Hydrothermal synthesis and electrochemical performance of Mn-doped V<Subscript>6</Subscript>O<Subscript>13</Subscript> as cathode material for lithium-ion battery

Mn_xV_6?xO₁₃ (x?=?0.01, 0.02, 0.03, 0.04) were successfully synthesized via a simple hydrothermal method followed by heat-treatment. Both crystal domain size, electronic conductivity and the lithium diffusion coefficient of the Mn_xV_6?xO₁₃ samples were influenced by the doping amount of Mn²⁺. When x?=?0.02, the product was nano-sized particles and exhibited the best electrochemical performance. The enhanced electrochemical performance originated from its higher total conductivity and higher lithium diffusion coefficient.     

Tailoring of electrochemical properties of V2O5 thin films grown on flexible substrates using plasma-assisted activated reactive evaporation

The vanadium pentoxide (V₂O₅) thin films have been deposited using home built activated reactive evaporation technique on indium tin oxide-coated flexible Kapton substrates and investigated their microstructural and electrochemical properties. X-ray diffraction pattern displayed predominant (001) orientation designating the orthorhombic structure of the films deposited at optimised growth conditions. The surface of the films is observed to be composed of vertical elliptical-shaped grains of size 98 nm distributed uniformly over the surface of the films provided with root mean square surface roughness of 9 nm as evidenced from atomic force microscopy studies. As-deposited V₂O₅ thin films demonstrated constant discharge capacity of about 60 μAh/(cm² _?μm) for 10 cycles at room temperature in the potential window of 4.0–2.5 V. The influence of silver (Ag) interlayer on electrochemical properties of V₂O₅ films was investigated and observed appreciable improvement in electrochemical performance of ‘V₂O₅/Ag/V₂O₅’ films. The multilayered V₂O₅/Ag/V₂O₅ films exhibited a discharge capacity of about 75 μAh/(cm² _?μm) provided with enhanced cycliability.     

Vanadium Pentoxide‐Based Cathode Materials for Lithium‐Ion Batteries: Morphology Control,Carbon Hybridization,and Cation Doping

Vanadium pentoxide (V₂O₅) is a promising cathode material for high‐performance lithium‐ion batteries (LIBs) because of its high specific capacity, low cost, and abundant source. However, the practical application of V₂O₅ in commercial LIBs is still hindered by its intrinsic low ionic diffusion coefficient and moderate electrical conductivity. In the past decades, progressive accomplishments have been achieved that rely on the synthesis of nanostructured materials, carbon hybridization, and cation doping. Generally, fabrication of nanostructured electrode materials can effectively decrease the ion and electron transport distances while carbon hybridization and cation doping are able to significantly increase the electrical conductivity and diffusion coefficient of Li⁺. Implementation of these strategies addresses the problems that are related to the ionic and electronic conductivity of V₂O₅. Accordingly, the electrochemical performances of V₂O₅‐based cathodes are significantly improved in terms of discharge capacity, cycling stability, and rate capability. In this review, the recent advances in the synthesis of V₂O₅‐based cathode materials are highlighted that focus on the fabrication of nanostructured materials, carbon hybridization, and cation doping.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Effects of lithium excess amount on the microstructure and electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode material

Spinel LiNi_0.5Mn_1.5O₄ cathode materials with different lithium excess amount (0, 2%, 6%, 10%) were synthesized by a facile solid-state method. The effect of lithium excess amount on the microstructure, morphology, and electrochemical properties of LiNi_0.5Mn_1.5O₄ materials was systematically investigated. The results show that the lithium excess amount does not change the particle morphology and size obviously; thus, the electrochemical properties of LiNi_0.5Mn_1.5O₄ are mainly determined by structural characteristics. With the increase of lithium excess amount, the cation disordering degree (Mn³⁺ content) and phase purity first increase and then decrease, while the cation mixing extent has the opposite trend. Among them, the LiNi_0.5Mn_1.5O₄ material with 6% lithium excess amount exhibits higher disordering degree and lower impurity content and cation mixing extent, thus leading to the optimum electrochemical properties, with discharge capacities of 125.0, 126.1, 124.2, and 118.9 mAh/g at 0.2-, 1-, 5-, and 10-C rates and capacity retention rate of 96.49% after 100 cycles at 1-C rate.     

Structure and lithium storage performances of nickel hydroxides synthesized with different nickel salts

Nickel hydroxides with hierarchical micro-nano structures are prepared by a facile homogeneous precipitation method with different nickel salts (Ni(NO₃)₂·6H₂O, NiCl₂·6H₂O, and NiSO₄·6H₂O) as raw materials. The effect of nickel sources on the microstructure and lithium storage performance of the nickel hydroxides is studied. It is found that all the three prepared samples are α-nickel hydroxide. The nickel hydroxides synthesized with Ni(NO₃)₂·6H₂ or NiCl₂·6H₂O show a similar particle size of 20–30 μm and are composed of very thin nano-sheets, while the nickel hydroxide synthesized with Ni(SO₄)₂·6H₂O shows a larger particle size (30–50 μm) and consists of very thin nano-walls. When applied as anode materials for lithium-ion batteries (LIBs), the nickel hydroxide synthesized with NiSO₄·6H₂O exhibits the highest discharge capacity, but its cyclic stability is very poor. The nickel hydroxides synthesized with NiCl₂·6H₂O exhibit higher discharge capacity than the nickel hydroxides synthesized with Ni(NO₃)₂·6H₂O, and both of them show much improved cyclic stability and rate capability as compared to the nickel hydroxide synthesized with Ni(SO₄)₂·6H₂O. Moreover, pseudocapacitive behavior makes a great contribution to the electrochemical energy storage of the three samples. The discrepancies of lithium storage performance of the three samples are analyzed by ex-situ XRD, FT-IR, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) tests.     

Influence of surface modification by vanadium oxide and carbon on the electrochemical performance of LiFePO4/C

Surface modification with metal oxides is an efficient method to improve the performance of LiFePO₄. Carbon and V₂O₃ co-coated LiFePO₄ is synthesized by carbothermal reduction method combined with star-balling technique, and vanadium oxide is produced in situ. The structure and pattern of LiFePO₄/C modified with different amounts of vanadium oxide (0–5 mol%) were studied by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy. The electrochemical performance of material electrodes was analyzed by constant current charge–discharge and electrochemical impedance spectra (EIS). Electrochemical test results show that sample B (1.0 mol%) exhibits the best electrochemical performance, whose discharge capacity is up to 160.1, 127.2, and 88.4 mAh?g^?1 at 1, 5, and 10 °C, respectively. It indicates that V₂O₃ modification efficiently improves specific capacity and rate capability. The EIS experiment demonstrates that catalytic activity and reversibility of the cathode electrode are obviously increased by the surface modification of vanadium oxide.     

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.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

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.     

Influence of post-calcination treatment on the spinel lithium titanium oxide anode material for lithium ion batteries

The influence of post-calcination treatment on spinel Li₄Ti₅O₁₂ anode material is extensively studied combining with a ball-milling-assisted rheological phase reaction method. The post-calcinated Li₄Ti₅O₁₂ shows a well distribution with expanded gaps between particles, which are beneficial for lithium ion mobility. Electrochemical results exhibit that the post-calcinated Li₄Ti₅O₁₂ delivers an improved specific capacity and rate capability. A high discharge capacity of 172.9 mAh g^?1 and a reversible charge capacity of 171.1 mAh g^?1 can be achieved at 1 C rate, which are very close to its theoretical capacity (175 mAh g^?1). Even at the rate of 20 C, the post-calcinated Li₄Ti₅O₁₂ still delivers a quite high charge capacity of 124.5 mAh g^?1 after 50 cycles, which is much improved over that (43.9 mAh g^?1) of the pure Li₄Ti₅O₁₂ without post-calcination treatment. This excellent electrochemical performance should be ascribed to the post-calcination process, which can greatly improve the lithium ion diffusion coefficient and further enhance the electrochemical kinetics significantly.     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

Nano Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> as sulfur host for high-performance Li-S battery

S/Li₄Ti₅O₁₂ cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li₄Ti₅O₁₂ is used as sulfur host and fast Li⁺ conductor, which can adsorb effectively polysulfides and improve remarkably Li⁺ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li₄Ti₅O₁₂ cathode has a stable discharge capacity of 616 mAh g^?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g^?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li₄Ti₅O₁₂ cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li₄Ti₅O₁₂ as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.     

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.     

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.     

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.     

Electrical and electrochemical properties of carbon nanotube-based free standing LTO electrodes for current collector-free Li-ion batteries

The spinel lithium titanate oxide (Li₄Ti₅O₁₂, LTO) has been extensively studied as one of the most promising alternatives to carbon materials in energy conversion and storage devices, due to its high structural and thermal stability, rate capability, and excellent cycling stability. In this study, Li₄Ti₅O₁₂/multi-walled carbon nanotubes (LTO-MWCNTs) free-standing and flexible composite electrodes/buckypapers were prepared via tape casting technique and well compared with commercially available LTO. The structural, morphological, electrical and electrochemical properties of LTO-MWCNTs buckypaper as well as LTO were studied. The electrical conductivity of LTO-based buckypaper was found to be very high i. e, 4.4 × 10² Scm⁻¹ at room temperature. Further, the buckypaper prepared by synthesized LTO showed higher specific capacity (166 mAhg⁻¹) compared to commercially available LTO (137 mAhg⁻¹) at 0.2 C rate. The enhanced electrochemical performance of as-synthesized LTO-based buckypaper is mainly attributed to the higher electronic conductivity and homogeneous distribution of particles with its small size which facilitates large amount of active sites for lithium insertion and also short diffusion paths.     

Enhancement of electrochemical properties of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> as anode materials for lithium-ion batteries by transition metal doping

Misfit-layered calcium cobaltites (Ca₃Co₄O₉, Ca₃Co_3.9Fe_0.1O₉, and Ca₃Co_3.9Mn_0.1O₉), as anode materials for lithium-ion batteries, were synthesized by a simple hydro-decomposition method. All synthesized samples do not show any impurity phase. They exhibited plate-like particle with the particle size of 1–2 μm. The specific capacities of doped samples showed higher electrochemical performance compared to the undoped sample. After charge/discharge of 50 cycles, the specific capacities of Ca₃Co₄O₉, Ca₃Co_3.9Fe_0.1O₉, and Ca₃Co_3.9Mn_0.1O₉ were 343, 562, and 581 mAh g^?1, respectively. The doped samples showed an increase of over 60% compared to the undoped sample. The cyclic voltammetry profile of the doped samples showed the enhanced reactivity corresponding to their improved electrochemical performance. The capacity improvement of doped samples resulted from the metal oxide/Li conversion reactions, volume change, and high reactivity.     

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.