity was 80 mAh g^?1 at 5 C. After 100 cycles at 2 C, the discharge specific capacity was 108.5 mAh g^?1. Compare with one step coating method, results showed the C/Li₄Ti₅O₁₂ prepared by pre-coat method can reduce the particle’s size and effectively improve the electrochemical performance.     

New-type low-cost cathode materials for Li-ion batteries: Mikasaite-type Fe2(SO4)3

In the present work, a new-type low-cost lithium ion battery cathode material, the Mikasaite-type iron sulfate, has been studied. It can be prepared by heating the water-containing iron sulfate raw chemicals in air atmosphere. The experimental results have shown that the oxidation and the reduction peaks are 3.92 and 3.37 V in the cyclic voltammogram, respectively, when the scanning rate is 0.05 mV s^?1. The galvanostatic measurements have explored that the voltage plateau during charging is slightly less than 3.70 V and the discharge voltage plateau is 3.40 V for the first cycle and 3.50 V for the following cycles at 0.1 C rate. The discharge capacity in the first cycle can reach 116 mAh g^?1, about 87 % of the theoretical capacity (134 mAh g^?1). It is believed that the product in the fully discharged state is Li₂Fe₂(SO₄)₃. However, the insertion reaction is reversible only for the second lithium ion. During cycling, the reversible capacity remains about 60 mAh g^?1. Further capacity fade is not found in the 20 discharge–charge cycles. The electrochemical impedance measurements have shown that there are two compressed semicircles in the Nyquist plots and a Warburg impedance in the low-frequency domain. The high-frequency semicircle is related with the electrode’s structural factor and the intermediate-frequency semicircle corresponds to the charge-transfer process.     

The synthesis, structure, and electrochemical properties of a novel rods-shaped Li6V10O28 for lithium-ion batteries

Rods-shaped Li₆V₁₀O₂₈ powders were synthesized by rheological phase reaction. The ratio of the Li/V of the product sintered at 600 °C for 8 h was characterized by inductively coupled plasma. The structure, composite, and morphology of the product have been investigated by X-ray diffraction, scan electron microscope, transmission electron microscopy, and X-ray photoelectron spectrometry, respectively. After charge–discharge test using the product as the cathode material of lithium-ion batteries, the product calcined at 600 °C for 8 h exhibited an initial high discharge specific capacity of 212.4 mAh/g at a rate of 1.0 mA/cm² in a potential range of 2.0 and 4.4 V, and its stabilized capacity still remained 167.7 mAh/g after 30 cycles, which indicates that the rods-shaped Li₆V₁₀O₂₈ are promising cathode materials in lithium-ion batteries.     

The all-solid-state battery with vanadate glass-ceramic cathode

The Ga-Ag-Li|Li₇La₃Zr_1.89Al_0.15O₁₂|(Li₂O–B₂O₃–V₂O₅ + Fe) all-solid-state electrochemical cell has been designed with a simple sintering process. The Li₇La₃Zr_1.89Al_0.15O₁₂ solid electrolyte was prepared by sol-gel method. The lithium borovanadate glass was obtained by a convenient melt quenching technique. Cycliс voltammetry has shown that the current densities of the cell at 300 °C can reach several hundreds of μA cm^?2. At this temperature, the single cell voltage is about 3.2 and 0.8 V in the charged and discharged state, correspondingly. This cell produces a current enough to make a single LED of white color working. The cell surface discharge capacity exceeds 230 μAh cm^?2.     

Oxalate precursor preparation of Li1.2Ni0.13Co0.13Mn0.54O2 for lithium ion battery positive electrode

Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ powders have been prepared through co-precipitation of metal oxalate precursor and subsequent solid state reaction with lithium carbonate. X-ray diffraction pattern shows that the massive rock-like structure has a good layered structure and solid solution characteristic. Scanning electron microscope and transition electron microscope images reveal that the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ composed of nanoparticles have the size of 1–2 μm. As a lithium ion battery positive electrode, the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ has an initial discharge capacity of 285.2 mAh g^?1 at 0.1 C within 2.0–4.8 V. When the cutoff voltage is decreased to 4.6 V, the cycling stability of product can be greatly improved, and a discharge capacity of 178.5 mAh g^?1 could be retained at 0.5 C after 100 cycles. At a high charge–discharge rate of 5 C (1,000 mAh g^?1), a stable discharge capacity of 121.4 mAh g^?1 also can be reached. As the experimental results, the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ prepared from oxalate precursor route is suitable as lithium ion battery positive electrode.     

Electrochemical behavior of Mg-doped 7LiFePO4–Li3V2(PO4)3 composite cathode material for lithium-ion batteries

Mg-doping effects on the electrochemical property of LiFePO₄–Li₃V₂(PO₄)₃ composite materials, a mutual-doping system, are investigated. X-ray diffraction study indicates that Mg doping decreases the cell volume of LiFePO₄ in the composite. The cyclic voltammograms reveal that the reversibility of the electrode reaction and the diffusion of lithium ion is enhanced by Mg doping. Mg doping also improves the conductivity and rate capacity of 7LiFePO₄–Li₃V₂(PO₄)₃ composite material and decreases the polarization of the electrode reaction. The discharge capacity of the Mg-doped composite was 93 mAh?g^?1 at the current density of 1,500 mA?g^?1, and Mg-doped composite has better discharge performance than the original 7LiFePO₄–Li₃V₂(PO₄)₃ composite at low temperature, too. At ?30 °C, the discharge capacity of Mg-doped LFVP is 89 mAh?g^?1, higher than that of the original composite. Electrochemical impedance spectroscopy study shows that Mg²⁺ doping could enhance the electrochemical activity of 7LiFePO₄–Li₃V₂(PO₄)₃ composite. Mg doping has a positive influence on the electrochemical performance of the LiFePO₄–Li₃V₂(PO₄)₃ composite material.     

Structure and electrochemical performance of LiCoO2 cathode material in different voltage ranges

LiCoO₂ sample prepared by high-temperature solid state calcination shows a typical hexagonal structure with a single phase and fine particle size distribution. The high-voltage electrolyte with additive fluoroethylene carbonate (FEC) has been used. Electrochemical results show that the initial discharge capacities of the prepared LiCoO₂ cathode are 157.7, 169.5, 191.0, and 217.5 mAh g^?1 in the voltage ranges of 3.0–4.3, 3.0–4.4, 3.0–4.5, and 3.0–4.6 V, respectively. The capacity increases, while the initial coulombic efficiency and capacity retention decrease with increasing the charge cutoff voltage. The capacity retention is only 10.4 % after 200 cycles at 1C rate in the voltage range of 3.0–4.6 V. X-ray diffraction measurements confirm structural changes of the layered material in the different voltage ranges. A phase transition from the O3 to the H1-3 phase can be observed when LiCoO₂ is charged above 4.5 V. The AC impedance analysis indicates that the resistances (R _(sf+b), R _ct) of the prepared LiCoO₂ rapidly increase when the cell is charged to higher voltage. The amount of dissolved Co into the electrolyte also greatly increases with increasing the charge cutoff voltage.     

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.     

CeO<Subscript>2</Subscript> coating to improve the performance of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript>

The Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ coated with CeO₂ has been fabricated by an ionic interfusion method. Both the bare and the CeO₂-coated samples have a typical layered structure with R-3m and C2/m space group. The results of XRD and TEM images display that the CeO₂ coating layer on the precursor could enhance the growth of electrochemically active surface planes ((010), (110), and (100) planes) in the following ionic interfusion process. The results of galvanostatic cycling tests demonstrate that the CeO₂-coated sample has a discharge capacity of 261.81 mAh g^?1 with an increased initial Coulombic efficiency from 62.4 to 69.1% at 0.05 °C compared with that of bare sample and delivers an improved capacity retention from 71.7 to 83.4% after 100 cycles at 1 °C (1 °C?=?250 mA g^?1). The results of electrochemical performances confirm that the surface modification sample exhibits less capacity fading, lower voltage decay, and less polarization.     

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.