Nano/micro-hybrid NiS cathodes for lithium ion batteries

The present study highlights a low temperature process by which 1D stacked 3D microstructures of nickel sulfide comprised of nanospikes have been synthesized and assembled as cathodes for lithium chalcogenide batteries. These micro/nano-clusters were synthesized hydrothermally under different conditions. These clusters exhibited a surface area of 15 m² g⁻¹. The present study also provides the first reports on the electrochemical performance of these NiS microclusters as cathode materials in lithium fluoro-Tris-sulfonimide electrolyte for lithium ion batteries. A detailed study has been performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes impact the cyclic behavior and specific capacity. This electrode−electrolyte combination showed minimal dissolution of the electrode in the electrolyte which was confirmed by inductively coupled plasma atomic emission spectroscopy. From the electrochemical analysis performed an intrinsic correlation between the capacity, self-discharge property and the surface morphology has been deduced and explained on the basis of relative contributions from the redox reactions of nickel sulfide in lithium fluoro-Tris-sulfonimide electrolyte. A working model of lithium battery in a coin cell form is also shown exhibiting a specific capacity of 550 mAh g⁻¹.     

Charge/discharge characteristics of sulfur composite cathode materials in rechargeable lithium batteries

The charge and discharge characteristics of lithium batteries with sulfur composite cathodes have been investigated. The sulfur composites showed novel electrochemical characteristics. The analysis of the differential capacity indicated that the discharge process showed two voltage plateaus of 2.10 V and 1.88 V, and the charge process also presented two voltage plateaus of 2.22 V and 2.36 V. The overcharge test showed that the composite cannot be charged over 4.0 V, the voltage always stopped at about 3.9 V during charging, indicating that the composite presented the intrinsic safety for the overcharge of lithium batteries. The overcharge can cause serious safety problem for the conventional Li-ion batteries. The overcharge test also showed that the batteries with sulfur composite were destroyed when the upper cut-off voltage was over 3.6 V. However, the composite presented good reversible capacity after it was deep discharged even to 0 V. It showed stable cycleability and high cycling capacity of 1000 mAh g⁻¹ when cycling between 0.1 V and 3.0 V, indicative of the different characteristic from the conventional oxide cathode materials. The prototype polymer battery with the composite cathode material presented the energy density of 246 Wh kg⁻¹ and 401 Wh L⁻¹.     

Electrochemical performances of Al-based composites as anode materials for Li-ion batteries

Al-C, Al-Fe and Al-Fe-C composite materials have been prepared by high-energy ball milling technique. The electrochemical measurements demonstrated that the Al-Fe-C composites have greatly improved electrochemical performances in comparison with Al, Al-C and Al-Fe anode. For example, Al₇₁Fe₉C₂₀ can deliver the reversible capacity of 436 mAh g⁻¹ at first cycle and 255 mAh g⁻¹ at 15th cycle. This improved electrochemical performance could be attributed to the alloying formation of Al with Fe and the buffering effect by the graphite matrix. This suggests that the Al-Fe-C composite has a potential possibility to be developed as an anode material for lithium-ion batteries.     

The preparation of nano-sulfur/MWCNTs and its electrochemical performance

In this work, a novel nano-sulfur/MWCNTs composite with modified multi-wall carbon nano-tubes (MWCNTs) as sulfur-fixed matrix for Li/S battery is reported. Based on different solubility of sulfur in different solvents, nano-sulfur/MWCNTs composite was prepared by solvents exchange method. The composite was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modified MWCNTs are considered that not only acts as a conducting material, but also a matrix for sulfur. The electrochemical performance of the nano-sulfur/MWCNTs composite was tested. The results indicated that nano-sulfur/MWCNTs composite had the specific capacity of 1380 mAh g⁻¹, 1326 mAh g⁻¹ and 1210 mAh g⁻¹ in the initial cycle at 100 mA g⁻¹, 200 mA g⁻¹ and 300 mAh g⁻¹ discharge rates respectively, and remained a reversible capacity of 1020 mAh g⁻¹, 870 mAh g⁻¹ and 810 mAh g⁻¹ after 30 cycles. The electrochemical performances confirm that the modified MWCNTs as sulfur-fixed matrix show better ability than any other carbon in cathode of Li/S batteries that had been reported.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

Flower-like ZnO-NiO-C films with high reversible capacity and rate capability for lithium-ion batteries

Flower-like ZnO-NiO-C films with high reversible capacity and rate capability for lithium-ion batteries were fabricated through simple solution-immersion steps and subsequent heat treatment at moderate temperature. At a rate of 0.5 C, reversible capacity greater than 485 mAh g⁻¹ could be retained at the 50th cycle for ZnO-NiO-C films. More importantly, the films delivered reversible capacities of 380, 300, 230, and 180 mAh g⁻¹ at 1, 2, 3 and 4 C rates, respectively. The superior electrochemical properties of the ZnO-NiO-C films resulted from the advantages of flower-like architecture as well as the catalytic and conductive effects of the Ni phase produced in the first discharge process. Owing to easy fabrication and excellent electrochemical performance, these ZnO-NiO-C films will be promising anodes for lithium-ion batteries. The results of this study also offer possibilities of improving the lithium storage capacity of transition metal oxides by controlling both architecture and composition.     

Vanadium nitride as a novel thin film anode material for rechargeable lithium batteries

Vanadium mononitride (VN) thin films have been successfully fabricated by magnetron sputtering. Its electrochemical behaviour with lithium was examined by galvanostatic cell cycling and cyclic voltammetry. The capacity of VN was found to be stable above 800 mAh g⁻¹ after 50 cycles. By using ex situ X-ray diffraction, high-resolution transmission electron microscopy and selected area electron diffraction as well as in situ spectroelectrochemical measurements, the electrochemical reaction mechanism of VN with lithium was investigated. The reversible conversion reaction of VN into metal V and Li₃N was revealed. The high reversible capacity and good stable cycle of VN thin film electrode made it a new promising lithium-ion storage material for future rechargeable lithium batteries.     

Evaluation of ZnO nanorod arrays with dandelion-like morphology as negative electrodes for lithium-ion batteries

In this study, ZnO nanorod arrays have been evaluated for the negative electrodes of lithium-ion batteries. The ZnO nanorod arrays with dandelion-like morphology were directly grown on copper substrates by a hydrothermal synthesis process at 80 °C. X-ray diffraction, scanning electron microscopy, galvanostatic discharge-charge, and cyclic voltammetry were employed to characterize the structure and electrochemical property of the arrays. The array electrodes showed a stable capacity over 310 mAh g⁻¹ after 40 cycles, and good capacity retention as the anodes of lithium-ion batteries. It was believed that the unique dandelion-like binary-structure played an important role in the electrochemical performance of the array electrodes. The present finding opens the possibility to fabricate micro/nanometer hierarchical ZnO films that might be applied in lithium-ion batteries.     

Electrochemical study of NiO nanoparticles electrode for application in rechargeable lithium-ion batteries

Nickel oxide nanoparticles were synthesized via a simple and inexpensive microwave-assisted synthesis method within a fast reaction time of less than 20 min. The calcination of as-prepared precursor at 600 °C produces single phase nickel oxide. The lattice structure and morphology of the sample were investigated by X-ray diffraction, field-emission scanning electron microscopy and field-emission transmission electron microscopy. The particle size range of the nickel oxide nanoparticles varied from 50 to 60 nm. Nickel oxide nanoparticles exhibited good electrochemical performances as an anode material for lithium-ion batteries. The prepared nickel oxide anode revealed a large initial discharge capacity of 1111.08 mAh g⁻¹ at 0.03 C rate and retained 80% of initial capacity (884.30 mAh g⁻¹) after 20 cycles. Furthermore, at elevated rate of 3.7 C, the charge capacity of the nickel oxide electrode was as high as 253.1 mAh g⁻¹, which was 35% greater than that of commercial bulk nickel oxide (188 mAh g⁻¹). The enhancement of the electrochemical performance was attributed to the high specific surface area, good electric contact among the particles and easier lithium ion diffusion.     

Purification and carbon-film-coating of natural graphite as anode materials for Li-ion batteries

A process of modification of natural graphite materials as anode for lithium ion batteries was attempted. The process started with the treatment of natural graphite with concentrated hydrochloric acid and concentrated sulfuric acid in a thermal autoclave, followed by the in situ polymerization of resorcinol-formaldehyde resin to coat the graphite, then heat-treatment. SEM, XRD, Raman and electrochemical charge-discharge analysis showed that the surface defects and impurities on natural graphite were eliminated by purification of the concentrated acids, and carbon-film encapsulation modified the surface structure of the graphite and reduced its BET surface area. The as-obtained natural graphite sample presented an initial charge-discharge coulombic efficiency of 88.4% and a reversible capacity of 355.8 mAh g⁻¹. The proposed process paves a way to prepare a promising anode material with excellent performance with low cost of natural graphite for rechargeable lithium ion batteries.     

Layered lithium transition metal nitrides as novel anodes for lithium secondary batteries

We report the approach to overcome the deterrents of the hexagonal Li_2.6Co_0.4N as potential insertion anode for lithium ion batteries: the rapid capacity fading upon long cycles and the fully Li-rich state before cycling. Research reveals that the appropriate amount of Co substituted by Cu can greatly improve the cycling performance of Li_2.6Co_0.4N. It is attributed to the enhanced electrochemical stability and interfacial comparability. However, doped Cu leads to a slightly decreased capacity. High energy mechanical milling (HEMM) was found to effectively improve the reversible capacity associated with the electrochemical kinetics by modifying the active hosts’ morphology characteristics. Moreover, the composite based on mesocarbon microbead (MCMB) and Li_2.6Co_0.4N was developed under HEMM. The composite demonstrates a high first cycle efficiency at 100% and a large reversible capacity of ca. 450 mAh g⁻¹, as well as a stable cycling performance. This work may contribute to a development of the lithium transition metal nitrides as novel anodes for lithium ion batteries.     

Carbon nanobeads as an anode material on high rate capability lithium ion batteries

Carbon nanobeads (CNBs) were prepared by reacting cyclohexachlorobenzene with dispersed sodium metal at 200 °C for 4 h. The CNBs prepared in this manner formed uniform nanobeads, with sizes ranging from 100 to 300 nm. Heating resulted in a reduction in the size of the CNBs, and improvements in their degree of crystallinity. The nanosized carbon materials considerably increased the surface area of the powder, reducing the distance of the intercalation/deintercalation pathway, substantially improving the charge capacity of the lithium ion battery at a high charging rate. The charge capacity of CNBs was found to be 238 mAh g⁻¹, while that of commercial MCMB reached only 36 mAh g⁻¹, when the charging rate was 1C (372 mAh g⁻¹). As the charging rate was further increased to 2C (744 mAh g⁻¹) and 3C (1116 mAh g⁻¹), the charge capacities of CNBs dropped to 173 and 111 mAh g⁻¹, respectively. The cyclic performance of the CNBs was measured and found to be significantly improved in comparison to other carbonaceous materials, for up to 100 cycles. Although cyclic performance did result in a gradual reduction in capacity, the CNBs still greatly exceeded the capacity of MCMB. These results clearly demonstrate the potential role of CNBs as anodes for high capacity Li ion batteries for use in the automobile industry.     

Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries

Poly(pyrrole-co-aniline) (PPyA) copolymer nanofibers were prepared by chemical oxidation method with cetyltrimethyl ammonium chloride (CTAC) as template, and the nano-sulfur/poly(pyrrole-co-aniline) (S/PPyA) composite material in lithium batteries was achieved via co-heating the mixture of PPyA and sublimed sulfur at 160 °C for 24 h. The component and structure of the materials were characterized by FTIR, Raman, XRD, and SEM. PPyA with nanofiber network structure was employed as a conductive matrix, adsorbing agent and firm reaction chamber for the sulfur cathode materials. The nano-dispersed composite exhibited a specific capacity up to 1285 mAh g⁻¹ in the initial cycle and remained 866 mAh g⁻¹ after 40 cycles.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Facile preparation and good electrochemical hydrogen storage properties of chain-like and rod-like Co-B nanomaterials

Chain-like and rod-like Co-B nanomaterials are prepared by chemical reduction method in cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) aqueous solution, respectively. XRD patterns demonstrate that the two materials both have amorphous structures. SEM and TEM images show that the chain-like Co-B constructs of one-by-one tactic ball-like particles with nanoflakes on the surface, whereas the rod-like Co-B alloy possesses a porous nanostructure. The results of electrochemical measurements indicate that, as negative electrode materials of Ni-MH batteries, their electrochemical properties are both better than those of regular Co-B alloy. At the discharge current density 25 mA g⁻¹, the discharge capacities of the chain-like and the rod-like Co-B alloys are 314 mAh g⁻¹ and 292 mAh g⁻¹ after 50 cycles, respectively, which are both higher than that of regular Co-B alloy. XRD patterns of the electrodes on different charge-discharge states illustrate that the discharge capacity is attributed to hydrogenation of Co-B alloy.     

Tin dioxide/carbon nanotube composites with high uniform SnO2 loading as anode materials for lithium ion batteries

SnO₂/multi-walled carbon nanotube (MWCNT) composites were prepared by the solvothermal method and subsequent heat treatment at 360 °C. The samples were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Results on the higher SnO₂ content composite sample indicate that a uniform layer of SnO₂ nanocrystals with crystal size around 5 nm was deposited on the surface of the carbon nanotubes. The composite demonstrates a reversible lithium storage capacity of 709.9 mAh g⁻¹ at the first cycle and excellent cyclic retention up to 100 cycles as anode for lithium ion batteries.     

Electrochemical properties of heat-treated polymer-derived SiCN anode for lithium ion batteries

Silicon-carbon-nitrogen material (SiCN) is pyrolyzed from polysilylethylenediamine (PSEDA) derivation, followed by a heat-treating process at 1000 °C in Ar atmosphere. This heat-treated SiCN material has an excellent electrochemical performance as an anode for lithium ion batteries. Charge-discharge cycle measurements show that the heat-treated SiCN material exhibits a high first cycle discharge capacity of 829.0 mAh g⁻¹ and stays between 400 and 370 mAh g⁻¹ after 30 cycles. The discharge capacity remains above 300 mAh g⁻¹ at the high current density of 80 and 160 mA g⁻¹. These values are higher than untreated SiCN and commercial graphite anodes, which indicates that the heat-treating process improves the charge-discharge capacity, cycle stability and high-rate ability of SiCN anode. It is seemed that changes of SiCN structure, the formation of loose nano-holes on material surface and the formation of graphitic carbon phase in heat-treating process contribute to the improvement of electrochemical properties for SiCN anode.     

Nanostructured Si/TiC composite anode for Li-ion batteries

Si/TiC nanocomposite anode was synthesized by a surface sol-gel method in combination with a following heat-treatment process. Through this process, nanosized Si was homogeneously distributed in a titanium carbide matrix. The electrochemically less active TiC working as a buffer matrix successfully prevented Si from cracking/crumbling during the charging/discharging process. The interspaces in the Si/TiC nanocomposite could offer convenient channels for Li ions to react with active Si. The Si/TiC composite exhibited a reversible charge/discharge capacity of about 1000 mAh g⁻¹ with average discharge capacity fading of 1.8 mAh g⁻¹ (0.18%) from 2nd to 100th cycle, indicating its excellent cyclability when used as anode materials for lithium-ion batteries.     

Characterization of silicon- and carbon-based composite anodes for lithium-ion batteries

In recent years development of active materials for negative electrodes has been of great interest. Special attention has been focused on the active materials possessing higher reversible capacity than that of conventional graphite. In the present work the electrochemical performance of some carbon/silicon-based materials has been analyzed. For this purpose various silicon-based composites were prepared using such carbon materials as graphite, hard carbon and graphitized carbon black. An analysis of charging-discharging processes at electrodes based on different carbon materials has shown that graphite modified with silicon is the most promising anode material. It has also been revealed that the irreversible capacity mainly depends on the content of Si. An optimum content of Si has been determined with taking into account that high irreversible capacity is not suitable for practical application in lithium-ion batteries. This content falls within the range of 8-10 wt%.The reversible capacity of graphite modified with 8 wt% carbon-coated Si was as high as 604 mAh g⁻¹. The irreversible capacity loss with this material was as low as 8.1%. The small irreversible capacity of the material allowed developing full lithium-ion rechargeable cells in the 2016 coin cell configuration. Lithium-ion batteries based on graphite modified with silicon show gravimetric and volumetric specific energy densities which are higher by approximately 20% than those for a lithium-ion battery based on natural graphite.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.