Graphene is a single atomic layer of carbon atoms, and has exceptional electrical, mechanical, and optical characteristics. It has been broadly utilized in the fields of material science, physics, chemistry, device fabrication, information, and biology. In this review paper, we briefly investigate the ideas, structure, characteristics, and fabrication techniques for graphene applications in lithium ion batteries (LIBs). In LIBs, a constant three-dimensional (3D) conductive system can adequately enhance the transportation of electrons and ions of the electrode material. The use of 3D graphene and graphene-expansion electrode materials can significantly upgrade LIBs characteristics to give higher electric conductivity, greater capacity, and good stability. This review demonstrates several recent advances in graphenecontaining LIB electrode materials, and addresses probable trends into the future.

Cathode materials and their precursors are prepared with transition metal solutions recycled from the thewaste lithium-ion batteries containing NCM (nickel-cobalt-manganese) cathodes by a H2 and C-reduction process. Therecycled transition metal sulfate solutions are used in a co-precipitation process in a CSTR reactor to obtain the tran-sition metal hydroxide. The NCM cathode materials (Ni:Mn:Co=5:3:2) are prepared from the transition metal hydroxideby calcining with lithium carbonate. X-ray diffraction and scanning electron microscopy analyses show that the cathodematerial has a layered structure and particle size of about 10 µm. The cathode materials also exhibited a capacity ofabout 160 mAh/g with a retention rate of 93~96% after 100 cycles.

Tungsten oxide films were prepared by an electrochemical deposition method for use as the anode in rechargeable lithium batteries. Continuous potentiostatic deposition of the film led to numerous cracks of the deposits while pulsed deposition significantly suppressed crack generation and film delamination. In particular, a crack-free dense tungsten oxide film with a thickness of ca. 210 nm was successfully created by pulsed deposition. The thickness of tungsten oxide was linearly proportional to deposition time. Compositional and structural analyses revealed that the as-prepared deposit was amorphous tungsten oxide and the heat treatment transformed it into crystalline triclinic tungsten oxide. Both the as-prepared and heat-treated samples reacted reversibly with lithium as the anode for rechargeable lithium batteries. Typical peaks for the conversion processes of tungsten oxides were observed in cyclic voltammograms, and the reversibility of the heat-treated sample exceeded that of the as-prepared one. Consistently, the cycling stability of the heat-treated sample proved to be much better than that of the as-prepared one in a galvanostatic charge/discharge experiment. These results demonstrate the feasibility of using electrolytic tungsten oxide films as the anode in rechargeable lithium batteries. However, further works are still needed to make a dense film with higher thickness and improved cycling stability for its practical use.

Silicon-based thin film was prepared at room temperature by an electrochemical deposition method and a feasibility study was conducted for its use as an anode material in a rechargeable lithium battery. The growth of the electrodeposits was mainly concentrated on the surface defects of the Cu substrate while that growth was trivial on the defect-free surface region. Intentional formation of random defects on the substrate by chemical etching led to uniform formation of deposits throughout the surface. The morphology of the electrodeposits reflected first the roughened surface of the substrate, but it became flattened as the deposition time increased, due primarily to the concentration of reduction current on the convex region of the deposits. The electrodeposits proved to be amorphous and to contain chlorine and carbon, together with silicon, indicating that the electrolyte is captured in the deposits during the fabrication process. The silicon in the deposits readily reacted with lithium, but thick deposits resulted in significant reaction overvoltage. The charge efficiency of oxidation (lithiation) to reduction (delithiation) was higher in the relatively thick deposit. This abnormal behavior needs to clarified in view of the thickness dependence of the internal residual stress and the relaxation tendency of the reaction-induced stress due to the porous structure of the deposits and the deposit components other than silicon.

A porous nickel-tin nano-dendritic electrode, for use as the anode in a rechargeable lithium battery, has been prepared by using an electrochemical deposition process. The adjustment of the complexing agent content in the deposition bath enabled the nickel-tin alloys to have specific stoichiometries while the amount of acid, as a dynamic template for micro-porous structure, was limited to a certain amount to prevent its undesirable side reaction with the complexing agent. The ratios of nickel to tin in the electro-deposits were nearly identical to the ratios of nickel ion to tin ion in the deposition bath; the particle changed from spherical to dendritic shape according to the tin content in the deposits. The nickel to tin ratio and the dendritic structure were quite uniform throughout the thickness of the deposits. The resulting nickel-tin alloy was reversibly lithiated and delithiated as an anode in rechargeable lithium battery. Furthermore, the resulting anode showed much more stable cycling performance up to 50 cycles, as compared to that resulting from dense electro-deposit with the same atomic composition and from tin electrodeposit with a similar porous structure. From the results, it is expected that highly-porous nickel-tin alloys presented in this work could provide a promising option for the high performance anode materials for rechargeable lithium batteries.