The study of lithium ion de-insertion/insertion in LiMn2O4 and determination of kinetic parameters in aqueous Li2SO4 solution using electrochemical impedance spectroscopy

In this work, we report a basic study on the mechanism of lithium ion de-insertion/insertion process from/into LiMn₂O₄ cathode material in aqueous Li₂SO₄ solution using electrochemical impedance spectroscopy (EIS). An equivalent circuit distinguishing the kinetic parameters of lithium ion de-insertion/insertion is used to simulate the experimental impedance data. The fitting results are in good agreement with the experimental results and the parameters of the kinetic process of Li⁺ de-insertion and insertion in LiMn₂O₄ at different potentials during charge and discharge are obtained using the same circuit. The results indicate that the de-insertion/insertion behavior of lithium ions at LiMn₂O₄ cathode in Li₂SO₄ aqueous solution is similar to that reported in the organic electrolytes. The charge transfer resistance (R_ct), warburg resistance, double layer capacitance and chemical diffusion coefficient (DLi+) vary with potentials during de-insertion/insertion processes. R_ct is lowest at the CV peak potentials and the important kinetic parameter, DLi+ exhibits two distinct minima at potentials corresponding to CV peaks during de-insertion–insertion and it was found to be between 10⁻⁸ and 10⁻¹⁰ cm² s⁻¹during lithium de-insertion/insertion processes.     

Improved performances of mechanical-activated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/MWNTs cathode for aqueous rechargeable lithium batteries

LiMn₂O₄/multi-walled carbon nanotubes (MWNTs) composite was synthesized by mechanical activation reaction followed by a heat-treatment (500 °C). The LiMn₂O₄ and LiMn₂O₄/MWNTs as cathodes were investigated in 1 M Li₂SO₄ by cyclic voltammetry (CV), galvanostatic charge/discharge (GC), and electrochemical impedance spectroscopy (EIS). The LiMn₂O₄/MWNTs cathode delivered higher discharge capacity (117 mAh g⁻¹) than LiMn₂O₄ (84.6 mAh g⁻¹). Furthermore, the results from EIS showed that LiMn₂O₄/MWNTs had a faster kinetic process for lithium ion intercalation/de-intercalation than LiMn₂O₄. Besides, LiMn₂O₄/MWNTs had better cycling stability and rate capability than LiMn₂O₄, which was confirmed by GC testing. SEM images showed that a three-dimensional network structure was formed during the mechanical activation, giving a decrease of particle size.     

Isothermal calorimetry investigation of Li1+xMn2−yAlzO4 spinel

The heat generation of LiMn₂O₄, Li_1.156Mn_1.844O₄, and Li_1.06Mn_1.89Al_0.05O₄ spinel cathode materials in a half-cell system was investigated by isothermal micro-calorimetry (IMC). The heat variations of the Li/LiMn₂O₄ cell during charging were attributed to the LiMn₂O₄ phase transition and order/disorder changes. This heat variation was largely suppressed when the stoichiometric spinel was doped with excess lithium or lithium and aluminum. The calculated entropy change (dE/dT) from the IMC confirmed that the order/disorder change of LiMn₂O₄, which occurs in the middle of the charge, was largely suppressed with lithium or lithium and aluminum doping. The dE/dT values obtained did not agree between the charge and the discharge at room temperature (25 °C), which was attributed to cell self-discharge. This discrepancy was not observed at low temperature (10 °C). Differential scanning calorimeter (DSC) results showed that the fully charged spinel with lithium doping has better thermal stability.     

Structural,microstructural and electrochemical studies on LiMn2-x(GdAl)xO4 with spinel structure as cathode material for Li-ion batteries

Gd and Al co-doped LiMn_2-x(GdAl)_xO₄ (x?=?0, 0.01, 0.02, 0.03, 0.04 and 0.05) materials with spinel structure were synthesized by sol–gel method. Powder X-ray diffraction results confirm the formation of cubic spinel structure and average particle sizes are found to be between 80 and 110?nm from FE-SEM and TEM analysis. Decrease in peak potential difference as a function of doping in Cyclic Voltammetry results establishes enhancement in Li⁺ intercalation and de-intercalation. Electrochemical Impedance Spectroscopy (EIS) results showed that accumulation of charges on electrode has improved with doping over pristine samples. At a doping of x?=?0.02 charge transfer resistance values were found to be least. First cycle charge–discharge profiles for LiMn_1.96(GdAl)_0.02O₄ shows 139.2?mAh/g discharge capacity over other doped derivatives and pure LiMn₂O₄ (119.6?mAh/g) in aqueous Li₂SO₄ electrolyte. Doping of x?=?0.02 exhibit good cycling performance with only a total 4% capacity loss after 30 cycles.     

From hydrated layered-spinel lithium manganate composite to high-performance spinel LiMn2O4: A novel synthesis tuned by the concentration of LiOH

To obtain high-performance spinel LiMn₂O₄, various types of hydrated layered-spinel lithium manganate composites have been controllably synthesized through the hydrothermal process. It is found that the composition and morphology of these intermediate products can be tuned by the concentration of LiOH: Li⁺ act as the template and OH^- provide the required alkaline environment. In particular, the nanostructure varies from nanowires to nanosheets at different levels, depending on the phase ratio of the spinel phase ranging from 0% to 100%. Phase purity and the corresponding electrochemical properties of the as-prepared LiMn₂O₄ products are further tailored through the subsequent heat treatment. With the optimized LiOH concentration of 0.08 M, the resulting LiMn₂O₄ cathode material exhibits the best electrochemical performance with the initial discharge capacity of 121.7 mA h g⁻¹ at 1 C and 117.8 mA h g⁻¹ at 30 C, while a retention over 90% can be achieved after 1500 cycles. This study will help deepen understanding of the function mechanisms and further direct the novel synthesis from hydrated layered-spinel lithium manganate composites to high-performance spinel LiMn₂O₄ cathode materials.     

Solid-state combustion synthesis of spinel LiMn2O4 using glucose as a fuel

Spinel LiMn₂O₄ cathode material was rapidly synthesized in 1 h by solid-state combustion synthesis using metal carbonates as metal ion sources and glucose as a fuel. The effect of different amounts of glucose on the structure and electrochemical performance of as-prepared LiMn₂O₄ was investigated by X-ray diffraction (XRD), scanning electron micrographs (SEM), galvanostatic charge–discharge test, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). LiMn₂O₄ spinel was identified as the main crystalline phase with the presence of minor Mn₃O₄. The amount of glucose greatly affected the formation of Mn₃O₄. The optimal content of glucose was found to be 10 wt%. Under this condition, the Mn₃O₄ peaks almost disappeared, and high-purity spinel LiMn₂O₄ was obtained. Its initial discharge specific capacity of was 125.9 mAh/g, and discharge specific capacity retained at 105.2 mAh/g after 40 cycles. The detail influence of glucose on the electrochemical activity, reversibility and cycling performance of LiMn₂O₄ was discussed.     

Synthesis and electrochemical characterization of LiMn2O4 cathode materials for lithium polymer batteries

Spinel LiMn₂O₄ powders with sub-micron, narrow particle-size distribution, and phase-pure particles were synthesized at low temperatures from aqueous solution of metal acetate containing glyoxylic acid as a chelating agent by a sol-gel method. The effects of the calcination temperature and glyoxylic acid quantity on the physicochemical properties of spinel LiMn₂O₄ powders were examined with X-ray diffractometry (XRD), the Brunauer-Emmett-Teller (BET) method and scanning electron microscopy (SEM). Porous LiMn₂O₄ electrode was characterized electrochemically with charge/discharge experiments and A.C. impedance spectroscopy. The cycling performance of a Li/polymer electrolyte/LiMn₂O₄ cell has been discussed in terms of contact and interfacial resistance by A. C. impedance spectroscopy.     

Electrochemical performance of single crystalline spinel LiMn2O4 nanowires in an aqueous LiNO3 solution

Single crystalline cubic spinel LiMn₂O₄ nanowires were synthesized by hydrothermal method and the precursor calcinations. The phase structures and morphologies were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Galvanostatic charging/discharging cycles of as-prepared LiMn₂O₄ nanowires were performed in an aqueous LiNO₃ solution. The initial discharge capacity of LiMn₂O₄ nanowires was 110 mAh g⁻¹, and the discharge capacity was still above 100 mAh g⁻¹ after 56 cycles at 10C-rate, and then 72 mAh g⁻¹ was registered after 130 cycles. This is the first report of a successful use of single crystalline spinel LiMn₂O₄ nanowire as cathode material for the aqueous rechargeable lithium battery (ARLB).     

Improvement of the high-rate discharge capability of phosphate-doped spinel LiMn2O4 by a hydrothermal method

Micrometer-scale pristine and phosphate-doped spinel LiMn₂O₄ materials with homogeneous size distribution were synthesized by a one-step hydrothermal method. The composition, structure and morphology of the as-prepared samples were characterized using inductively coupled plasma atomic emission spectroscopy (ICP-AES), chemical analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of phosphate doping on the structural and electrochemical properties of spinel LiMn₂O₄ was investigated by Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The phosphate-doped LiMn₂O₄ cathode (with a molar ratio of PO₄³⁻:LiMn₂O₄ = 1.5%) exhibits good high-rate discharge capability with 94 mAh/g at a current density of 2960 mA/g. The analyses demonstrate that compared with the pristine LiMn₂O₄ sample, the phosphate-doped samples have a relatively large Li-ion diffusion coefficient and smaller charge-transfer resistance due to the increase of the unit cell volume of spinel LiMn₂O₄ caused by the doping of phosphate.     

Preparation and electrochemical properties of LiMn2O4 by the microwave-assisted rheological phase method

Pure-phase and well-crystallized spinel LiMn₂O₄ powders as cathode materials for lithium-ion batteries were successfully synthesized by a new simple microwave-assisted rheological phase method, which was a timesaving and efficient method. The physical properties of the as-synthesized samples compared with the pristine LiMn₂O₄ obtained from the rheological phase method were investigated by thermogravimetry analysis (TGA), X-ray diffraction (XRD) and scanning electronic microscope (SEM). The as-prepared powders were used as positive materials for lithium-ion battery, whose charge/discharge properties and cycle performance were examined in detail. The powders resulting from the microwave-assisted rheological phase method were pure, spinel structure LiMn₂O₄ particles of regular shapes with distribution uniformly, and exhibited promising electrochemical properties for battery. Furthermore, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the reactions of Li-ion insertion into and extraction from LiMn₂O₄ electrode.     

Electrochemical behavior of LiCoO2 in a saturated aqueous Li2SO4 solution

The electrochemical behavior of a commercial LiCoO₂ with spherical shape in a saturated Li₂SO₄ aqueous solution was investigated with cyclic voltammetry and electrochemical impedance spectroscopy. Three redox couples at E_SCE = 0.87/0.71, 0.95/0.90 and 1.06/1.01 V corresponding to those found at ELi/Li⁺=4.08/3.83, 4.13/4.03 and 4.21/4.14 V in organic electrolyte solutions were observed. The diffusion coefficient of lithium ions is 1.649 × 10⁻¹⁰ cm² s⁻¹, close to the value in organic electrolyte solutions. The results indicate that the intercalation and deintercalation behavior of lithium ions in the Li₂SO₄ solution is similar to that in the organic electrolyte solutions. However, due to the higher ionic conductivity of the aqueous solution, current response and reversibility of redox behavior in the aqueous solution are better than in the organic electrolyte solutions, suggesting that the aqueous solution is favorable for high rate capability. The charge transfer resistance, the exchange current and the capacitance of the double layer vary with the charge voltage during the deintercalation process. At the peak of the oxidation (0.87 V), the charge transfer resistance is the lowest. These fundamental results provide a good base for exploring new safe power sources for large scale energy storage.     

LiMn2O4 spinel direct synthesis and lithium ion selective adsorption

The cubic phase LiMn₂O₄ spinel is synthesized via a directly soft chemistry method via hydrothermal reaction of Mn(NO₃)₂, LiOH and H₂O₂ at 383 K for 5–10 h, more favorable to control the nanocrystalline structure with well-defined pore-size distribution and high surface area than traditional solid-phase reaction at high temperature. Further, the 1D MnO₂ nanorod ion-sieves with lithium ion selective adsorption property is prepared by the acid treatment process to completely extract lithium ions from the LiMn₂O₄ lattice. The effects of hydrothermal conditions on the nanostructure, chemical stability and ion-exchange property of the LiMn₂O₄ spinel and MnO₂ ion-sieve are examined via powder X-ray diffraction (XRD), N₂ adsorption–desorption at 77 K, high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED) and lithium ion selective adsorption measurements. The results show that the 1D MnO₂ nanorods might be utilized in lithium extraction from aqueous environment including brine, seawater and waste water.     

Electrochemical characterization of P2-type layered Na2/3Ni1/4Mn3/4O2 cathode in aqueous hybrid sodium/lithium ion electrolyte

P2-type layered Na_2/3Ni_1/4Mn_3/4O₂ has been synthesized by a solid-state method and its electrochemical behavior has been investigated as a potential cathode material in aqueous hybrid sodium/lithium ion electrolyte by adopting activated carbon as the counter electrode. The results indicate that the Na⁺/Li⁺ ratio in aqueous electrolyte has a strong influence on the capacity and cyclic stability of the Na_2/3Ni_1/4Mn_3/4O₂ electrode. Increase on the Li⁺ content leads to a shift of the redox potential towards a high value, which is favorable for the improvement of the working voltage of the layered material as cathode. It is found that the coexistence of Na⁺ and Li⁺ in aqueous electrolyte can improve the cyclic stability for the Na_2/3Ni_1/4Mn_3/4O₂ electrode. A reversible capacity of 54 mAh g⁻¹ was obtained with a high cyclability as the Na⁺/Li⁺ ratio was 2:2. Furthermore, an aqueous hybrid ion cell was assembled with the as-proposed Na_2/3Ni_1/4Mn_3/4O₂ as cathode and NaTi₂(PO₄)₃/graphite synthesized in this work as anode in 1 M Na₂SO₄/Li₂SO₄ (mole ratio as 2:2) mixed electrolyte. The cell shows an average discharge voltage at 1.2 V, delivering an energy density of 36 Wh kg⁻¹ at a power density of 16 W kg⁻¹ based on the total mass of the active materials.     

Effect of additives in PEO/PAA/PMAA composite solid polymer electrolytes on the ionic conductivity and Li ion battery performance

Polyethylene oxide (PEO) based-solid polymer electrolytes were prepared with low weight polymers bearing carboxylic acid groups added onto the polymer backbone, and the variation of the conductivity and performance of the resulting Li ion battery system was examined. The composite solid polymer electrolytes (CSPEs) were composed of PEO, LiClO_4, PAA (polyacrylic acid), PMAA (polymethacrylic acid), and Al₂O₃. The addition of additives to the PEO matrix enhanced the ionic conductivities of the electrolyte. The composite electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 exhibited a low polarization resistance of 881.5 ohms in its impedance spectra, while the PEO:LiClO₄ film showed a high value of 4,592 ohms. The highest ionic conductivity of 9.87 × 10⁻⁴ S cm⁻¹ was attained for the electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 at 20 °C. The cyclic voltammogram of Li⁺ recorded for the cell consisting of the PEO:LiClO₄:PAA/PMAA/Li_0.3:Al₂O₃ composite electrolyte exhibited the same diffusion process as that obtained with an ultra-microelectrode. Based on this electrolyte, the applicability of the solid polymer electrolytes to lithium batteries was examined for an Li/SPE/LiNi_0.5Co_0.5O₂ cell.     

Electrochemical investigation of LiMn2O4 cathodes in gel electrolyte at various temperatures

A composite lithium battery electrode of LiMn₂O₄ in combination with a gel electrolyte (1 M LiBF₄/24 wt% PMMA/1:1 EC:DEC) has been investigated by galvanostatic cycling experiments and electrochemical impedance spectroscopy (EIS) at various temperatures, i.e. −3<T<56 °C. For analysis of EIS data, a mathematical model taking into account local kinetics and potential distribution in the liquid phase within the porous electrode structure was used. Reasonable values of the double-layer capacitance, the exchange-current density and the solid phase diffusion were found as a function of temperature. The apparent activation energy of the charge-transfer (∼65 kJ mol⁻¹), the solid phase transfer (∼45 kJ mol⁻¹) and of the ionic bulk and effective conductance in the gel phase (∼34 kJ mol⁻¹), respectively, were also determined. The kinetic results related to ambient temperature were compared to those obtained in the corresponding liquid electrolyte. The incorporated PMMA was found to reduce the ionic conductivity of the free electrolyte, and it was concluded that the presence of 24 wt% PMMA does not have a significant influence on the kinetic properties of LiMn₂O₄.     

Preparation of spinel LiMn2O4 cathode material from used zinc-carbon and lithium-ion batteries

Due to the progressive shortage of primary resources and growing environmental concerns over industrial and household residues, proper management of electronic wastes is of great importance in addressing sustainability issues. Spent batteries are considered as important secondary sources of their constituting components. In this study, the co-recycling of used zinc-carbon and lithium-ion batteries was performed aiming at the recovery of their manganese and lithium contents as compounds which can be used as precursors for the synthesis of spinel LiMn₂O₄. Manganese was recovered in the form of amorphous, submicron, spherical nodules of MnO₂ after acid leaching of zinc-carbon battery pastes. Lithium was obtained from nickel-manganese-cobalt (NMC) batteries as its monohydrate oxalate (C₂HLiO₄.H₂O) through selective leaching in oxalic acid followed by crystallization. Lithium carbonate was also prepared by subsequent calcination of the oxalate. The synthesis of LiMn₂O₄ spinel cathode was investigated using the reclaimed Li- and Mn-containing compounds via solid-state synthesis method. The effect of such parameters as type of precursors (C₂HLiO₄.H₂O/Li₂CO₃ with Mn₂O₃/MnO₂), temperature (750, 800, and 850 °C), and time (8 and 10 h) on the synthesis of LiMn₂O₄ was investigated. The products were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The crystallographic parameters from XRD analysis were used to predict the electrochemical behavior of the synthesized cathode materials. Based on these, the spinel powder synthesized at 850°C?10h from Li₂CO₃?Mn₂O₃ starting mixture was determined as the cathode material with the best electrochemical properties among the synthesized samples. The galvanostatic charge/discharge evaluation within the voltage range of 2.5–4.3 V showed the specific capacity of the 850°C-10 h sample to be 127.87 mAhg^?1.     

Controllable Li3PS4–Li4SnS4 solid electrolytes with affordable conductor and high conductivity for solid-state battery

High ionic conductivity, low grain boundary impedance, and stable electrochemical property have become the focus for all-solid-state lithium–sulfur batteries (ASSLSB). One of the approaches is to promote the rapid diffusion of lithium ions by regulating the chemical bond interactions within the framework. The structure control of P⁵⁺ substitution for Sn⁴⁺ on lithium-ion transport was explored for a series of Li₃PS₄–Li₄SnS₄ glass–ceramic electrolytes. Results showed that the grain boundary impedance of the glass electrolyte was reduced after heat treatments. The formation of LiSnPS microcrystals, a good superionic conductor, was detected by X-ray diffraction tests. Electrochemical experiments obtained the highest conductivity of 29.5 S cm⁻¹ at 100°C and stable electrochemical window from –0.1 to 5 V at 25°C. In addition, the cell battery was assembled with prepared electrolyte, which is promoted as a candidate solid electrolyte material with improved performance for ASSLSB.     

Submicro-sized LiMn2O4 prepared by a sol–gel, spray-drying method

Submicro-sized LiMn₂O₄ powders were produced by a sol–gel, spray-drying method in which a brown gel precursor was prepared via the reaction of LiOH alkaline solution with 1 M Mn(CH₃COO)₂. The gel precursor was then transferred into a dry precursor powder via a spray-dry process. After heating treatment the spinel LiMn₂O₄ powder was obtained. The composition and the crystal size of the samples were strongly affected by the spray speed in the drying process and the heating temperature. The structure and the morphology of LiMn₂O₄ powder were investigated by DTA, TGA, IR, XRD and SEM methods. It was discovered that submicro-sized LiMn₂O₄ powder could be formed under the conditions of rotating spray speed of 15 000 rpm and syntheses temperature of 700 °C. The electrochemical properties of LiMn₂O₄ samples in 1 M LiPF₆, EC:DMC = 1:1 solution were tested by measuring the voltammograms and charge–discharge curves. The submicro-sized LiMn₂O₄ sample made at 700 °C has a capacity of 128 mAh g^–1 and good cycle stability for Li⁺ intercalation reaction. This method may be applied to the industrial-scale production of superfine LiMn₂O₄ powder for use in lithium ion batteries.     

Electrochemical insertion and extraction of lithium-ion at nano-sized LiMn2O4 particles prepared by a spray pyrolysis method

Nano-sized LiMn₂O₄ particles were prepared at 1023 K by electrospray pyrolysis in which they were directly deposited on a Pt substrate in gas phase. Cyclic voltammetry gave very sharp and symmetrical redox peaks at ca. 4.0 and 4.1 V vs. Li/Li⁺ owing to the insertion and extraction of lithium-ion at LiMn₂O₄. However, the redox peaks broadened and their peak separation in an electrode potential increased when aggregated nano-sized LiMn₂O₄ particles were used. In Nyquist plots, a semi-circle due to lithium-ion transfer resistance appeared at potentials above 3.90 V. The values of the lithium-ion transfer resistances were small for dispersed nano-sized LiMn₂O₄ particles. On the other hand, the lithium-ion transfer resistances increased and the Warburg impedance became obvious as the nano-sized LiMn₂O₄ particles aggregated. These results clearly indicate that the apparent rapid diffusion of lithium-ion can be attained using well-dispersed nano-sized particles of electroactive materials.     

A comparative electrochemical study of LiMn2O4 spinel thin-film and porous laminate

Novel Electrostatic Spray Deposition (ESD) technique was used to fabricate LiMn₂O₄ spinel thin-films. Cyclic voltammograms of both the ESD and porous laminate films show the double peaks in the 4.0 V range characteristic of the LiMn₂O₄ spinel materials. The porous laminates exhibit two semicircles in the impedance spectra while the ESD films show only one single semicircle. The diffusion time constant in the laminate films was typically one order of magnitude larger than that in the ESD thin-films. The apparent lithium-ion chemical diffusion coefficient in LiMn₂O₄ was found to be of the order of 10⁻⁹ cm²/s for both the porous laminate film and the ESD films despite the difference in the diffusion time constants.