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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: 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]