Synthesis and electrochemical properties of nanostructured LiMn2O4 for lithium-ion batteries

Spinel LiMn₂O₄ crystal with the grain sizes of about 15 nm is firstly synthesized by hydrothermal route at 180 °C using MnO₂ as a precursor. The LiMn₂O₄ powders synthesized by hydrothermal technique and sol-gel reaction were investigated by X-ray diffraction (XRD) and Transmission electron microscopy (TEM). The LiMn₂O₄ samples were used as cathode materials for lithium-ion battery, whose electrochemical properties were investigated. The results show that the sample obtained by hydrothermal route has higher capacity than that prepared by sol-gel method.     

Glycerol-assisted solution combustion synthesis of improved LiMn2O4

Spinel LiMn₂O₄ has been synthesized by a glycerol-assisted combustion synthesis method. The phase composition and morphologies of the compound were ascertained by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical characterization was performed by using CR2032 coin-type cell. XRD analysis indicates that single phase spinel LiMn₂O₄ with good crystallinity has been obtained as a result of 5 h treatment at 600 °C. SEM investigation indicates that the average particle size of the sample is 200 nm. The initial discharge specific capacity of the LiMn₂O₄ is 123 mAh/g at a current density of 30 mA/g. When the current density increased to 300 mA/g, the LiMn₂O₄ offered a discharge specific capacity of 86 mAh/g. Compared with the LiMn₂O₄ prepared by a conventional solution combustion synthesis method at the same temperature, the prepared LiMn₂O₄ possesses higher purity, better crystallinity and more uniformly dispersed particles. Moreover, the initial discharge specific capacity, rate capability and cycling performance of the prepared LiMn₂O₄ are significantly improved.     

Electrochemical properties of LiMn1.5Ni0.5O4 powders synthesized by solution combustion method: Effect of CTAB as a fuel

LiMn_1.5Ni_0.5O₄ powders were prepared by solution combustion synthesis using cetyltrimethylammonium bromide (CTAB) as fuel. The spinel LiMn_1.5Ni_0.5O₄ powders were directly formed due to the low decomposition rate as characterized by thermal analysis and X-ray powder diffraction techniques. The microstructure observed by electron microscopy showed the particle size increased from 10 to 90 nm with the increase of fuel amount. However, the specific surface area decreased from 211 to 105 m² g⁻¹. The highest discharge capacity at 1C obtained for the LiMn_1.5Ni_0.5O₄ powders synthesized at low fuel contents, which retain a capacity of 90 mAh g⁻¹ after 30 cycles due to the lower electrode resistance as confirmed by electrochemical impedance analysis. The high electrode kinetics was attributed to the small particle size and high specific surface area.     

Enhanced high temperature performance of LiMn 2 O 4 coated with Li 3 BO 3 solid electrolyte

Cathode material, LiMn₂O₄, was synthesized by solid-state reaction followed by surface coating of Li₃BO₃ solid electrolyte. Structure and electrochemical performance of the prepared powders were characterized by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge techniques, respectively. Results show that Li₃BO₃ coated LiMn₂O₄ has similar X-ray diffraction patterns as LiMn₂O₄. The discharge specific capacities of LiMn₂O₄ coated with 0·1, 0·3 and 0·6 wt% Li₃BO₃ are 123·3, 118·2 and 110 mAh/g, respectively, which is slightly smaller than that of 124·4 mAh/g for LiMn₂O₄. However, the capacity retention of Li₃BO₃ coated LiMn₂O₄ is at least 5·6 and 7·6% higher than LiMn₂O₄ when cycled at room temperature and 55 °C, respectively. Li₃BO₃ coated LiMn₂O₄ shows much better cycling behaviours than LiMn₂O₄.     

Comparison of microwave-induced combustion and solid-state reaction method for synthesis of LiMn2− x Co x O4 powders and their electrochemical properties

Spinel LiMn_{2 − x}Co_xO₄ (0.00 ≦ x ≦ 0.20) powders with small and uniform particle size were successfully synthesized by microwave-induced combustion using lithium nitrate, manganese nitrate, cobalt nitrate, and urea as the starting materials. The LiMn_{2 − x}Co_xO₄ powders synthesized by microwave-induced combustion were investigated by X-ray diffractometer (XRD), thermogravimeter analyzer (TG), and scanning electron microscopy (SEM). The LiMn_{2 − x}Co_xO₄ samples were used as cathode materials in lithium-ion batteries, whose discharge capacity and electrochemical characteristics such as the cycling performance were also investigated. The results revealed that the LiMn_{2 − x}Co_xO₄ cell synthesized by microwave-induced combustion provided a high initial capacity and excellent reversibility compared to the material prepared by solid-state reaction method.     

Enhanced electrochemical properties of nano-Li3PO4 coated on the LiMn2O4 cathode material for lithium ion battery at 55 °C

The electrochemical performance of LiMn₂O₄ is improved by the surface coating of nano-Li₃PO₄ via ball milling and high-temperature heating. The Li₃PO₄-coated LiMn₂O₄ powders are characterized by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). At 55 °C, capacity retention of 85% after 100 cycles was obtained for Li/Li₃PO₄-coated LiMn₂O₄ electrode at 1C rate, while that of pristine sample was only 65.6%. The Li/Li₃PO₄-coated LiMn₂O₄ electrode also showed improved rate capability especially at high C rates. At 5C-rates, the delivered capacities of pristine and Li₃PO₄-coated LiMn₂O₄ electrodes were 80.7 mAh/g and 112.4 mAh/g, respectively. The electrochemical impedance spectroscopy (EIS) indicates that the charge transfer resistance for Li/Li₃PO₄-coated LiMn₂O₄ cell was reduced compared to Li/LiMn₂O₄ cell.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Effects of different particle sizes on electrochemical performance of spinel LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode materials

Spinel LiMn₂O₄ were prepared by adipic acid-assisted sol–gel method at 800 °C, and the cathode materials with different particle sizes were obtained through ball milling. The effects of different particle sizes on electrochemical performance of LiMn₂O₄ sample were investigated by X-ray diffraction (XRD), galvanostatic charge–discharge test, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), respectively. XRD data exhibits that all samples exhibit the same pure spinel phase; EIS and CV indicate that LiMn₂O₄ samples with smaller particle size have higher charge transfer resistance and oxidation potential than that of other samples corresponding to the extraction of Li⁺ ions, respectively; galvanostatic charge–discharge test shows that the particle size has significant effects on the electrochemical performance of spinel LiMn₂O₄ cathode materials.     

Synthesis of LiMn2O4 via high-temperature ball milling process

Spinel LiMn₂O₄ powder was prepared by a novel process of high-temperature ball milling. For comparison, the spinel LiMn₂O₄ powder was also synthesized by the traditional method of solid state reaction. It was found that high-temperature ball milling significantly decreased the synthesis temperature and time. LiMn₂O₄ with pure spinel phase could be successfully synthesized only by 2?h high-temperature ball milling at 500°C and 600°C. However, pure spinel LiMn₂O₄ could not be completely synthesized by 2?h solid state reaction at 800°C. The LiMn₂O₄ particles prepared by high-temperature ball milling are nano-sized (<100?nm) and much smaller than that prepared using solid state reaction. The electrochemical tests results indicated that the as-synthesized LiMn₂O₄ by 2?h high-temperature ball milling at 600°C showed a favorable initial discharge capacity of 124.2 mAh g^?1 at current rate of 0.1 C and still retained a capacity of 119.8 mAh g^?1 at 0.1 C after 80 continuous cycles from 0.1 to 2.0 C.     

Spray-drying technology for the synthesis of nanosized LiMn2O4 cathode material

Spinel LiMn₂O₄ cathode material has been synthesized by a spray-drying method for lithium ion batteries. During the entire process, the as-prepared powders were characterized using TGA/DTA, XRD, FTIR, SEM and TEM. The results showed that this method not only reduces the sintering time to 5 h at 750 °C, but also decreases the average particle size of LiMn₂O₄ powders to the order of nanometers. The electrochemical performance of nanosized LiMn₂O₄ was investigated by the galvanostatic charge-discharge tests. The data indicate that the nanosized LiMn₂O₄ has a specific capacity of about 130 mA h g^− 1 (1/5 C), and at higher rate (1 C), still has good cycling stability.     

LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> particles prepared by spray pyrolysis from spray solution with citric acid and ethylene glycol

Spinel LiMn₂O₄ particles with fine sizes and regular morphologies were successfully synthesized by ultrasonic spray pyrolysis at the severe preparation conditions from a spray solution with citric acid and ethylene glycol. The as-prepared particles with spherical shapes, porous structures and micron sizes turned into LiMn₂O₄ particles with submicron size and narrow size distribution at the post-treatment temperature of 800 °C. The discharge capacities of the particles prepared from the spray solution with citric acid and ethylene glycol changed from 90 to 127 mAh/g when the post-treatment temperature was changed from 700 to 1,000 °C. The LiMn₂O₄ particles had maximum discharge capacities at the post-treatment temperature of 800 °C. The discharge capacity of the LiMn₂O₄ particles dropped from 127 to 108 mAh/g by the 30th cycle.     

Preparation and electrochemical properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by a rheological-phase-assisted microwave synthesis method

By using LiCO₃ and MnO₂, a rheological-phase-assisted microwave synthesis method has been applied in the fast preparation of spinel LiMn₂O₄ in order to reduce the cost of cathode materials. Comparing with the pristine LiMn₂O₄ obtained by the traditional solid-state reaction method, the structure and surface morphology of the samples synthesized by the rheological-phase-assisted microwave synthesis method have been investigated. The powders were used as positive materials for lithium-ion battery, whose charge/discharge properties and cycle performance have been examined in detail. As a result, the powders prepared by the rheologicalphase-assisted microwave synthesis method at 750°C are pure spinel LiMn₂O₄ with regular shapes and uniform distribution, which exhibit higher capacity and much better reversibility than the sample prepared by the traditional solid-state reaction. The text was submitted by the authors in English.     

Synthesis and performance of LiMn0.7Fe0.3PO4 cathode material for lithium ion batteries

Pure and carbon-containing olivine LiMn_0.7Fe_0.3O₄ were synthesized at 600 °C by the method of solid-state reaction. Structure, surface morphology and charge/discharge performance of LiMn_0.7Fe_0.3O₄ were characterized by X-ray diffraction, scanning electron microscopy, and electrochemical measurement, respectively. The prepared materials with and without carbon both show the single olivine structure. The morphologies of primary particles are greatly affected by the addition of carbon. Large particles (500-1000 nm) and densely sintered blocks were observed in pure LiMn_0.7Fe_0.3PO₄, which made the insertion and extraction of lithium ions difficult. Battery made from this sample can not charge and discharge effectively. The carbon-containing LiMn_0.7Fe_0.3PO₄ has a small particle size (100-200 nm) and a regular appearance. This material demonstrates high reversible capacity of about 120 mAh g⁻¹, perfect cycling performance, and excellent rate capability. It is obvious that the addition of carbon plays an important role in restricting the particle size of the material, which helps to prepare LiMn_0.7Fe_0.3PO₄ with excellent electrochemical performance. The electrochemical reaction resistance is much lower in the partly discharged state than in the fully charged or fully discharged state by the measurement of ac impedance for carbon-containing LiMn_0.7Fe_0.3PO₄. It is indicated that the mixed-valence of Fe³⁺/Fe²⁺ or Mn³⁺/Mn²⁺ is beneficial to the transfer of electron which happens between the interface.     

Solution combustion synthesis of LiMn2O4 fine powders for lithium ion batteries

In this work, fine powders of spinel-type LiMn₂O₄ as cathode materials for lithium ion batteries (LIBs) were produced by a facile solution combustion synthesis using glycine as fuel and metal nitrates as oxidizers. Single phase of LiMn₂O₄ products were successfully prepared by SCS with a subsequent calcination treatment at 600–1000 °C. The structure and morphology of the powders were studied in detail by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical properties were characterized by galvanostatic charge–discharge cycling and cyclic voltammetry. The crystallinity, morphology, and size of the products were greatly influenced by the calcination temperature. The sample calcined at 900 °C had good crystallinity and particle sizes between 500 and 1000 nm. It showed the best performance with an initial discharge capacity of 115.6 mAh g⁻¹ and a capacity retention of 93% after 50 cycles at a 1 C rate. In comparison, the LiMn₂O₄ sample prepared by the solid-state reaction showed a lower capacity of around 80 mAh g⁻¹.     

Effect of cooling rate on the electrochemical properties of solid-state synthesized spinel LiMn2O4

LiMn₂O₄ samples were prepared by solid-state reaction with different cooling rates (0.5, 1, 3, 5 °C min^− 1, and quenching) from Li₂CO₃ and electrolytic MnO₂. X-ray diffraction patterns of the prepared samples are identified as the spinel structure with a space group of Fd3¯m. The lattice parameters increase gradually as the cooling rates rise. The quickly cooled samples show better capacity properties at high current densities and a capacity fade when cycling at lower current density. Varieties of electrochemical methods were introduced to investigate the electrochemical properties of spinel LiMn₂O₄.     

Effects of copper and Al2O3 particles on characteristics of Cu–Al2O3 composites

High-energy milling was used for production of Cu–Al₂O₃ composites. The inert gas-atomized prealloyed copper powder containing 2 wt.%Al and the mixture of the different sized electrolytic copper powders with 4 wt.% commercial Al₂O₃ powders served as starting materials. Milling of prealloyed copper powders promotes formation of nano-sized Al₂O₃ particles by internal oxidation with oxygen from air. Hot-pressed compacts of composites obtained from 5 and 20 h milled powders were additionally subjected to the high-temperature exposure in argon at 800 °C for 1 and 5 h. Characterization of processed material was performed by optical and scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), microhardness, as well as density and electrical conductivity measurements. Due to nano-sized Al₂O₃ particles microhardness and thermal stability of composite processed from milled prealloyed powders are higher than corresponding properties of composites processed from the milled powder mixtures. The results were discussed in terms of the effects of different size of starting copper powders and Al₂O₃ particles on the structure, strengthening of copper matrix, thermal stability and electrical conductivity of Cu–Al₂O₃ composites.     

Synthesis and electrochemical properties of nanorod-shaped LiMn1.5Ni0.5O4 cathode materials for lithium-ion batteries

Nanorod-shaped LiMn_1.5Ni_0.5O₄ cathode powders were synthesized by a co-precipitation method with oxalic acid. Their structures and electrochemical properties were characterized by SEM, XRD and galvanostatic charge-discharge tests. The resulting nanorod-shaped LiMn_1.5Ni_0.5O₄ cathode active materials delivered a specific discharge capacity of 126 mAh g⁻¹ at 0.1 C rate. These active materials exhibited better capacity retention and higher rate performance than those of LiMn_1.5Ni_0.5O₄ cathode powders with irregular morphology.     

The effect of ZnO coating on LiMn2O4 cycle life in high temperature for lithium secondary batteries

The surface of the spinel LiMn₂O₄ was modified with zinc oxide by a chemical process to improve its electrochemical performance at high temperatures. The physical properties of the prepared products have been investigated by thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-rays analysis (EDAX). The charge/discharge of the materials was carried at 1 mA/cm² in the range of 3.0 and 4.4 V at 55 °C. The discharge capacity of ZnO-coated LiMn₂O₄ (117 mAh/g) showed only 3% loss of the initial capacity (121 mAh/g) over 60 cycles. The cycle ability improvement of the spinel LiMn₂O₄ coated with ZnO is demonstrated at high temperatures. From the analysis of electrochemical impedance spectroscopy (EIS), the improvement of cycle ability may be attributed to the suppression on the formation of the passivation film and the reduction of Mn dissolution, which result from the modifying the surface of the spinel LiMn₂O₄ with zinc oxide.     

Preparation,microstructure and electrochemical performance of nanoparticles LiMn2O3.9Br0.1

LiMn₂O_3.9Br_0.1 nanoparticles were prepared by a room-temperature solid-state coordination method. The structure and morphology of the as-prepared materials were analyzed by X-ray diffractometry and transmission electron microscopy. The results show that the LiMn₂O_3.9Br_0.1 is well-crystallized and consists of monodispersed nanoparticles 80–100 nm in size. Results of electrochemical testing show that the samples prepared at different temperatures have similar electrochemical performance. The initial discharge capacities of LiMn₂O_3.9Br_0.1 prepared at 800 °C and 700 °C are 121 mAh g^? 1 and 118.9 mAh g^? 1, respectively, higher than for LiMn₂O₄ prepared using the same method.     

Synthesis and electrochemical properties of Indium doped spinel LiMn2O4

In this paper, spinel LiMn_2–x In _x O₄ powder were prepared by rheological phase reaction method with the CH₃COOLi·2H₂O, (CH₃CO₂)₂Mn·4H₂O, and In₂O₃. The structures were characterized by X-ray diffraction and the electrochemical cycling performance were also observed. The results showed that the spinel LiMn_2–x In _x O₄ were pure phase with very excellent performance. As a cathode material for lithium secondary batteries, LiMn_1.98In₂O₄ had a high initial discharge-capacity with 132.42 mAh/g and a good cyclic reversibility with 98.9%. Even after 60 cycles, the discharge capacity still kept 126.29 mAh/g.