Impedance spectroscopy analysis of LiZnVO4 and LiMgVO4

A comparative LiZnVO₄ and LiMgVO₄ conductivity study was done from room temperature to 500 °C and at frequencies from 42 to 1 MHz. The impact of moisture absorption to the materials’ conductivity was investigated. It was shown for LiZnVO₄ that moisture absorption is responsible for the decrease of the compound’s conductivity as the material is heated up to 150 °C. The LiZnVO₄ bulk activation energy value was calculated to be 1.20 eV. Two grain boundary activation energy values were calculated for the LiZnVO₄, 0.59 eV at the lower temperature range and 1.37 eV at the higher temperature range. An explanation for the existence of these two values was given. Both materials’ plots of the loss factor (tanδ) versus frequency at different temperatures were found to display a peak, and the modulus master curves present a scaling behavior that suggests non Debye type conductivity relaxation and ion migration via hopping.     

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.     

Enhanced lithium storage performance of a self-assembled hierarchical porous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/VGCF hybrid high-capacity anode material for lithium-ion batteries

A Co₃O₄/vapor-grown carbon fiber (VGCF) hybrid material is prepared by a facile approach, namely, via liquid-phase carbonate precipitation followed by thermal decomposition of the precipitate at 380 °C for 2 h in argon gas flow. The material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller specific surface area analysis, and carbon elemental analysis. The Co₃O₄ in the hybrid material exhibits the morphology of porous submicron secondary particles which are self assembled from enormous cubic-phase crystalline Co₃O₄ nanograins. The electrochemical performance of the hybrid as a high-capacity conversion-type anode material for lithium-ion batteries is investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic discharge/charge methods. The hybrid material demonstrates high specific capacity, good rate capability, and good long-term cyclability, which are far superior to those of the pristine Co₃O₄ material prepared under similar conditions. For example, the reversible charge capacities of the hybrid can reach 1100–1150 mAh g^?1 at a lower current density of 0.1 or 0.2 A g^?1 and remain 600 mAh g^?1 at the high current density of 5 A g^?1. After 300 cycles at 0.5 A g^?1, a high charge capacity of 850 mAh g^?1 is retained. The enhanced electrochemical performance is attributed to the incorporated VGCFs as well as the porous structure and the smaller nanograins of the Co₃O₄ active material.     

Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@C hollow microspheres with high capacity as an anode material for lithium-ion batteries

Three-dimensional hierarchical Co₃O₄@C hollow microspheres (Co₃O₄@C HSs) are successfully fabricated by a facile and scalable method. The Co₃O₄@C HSs are composed of numerous Co₃O₄ nanoparticles uniformly coated by a thin layer of carbon. Due to its stable 3D hierarchical hollow structure and uniform carbon coating, the Co₃O₄@C HSs exhibit excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs). The Co₃O₄@C HSs electrode delivers a high reversible specific capacity, excellent cycling stability (1672 mAh g^?1 after 100 cycles at 0.2 A g^?1 and 842.7 mAh g^?1 after 600 cycles at 1 A g^?1), and prominent rate performance (580.9 mAh g^?1 at 5 A g^?1). The excellent electrochemical performance makes this 3D hierarchical Co₃O₄@C HS a potential candidate for the anode materials of the next-generation LIBs. In addition, this simple synthetic strategy should also be applicable for synthesizing other 3D hierarchical metal oxide/C composites for energy storage and conversion.     

Promising anode material for lithium-ion cells based on cobalt oxide synthesized by microwave heating

High-performance anode material for lithium-ion cell based on cobalt oxide was synthesized through a combination of sol-gel route and subsequent microwave heating. The influence of microwave irradiation temperature of the precursor on the characteristics of the active materials formed was studied. The physicochemical, structural, and morphological properties of the materials were studied in addition to the electrochemical performance by cyclic voltammetry and charge-discharge cycling vs. Li⁺/Li. Microwave heating at 350 °C resulted in the formation of Co₃O₄, whereas at 450 and 550 °C, a mixture of Co₃O₄, CoO, and Co was formed. Co₃O₄ synthesized at 350 °C possessed porous morphology with high specific surface area and exhibited superior electrochemical performance with initial specific capacity of 982 mAh g^?1 and coulombic efficiency of ~75% along with good cycle performance retaining ~87% of initial capacity after 60 cycles.     

Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres and their lithium storage properties

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo₂O₄ microspheres have been fabricated by calcinating the Zn_1/3Co_2/3CO₃ precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo₂O₄ microspheres exhibit an initial discharge capacity of 1,369 mAh g^?1 (3,244.5 F cm^?3) and retain stable capacity of 800 mAh g^?1 (1,896 F cm^?3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo₂O₄ 3D hierarchical structures provide a large number of active surface position for Li⁺ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.     

Scalable synthesis and superior performance of TiO<Subscript>2</Subscript>-reduced graphene oxide composite anode for sodium-ion batteries

TiO₂-reduced graphene oxide (RGO) composite was synthesized via a sol-gel process and investigated as an anode material for sodium-ion batteries (SIBs). A remarkable improvement in sodium ion storage with a reversible capacity of 227 mAh g^?1 after 50 cycles at 50 mA g^?1 is achieved, compared to that (33 mAh g^?1) for TiO₂. The enhanced electrochemical performance of TiO₂-RGO composite is attributed to the larger specific surface area and better electrical conductivity of TiO₂-RGO composite. The excellent performance of TiO₂-RGO composite enables it a potential electrode material for SIBs.     

Nanocrystalline Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> electrodes for supercapattery application

Nanocrystalline Li₂TiO₃ was successfully synthesized using solid-state reaction method. The microstructural and electrochemical properties of the prepared material are systematically characterized. The X-ray diffraction pattern of the prepared material exhibits predominant (002) orientation related to the monoclinic structure with C2/c space group. HRTEM images and SAED analysis reveal the well-developed nanostructured particles with average size of ～40 nm. The electrochemical properties of the prepared sample are carried out using cyclic voltammetry (CV) and chronopotentiometry (CP) using Pt//Li₂TiO₃ cell in 1 mol L^?1 Li₂SO₄ aqueous electrolyte. The Li₂TiO₃ electrode exhibits a specific discharge capacity of 122 mAh g^?1; it can be used as anode in Li battery within the potential window 0.0–1.0 V, while investigated as a supercapacitor electrode, it delivers a specific capacitance of 317 F g^?1 at a current density of 1 mA g^?1 within the potential range ?0.4 to +0.4 V. The demonstration of both anodic and supercapacitor behavior concludes that the nanocrystalline Li₂TiO₃ is a suitable electrode material for supercapattery application.     

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.     

Hydrothermal impregnation synthesis of cobalt pentlandite as anode material of H<Subscript>2</Subscript>S SOFC

In the present work, cobalt pentlandite (Co₉S₈) is studied as a solid oxide fuel cells (SOFC) anode material which is stable in H₂S-containing fuels and is promising in coal-based SOFCs. Co₉S₈ is synthesized via a simple hydrothermal method. Uniform and fine Co₉S₈ particles are deposited on to the YSZ skeleton directly by using hydrothermal impregnation method and adhered to the skeleton closely after heat treating in N₂. The symmetrical cells are measured in the presence of 50 ppm H₂S–H₂ to determine the electrochemical performance at intermediate temperatures. The polarization resistance is only 0.3385 Ω cm² at 650 °C. It is concluded that Co₉S₈ exhibits a combination of good electronic conductivity and catalytic activity and has the potential to be used as a sulfur-tolerant anode material of SOFCs.     

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.     

Electrospinning preparation of one-dimensional Co<Superscript>2+</Superscript>-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers for high-performance lithium ion battery

One-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofibers with a diameter of approximately 500 nm have been synthesized via a one-step controllable electrospinning method. The Co²⁺-doped Li₄Ti₅O₁₂ nanofibers were systematically characterized by XRD, ICP, TEM, SEM, BET, EDS mapping, and XPS. Based on the cubic spinel structure and one-dimensional effect of Li₄Ti₅O₁₂, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers exhibit the enlarged lattice volume, reduced particle size and enhanced electrical conductivity. More importantly, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers as a lithium ion battery anode electrode performs superior electrochemical performance than undoped Li₄Ti₅O₁₂ electrode in terms of electrochemical measurements. Particularly, the reversible capacity of Co²⁺-doped Li₄Ti₅O₁₂ electrode reaches up to 140.1 mAh g^?1 and still maintains 136.5 mAh g^?1 after 200 cycles at a current rate of 5 C. Therefore, one-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofiber electrodes, showing high reversible capacity and remarkable recycling property, could be a potential candidate as an anode material.     

S/N dual-doped carbon nanosheets decorated with Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanoparticles as high-performance anodes for lithium-ion batteries

In this work, we have successfully synthesized the S/N dual-doped carbon nanosheets which are strongly coupled with Co _x O _y nanoparticles (SNCC) by calcinating cobalt/dithizone complex precursor following KOH activation. The SNCC as anode shows the wonderful charge capacity of 1200 mAh g^?1 after 400th cycles at 1000 mA g^?1 for Li-ion storage. The superior electrochemical properties illustrate that the SNCC can be a candidate for high-performance anode material of lithium-ion batteries (LIBs) because of the facile preparation method and excellent performance. Significantly, we also discuss the mechanism for the SNCC from the strong synergistic effect perspective.     

Synthesis and performance of Li2NiTi3O8 as a new anode material for lithium-ion batteries

The titanate spinel Li₂NiTi₃O₈ is proposed for the first time as a new anode for lithium-ion batteries and successfully synthesized via a facile ball-milling assisted solid-state reaction method. The sample is characterized by X-ray diffraction patterns (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, cyclic voltammetry (CV) tests, and electrochemical impedance spectroscopy (EIS). The results reveal that the Li₂NiTi₃O₈ nanoparticles have well-distributed morphology, and the particle size ranges between 100 and 300 nm. Although the initial coulombic efficiency is only 56.3 %, the Li₂NiTi₃O₈ electrode still exhibits a high rate capability and excellent cycling stability. The Li₂NiTi₃O₈ anode provides a large capacity of 212.3 mAh g^?1 at 0.1 A g^?1 after 10 cycle, which is close to its theoretical capacity (223.6 mAh g^?1). Even after 100 cycles, it still delivers a quite high capacity of 203.98 mAh g^?1, with no significant capacity fading. This indicates that the as-synthesized Li₂NiTi₃O₈ material is a promising anode material for lithium-ion batteries.     

Fabrication and electrochemical investigation of MWO<Subscript>4</Subscript> (M = Co,Ni) nanoparticles as high-performance anode materials for lithium-ion batteries

In this work, the MWO₄ (M = Co, Ni) nanoparticles were successfully synthesized by a facile one-step hydrothermal method and used as novel anode materials for LIBs. The micromorphology of obtained CoWO₄ and NiWO₄ was uniform nanoparticles with the size of ~60 and ~40 nm, respectively, by structural characterization including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). When tested as lithium-ion battery anode, CoWO₄ nanoparticles exhibited a stabilized reversible capacity of 980 mA h g^?1 at 200 mA g^?1 after 120 cycles and 632 mA h g^?1 at 1000 mA g^?1 even after 400 cycles. And, the discharge capacity was as high as 550 mA h g^?1 at the 400th cycle for NiWO₄ nanoparticles. The excellent electrochemical performance could be attributed to the unique nanoparticles structure of the materials, which can not only shorten the diffusion length for electrons and lithium ions but also provide a large specific surface area for lithium storage.     

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.     

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.     

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.     

Synthesis of hierarchical Na<Subscript>2</Subscript>FeP<Subscript>2</Subscript>O<Subscript>7</Subscript> spheres with high electrochemical performance via spray drying

Hierarchical Na₂FeP₂O₇ spheres with nanoparticles were successfully fabricated by a facile spray drying method. A relatively low drying temperature was introduced in order to form a carbon layer on the surface. As a cathode material for sodium-ion batteries, it delivered a reversible capacity of 84.4 mAh g^?1 at 0.1 C and showed excellent cycling and rate performance (64.7 mAh g^?1 at 5 C). Furthermore, a full sodium battery was fabricated using SP-Na₂FeP₂O₇ as the cathode and hard carbon as the anode, suffering almost no capacity loss after 400 cycles at 1 C. Due to its superior electrochemical property and the low materials cost, Na₂FeP₂O₇ is becoming a promising cathode material for large-scale energy storage systems.     

Preparation of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries

A flexible Co₃O₄ hollow microsphere/graphene/carbon nanotube hybrid film is successfully prepared through a facile filtration strategy and a subsequent thermally treated process. The composition, morphology, and structure of the as-prepared film are characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscopy, and transmission electron microscopy. Based on the morphology characterizations on the hybrid film, the Co₃O₄ hollow microspheres are uniformly and closely attached on three-dimensional (3D) graphene/carbon nanotubes (GR/CNTs) network, which decreases the agglomeration of Co₃O₄ microspheres effectively. In this hybrid film, the 3D GR/CNT network which enhances conductance as well as prevents aggregation is a benefit to help Co₃O₄ to exert its lithium storage capabilities sufficiently. When used as a binder-free anode material for lithium-ion batteries, the hybrid film delivers excellent electrochemical properties involving reversible capacity (863 mAh g^?1 at a current density of 100 mA g^?1) and rate performance (185 mAh g^?1 at a current density of 1600 mA g^?1).