Nano-sized lithium manganese oxide dispersed on carbon nanotubes for energy storage applications

Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 °C for 30 min using MnO₂-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite.     

A novel concept of hybrid capacitor based on manganese oxide materials

A novel asymmetric hybrid capacitor using LiMn₂O₄ and manganese oxide (MnO₂)/carbon nanotube (CNT) nanocomposite as the positive and negative electrode materials, respectively, and 1 M LiClO₄ in propylene carbonate (PC) as the electrolyte has been developed. To the best of our knowledge, this is the first reported assembly of an asymmetric hybrid capacitor with metal oxides for both electrode materials, and, especially, with MnO₂ as the negative electrode material. The discharge profile of the asymmetric hybrid capacitor shows a typical capacitive behavior with a linear slope. The asymmetric hybrid capacitor was able to deliver a specific energy as high as 56 Wh/kg at a specific power of 300 W/kg, based on the total weight of LiMn₂O₄ and MnO₂/CNT nanocomposite in both electrodes. These results clearly demonstrated a superior performance of this new type of capacitor with a higher specific energy compared to other types of asymmetric hybrid capacitors.     

Zinc and aluminium: glutamic acid assisted dual-doped LiMn2O4 spinels via sol–gel method as cathode material for use in lithium rechargeable batteries

Journal of Sol-Gel Science and Technology - LiMn2O4 and LiZnxAlyMn2-x-yO4 (x = 0.07–0.10; y = 0.15–0.18) powders have been synthesized by...     

The phase transition behaviors of Li1−xMn0.5Fe0.5PO4 during lithium extraction studied by in situ X-ray absorption and diffraction techniques

How the structural changes take place in LiMn_yFe_1−yPO₄-type cathode materials during lithium extraction/insertion is an important issue, especially on if they go through the single-phase reaction (i.e., solid solution reaction) or the two-phase reaction regions. Here we report the studies on the phase transition behaviors of a carbon coated Li_1−xMn_0.5Fe_0.5PO₄ (CLi₁₋xMn_0.5Fe0_.5PO₄, 0.0  x  1.0) sample during the first charge using in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques. The combination of in situ XAS and XRD results clearly identify two two-phase coexistence regions at two voltage plateaus of 3.6 (Fe²⁺/Fe³⁺) and 4.2 V (Mn²⁺/Mn³⁺) and a narrow intermediate region which proceeds via single-phase reaction in between two two-phase regions. In addition, simultaneous redox reactions of Fe²⁺/Fe³⁺ and Mn²⁺/Mn³⁺ in the narrow single-phase region are reported and discussed for the first time.     

The condition for the evolution of extra current peak in the cyclic voltammogram of LixMn2O4 investigated by in situ bending beam method

The condition for the occurrence of extra current peak near 3.7 ～ 3.9 V in CV and the relationship between the intensity of the extra current peak and the volume of phase transformation from tetragonal to cubic phase was investigated using in situ bending beam method. It was found that the extra current peak evolved when the sample was subject to the 3 V range and its intensity increased as the excursion depth to the 3 V range was increased. The in situ bending beam method data revealed that the extra current peak accompanied the tensile strain variation which is due to the phase transformation of a residual tetragonal phase to a cubic phase. Further, it was found that the amount of the phase transformation increased as the excursion depth to the 3 V range increased, i.e. the volume of the phase transformation was proportional to the intensity of the extra current peak. It seems that the phase transformation from tetragonal phase to cubic phase cannot be completed during the voltage sweep at the 3 V peak. On the contrary, the voltage excursions to 4 V range did not affect the evolution of the extra current peak.     

Novel concept of pseudocapacitor using stabilized lithium metal powder and non-lithiated metal oxide electrodes in organic electrolyte

A concept of using two non-prelithiated metal oxides (e.g., MnO₂, V₂O₅, and FeO_x) in both positive and negative electrodes in organic Li-ion electrolytes has been proposed and tested to improve the energy density of pseudocapacitors. To take the advantages of this concept, additional lithium source is essential to provide lithium ions during the charge–discharge cycles. The stabilized lithium metal powder (SLMP^?) developed by FMC Corp., provides such an essential Li⁺ source. Here we report the first result of the symmetric pseudocapacitor using two non-prelithiated metal oxide (i.e., manganese oxide/carbon nanotube (MnO₂/CNT)) electrodes, with added SLMP in one of them. The capacitor using the SLMP added MnO₂/CNT (positive) and pure MnO₂/CNT (negative) electrode in 1.2 M LiPF₆-EC:EMC electrolyte shows supercapacitive behaviors in 3.0 V voltage range. The addition of SLMP opens new opportunities of using the non-lithiated metal oxide electrodes in pseudocapacitors and hybrid electrochemical capacitors (ECs), which has not been possible before.     

Investigation of the charge compensation mechanism on the electrochemically Li-ion deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 electrode system by combination of soft and hard X-ray absorption spectroscopy

In situ hard X-ray absorption spectroscopy (XAS) at metal K-edges and soft XAS at O K-edge and metal L-edges have been carried out during the first charging process for the layered Li1-xCo1/3Ni1/3Mn1/3O2 cathode material. The metal K-edge XANES results show that the major charge compensation at the metal site during Li-ion deintercalation is achieved by the oxidation of Ni2+ ions, while the manganese ions and the cobalt ions remain mostly unchanged in the Mn4+ and Co3+ state. These conclusions are in good agreement with the results of the metal K-edge EXAFS data. Metal L-edge XAS results at different charge states in both the FY and PEY modes show that, unlike Mn and Co ions, Ni ions at the surface are oxidized to Ni3+ during charge, whereas Ni ions in the bulk are further oxidized to Ni4+ during charge. From the observation of O K-edge XAS results, we can conclude that a large portion of the charge compensation during Li-ion deintercalation is achieved in the oxygen site. By comparison to our earlier results on the Li1-xNi0.5Mn0.5O2 system, we attribute the active participation of oxygen in the redox process in Li1-xCo1/3Ni1/3Mn1/3O2 to be related to the presence of Co in this system.     

In situ X-ray absorption and diffraction studies of carbon coated LiFe1/4Mn1/4Co1/4Ni1/4PO4 cathode during first charge

Synchrotron based in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques are used to study electronic and crystal structure changes of the carbon coated LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄ (LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄/C) cathode material for Li-ion batteries during the first charge. In situ Fe, Mn, Co and Ni K-edge XAS results revealed that the three voltage plateaus at ～3.6, 4.2 and 4.7 V vs. Li/Li⁺ are attributed to the redox reactions of Fe²⁺/Fe³⁺, Mn²⁺/Mn³⁺ and Co²⁺/Co³⁺, respectively, while the apparent capacities above 4.9 V is not originated from the Ni²⁺/Ni³⁺ redox, but very likely from the electrolyte decomposition. Interesting phase transition behaviors of LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄/C were observed with the formation of an intermediate phase and the solid solution regions. Combined in situ XAS and XRD techniques indicate fast electronic structural changes and slow bulk crystal structural changes.