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Abstract: The co-existence of two mechanisms, the surface chemisorption mechanism (SCM) and the tunnel storage mechanism (TSM), for the charge storage of MnO2 is investigated. Sample α-MnO2 whose tunnels (2×2) are almost vacant is synthesized by chemical co-precipitation technique. To verify whether the charge storage of as-prepared α-MnO2 involves the charges based on the SCM besides the TSM, Ba2+ and K+ are intercalated into the tunnels of α-MnO2 by refluxing and samples Ba-MnO2 and K-MnO2 are obtained, respectively. By powder X-ray diffraction, ICP and the extraction test, it is confirmed that Ba2+ and K+ occupy the tunnels and are difficult to remove. By electrochemical analyses, we have found that the charge storage of Ba-MnO2 and K-MnO2 basically depends on the SCM, as Ba2+ and K+ stabilized in the tunnels in advance block the intercalation/deintercalation of cations from the electrolyte. Thus, it can be inferred that for α-MnO2 two mechanisms contribute to the charge storage. The contributions of α-MnO2''s mechanisms are estimated. The charges based on the TSM predominantly account for 81.2–89.9% of the total charges. The charges on the SCM may contribute to 7.9–16.8% and are not negligible. The charges from double-layer capacitance may be negligible, since it is only 1.1–4.1%. [Copyright &y& Elsevier]

Abstract: Manganese dioxide has been synthesized by a self-reacting microemulsion method. The result of X-ray diffraction shows that lack of clear peaks and broadening of peaks indicate its amorphous nature. Typical cyclic voltammograms were measured in 0.5molL−1 Na2SO4 aqueous solution and the potential ranges were controlled from −0.5 to 0.5, from −0.65 to 0.65, and from −0.75 to 0.75V versus Hg/Hg2SO4 at a sweep rate of 2mVs−1. Rectangular and symmetric image was observed between −0.5 and 0.5V indicating high electrochemical reversibility in this potential and sweep rate. The influence of cation species and concentration (activity) on electrochemical performances of MnO2 is also discussed in this work. Cyclic voltammetric experiments have been performed between −0.5 and 0.5V versus Hg/Hg2SO4 in Li2SO4, Na2SO4 and K2SO4 aqueous solutions with different salt concentrations ranging from 0.05 to 1molL−1. The specific capacitance of MnO2 was found to depend strongly on the cation concentration and species, and specific capacitance value will increase with the increase of cation concentration for all electrolytes. The logarithmic dependence of capacitance of MnO2 on cation activity indicates that the charge storage for MnO2 is involved in a fast redox reaction through cation insertion. [Copyright &y& Elsevier]

Abstract: The lithium ion batteries using Li4Ti5O12 as the anode material are easily being inflated during charge and discharge, which, however, does not occur in the batteries using graphite as the anode material. The high reduction reactivity of electrolyte on the Li4Ti5O12 material may be the main reason. In this work, the reduction reactivities of electrolyte on the uncoated and carbon-coated Li4Ti5O12 electrodes are compared for the first time. The results show that the reduction decomposition of electrolyte does occur on the uncoated Li4Ti5O12 electrode at around 0.7V, while it only takes place at the first cycle on the carbon-coated Li4Ti5O12 electrode. The carbon coating layers cover the catalytic active sites of Li4Ti5O12 particles and separate the Li4Ti5O12 particles from the electrolyte. A successive solid electrolyte interface (SEI) film is formed on the carbon layer during the formation process, which can prevent the further reduction decomposition of electrolyte at around 0.7V. The impurity phases of rutile and anatase TiO2 do not influence the reduction reactivity of electrolyte. This work is not only important to understand the reduction decomposition mechanism of electrolyte on the Li4Ti5O12 electrode, but also provides an effective solution to suppress the reduction decomposition of electrolyte in the batteries. [Copyright &y& Elsevier]

Abstract: Understanding the formation of SEI films on Li4Ti5O12 (LTO) anodes offers a major benefit to large-scale applications of lithium ion batteries made therefrom. This paper reveals that an SEI film is formed above 1 V due to the interfacial reaction between the electrode and electrolyte: LTO anodes are previously considered free from SEI films when cycled between 1 and 3 V. The reactivity and the formation of SEI films are much affected by the morphology and surface area of the electrode. To study the above, LTO powders with different morphologies are synthesized using lithium acetate (LA) and lithium hydroxide (LH) as the lithium sources. LTO–LH consisting of agglomerates of primary small particles with a large surface area has higher reactivity than LTO–LA with a cubic structure and small surface area. As a result, the LTO–LH anode with a smooth SEI film offers better cyclic performance than the LTO–LA anode with a porous SEI film. The addition of vinylene carbonate to the electrolyte facilitates rapid formation of a protective SEI film on LTO–LA, greatly improving the rate and cyclic performance: stable specific capacity of 155.6 mAh g−1 and remarkable 135.2 mAh g−1 after 500 cycles at 10 C are recorded. [Copyright &y& Elsevier]

Abstract: The structural and thermal stabilities of the layered Li(Ni1/3Co1/3Mn1/3)O2 cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni1/3Co1/3Mn1/3)O2/graphite high power batteries. The Li(Ni1/3Co1/3Mn1/3)O2 materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10C discharge rate at temperatures of 25 and 50°C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni1/3Co1/3Mn1/3)O2 cathode and the Joule heat that results from the great increase in the total resistance (R cell) of batteries. The reactions of fully charged Li(Ni1/3Co1/3Mn1/3)O2 cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140°C in the fully charged batteries during oven test, which is much lower than the temperature of about 240°C required for the reactions outside batteries. [Copyright &y& Elsevier]