La2O3-coated Li1.2Mn0.54Ni0.13Co0.13O2 as cathode materials with enhanced specific capacity and cycling stability for lithium-ion batteries

Li-rich layered oxides are the most promising cathode candidate for new generation rechargeable lithium-ion batteries. In this work, La₂O₃-coated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode materials were fabricated via a combined method of sol-gel and wet chemical processes. The structural and morphological characterizations of the materials demonstrate that a thin layer of La₂O₃ is uniformly covered on the surface of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ particles, and the coating of La₂O₃ has no obvious effect on the crystal structure of Li-rich oxide. The electrochemical performance of La₂O₃-coated Li-rich cathodes including specific capacity, cycling stability and rate capability has been significantly improved with the coating of La₂O₃. The Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ coated with 2.5 wt% La₂O₃ exhibits the highest discharge capacity, improved cycling stability and reduced charge transfer resistance, delivering a large discharge capacity of 276.9 mAh g⁻¹ in the 1st cycle and a high capacity retention of 71% (201.4 mAh g⁻¹) after 100 cycles. The optimal rate capability of the materials is observed at the coating level of 1.5 wt% La₂O₃ such that the material exhibits the highest discharge capacity of 90.2 mAh g⁻¹ at 5 C. The surface coating of La₂O₃ can effectively facilitate Li⁺ interfacial diffusion, reduce the structural change and secondary reactions between cathode materials and electrolyte during the charge-discharge process, and thus induce the great enhancement in the electrochemical properties of the Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ materials.     

The effect of AlF3 modification on the physicochemical and electrochemical properties of Li-rich layered oxide

Lithium (Li)-rich layered oxides are considered promising cathode materials for Li-ion batteries because of their favorable properties. Here, we report our recent finding in the novel oxide, aluminum fluoride (AlF₃)-modified Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (LMNCAF), which was synthesized via a facile, cost-effective and readily scalable solid-state reaction. LMNCAF possess an F and Al co-doped core structure with a LiF nano-coating on its surface which leads to considerably enhancement in the electrochemical performance of the oxide. The initial discharge capacity (at 0.05 C) increased from 212 mA h g⁻¹ for Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ to 291 mA h g⁻¹ for LMNCAF. A much higher discharge capacity of 211 mA h g⁻¹ was obtained for LMNCAF after 99 charge/discharge cycles at 0.2 C compared with that of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (160 mA h g⁻¹). Our preliminary results suggest that AlF₃ modification is an effective strategy to tailor the physicochemical and electrochemical properties of Li-rich layered oxides.     

Investigation on performances of Li1.2Co0.4Mn0.4O2 prepared by self-combustion reaction as stable cathode for lithium-ion batteries

Poor rate capability and cycling performance are the major barriers for Li-rich layered cathode materials to be applied as the next generation cathode materials for lithium-ion batteries. In our work, Li_1.2Co_0.4Mn_0.4O₂ has been successfully synthesized via a self-combustion reaction (SCR) and a calcination procedure. Compared with the material produced by the solid state method (SSM), the one by SCR exhibits both better rate capability and cycling performance. Its initial discharge capacity is 166.01 mA h g⁻¹ with the capacity retention of 85.98% after 50 cycles at a current density of 200 mA h g⁻¹. Its remarkable performance is attributed to a thin carbon coating layer, which not only slows down the transformation rate of layered to spinel structure, but provides a good electronic pathway to increase the Li⁺ diffusion coefficient.     

Enhanced electrochemical performance of Li1.2(Ni0.17Co0.07Mn0.56)O2 via constructing double protection layers by facile phytic acid treatment

As one of the most promising cathode materials for next-generation of lithium-ion batteries, Li-rich Mn-based oxides are still hindered by inferior cycling properties and poor rate performance. Surface modification is proved to be feasible to tackle these problems. Herein, we chose phytic acid to construct spinel and Li₃PO₄ double protection layers on the Li_1.2(Ni_0.17Co_0.07Mn_0.56)O₂ cathode material via a simple synchronous approach. The 3 wt% phytic acid treated sample achieves markedly enhanced electrochemical performance, such as elevated initial Coulombic efficiency reaching 90.0%, increased capacity retention of 87.8% after 150 cycles at 1 C and alleviated average discharge voltage drop of 1.63 mV per cycle. These impressive electrochemical properties can be ascribed to the designed hierarchical interface, which not only can synergistically retain structural stability but also provide fast Li⁺ transport channels. Taken together, this work employs a facile and novel route to enhance the electrochemical performance of Li_1.2(Ni_0.17Co_0.07Mn_0.56)O₂, which may afford inspiration to the commercialization of Li-rich cathode materials.     

Stabilizing the structure and suppressing the voltage decay of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode materials for Li-ion batteries via multifunctional Pr oxide surface modification

The development of Li-rich layer cathode materials has been limited by poor cycle, rate performance, phase transformation and voltage decay. To improve these properties, a facile and low-cost wet method is employed to fabricate Pr₆O₁₁ coating layer on Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles. The 3–6 nm Pr₆O₁₁ coating layer is observed on the surface of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ by HRTEM. Interestingly, HAADF-STEM and EDS analyses show that the transition metal ions and the praseodymium ions mutually infiltrate in the Pr₆O₁₁ coating layer and Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles during calcination. A combination of HAADF-STEM with EDS and XPS studies reveals that Pr₆O₁₁ coating layer is bridged to Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles by the chemical bonds of transition phase Li_1.2M_XPr_1−xO₂. XRD patterns show that all samples are indexed to the layered structure α-NaFeO₂, but the lattice parameters are influenced lightly after Pr₆O₁₁ coating. HRTEM and SAED analyses elucidate that the super large Pr ions surface-doping and the Pr₆O₁₁ coating are verified to suppress the transformation of layer to spinel structure in the bulk nanoparticles after cycles. The sample coated with 3 wt% Pr₆O₁₁ exhibits wonderful electrochemical performance with the first coulomb efficiency of 85.6%, the capacity retention ratio of 97.9% after 50 cycles and the discharge capacity of 162.2 mAh g⁻¹ at 5 C. The resistant of charge transfer and the electrodes polarization are reduced by Pr₆O₁₁ coating according to EIS. Therefore, Pr₆O₁₁, which contains the super large Pr ions, plays two roles: the first one, it is coated on the Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles to optimize the environment of the interface reaction between electrodes and electrolyte; the other one, its Pr ions surface-doping stabilizes the structure in the superficial region of Li[Li_0.2Mn_0.54Co_0.13Ni_0.13]O₂ nanoparticles and suppresses the voltage decay. The multifunctional Pr₆O₁₁ can play a significant role in accelerating development of new materials with excellent stabilization and high capacity.     

SmPO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 as a cathode material with enhanced cycling stability for lithium ion batteries

SmPO₄ coated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode materials were prepared by the precipitation method and calcined at 450 °C. The crystal structures and electrochemical properties of the pristine and coated samples are studied by X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, electron diffraction spectroscopy, galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). It has been found that the electrochemical performances of the Li-rich cathode material have been substantially improved by SmPO₄ surface coating. Especially, the 2 wt% SmPO₄-coated sample demonstrates the best cycling performance, with capacity retention of 88.4% at 1 C rate after 100 cycles, which is much better than that of 72.3% in the pristine sample. The improved electrochemical properties have been ascribed to the SmPO₄ coating layer, which not only stabilizes the cathode structure by decreasing the loss of oxygen, but also protects the Li-rich cathode material from side reaction with the electrolyte and increases the Li⁺ migration rate at the cathode interface.     

Improvement the electrochemical performance of Cr doped layered-spinel composite cathode material Li1.1Ni0.235Mn0.735Cr0.03O2.3 with Li4Ti5O12 coating

The Cr doped layered-spinel composite cathode material Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3 was synthesized and coated with different content of Li₄Ti₅O₁₂ by a sol–gel method. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The effect of Li₄Ti₅O₁₂ coatings on the electrochemical performance of the pristine material was evaluated from charge/discharge cycles, rate performance, and electrochemical impedance spectroscopy (EIS). The XRD results show that the lattice crystal and the content of spinel phase have been increased in the Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3 materials after Li₄Ti₅O₁₂ coating. The results from TEM and selected area electron diffraction (SAED) indicate that the Li₄Ti₅O₁₂ coating assumes a spinel structure on the Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3. The discharge capacities, cycling and rate performances of the Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3 materials in the first cycle are improved with the addition of Li₄Ti₅O₁₂. Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3 coated with 3 wt% Li₄Ti₅O₁₂ shows the highest discharge capacity (271.7 mA h g⁻¹), highest capacity retention (99.4% for 100 cycles), and best rate capability (132 mA h g⁻¹ at 10 C). EIS result indicates that the resistance of Li_1.1Ni_0.235Mn_0.735Cr_0.03O_2.3 electrode decreases with the addition of Li₄Ti₅O₁₂. The enhanced electrochemical performance can be ascribed to the increased spinel content, lower resistance and the enhanced lithium-ion diffusion kinetics.     

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 niobium doping on the structure and electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode materials for lithium ion batteries

Key issues including poor rate capability and limited cycle life span should be addressed for the extended application of LiNi_0.5Co_0.2Mn_0.3O₂ cathode. The suppressed Li⁺/Ni²⁺ site exchange, enlarged LiO₂ inter-slab space and reduced impedance, which could facilitate the structure stability, were achieved by controlled Niobium (Nb) doping and contributed to enhanced performance even at elevated temperature (55 °C). The detailed role of the doped Nb was investigated thoroughly and systematically with the help of XRD, SEM, XPS and related electrochemical tests. The full and accurate results demonstrate that the Li(Ni_0.5Co_0.2Mn_0.3)_0.99Nb_0.01O₂ sample with appropriate Nb doping amount possess high capacity retention of 93.77% after 100 cycles at 1.0 C and improved rate performance with 125.5 mA h g⁻¹ at 5.0 C, which are much better than that of the LiNi_0.5Co_0.2Mn_0.3O₂. Moreover, at high temperature of 55 °C, Nb doping shows more remarkable effect on stabilizing the structure and 88.63% of the initial reversible capacity could be retained, which is ~20% higher than the LiNi_0.5Co_0.2Mn_0.3O₂. This study intensively determines that controlled Nb doping could be effectively maintain the structure stability of advanced LiNi_0.5Co_0.2Mn_0.3O₂ cathode and promote the development of high energy density lithium ion batteries.     

Polymer microsphere-assisted synthesis of lithium-rich cathode with improved electrochemical performance

The Li-rich layered cathode material Li_1.165Mn_0.501Ni_0.167Co_0.167O₂ with porous structure has been successfully synthesized through a facile co-precipitation approach followed with a high-temperature calcination treatment, adopting polymer microsphere (PSA) as a template and conductive agent. The PSA-assisted Li_1.165Mn_0.501Ni_0.167Co_0.167O₂ composite exhibits remarkably improved cycling stability and rate capability compared with the bare composite. It delivers a high initial discharge capacity of 267.0 mA h g⁻¹ at 0.1 C (1 C=250 mA g⁻¹) between 2.0 V and 4.65 V. A discharge capacity of 214.9 mA h g ⁻¹ is still obtained after 100 cycles. Furthermore, the diffusion coefficients of Li⁺ investigated by the cyclic voltammetry technique are approximately 10⁻¹⁵–10⁻¹⁴ cm² s⁻¹. Such outstanding performance is mainly ascribed to: on one hand, the carbon residue of PSA after being calcined at high temperature contributes to enhance the electronic conductivity of the electrode and alleviates the volume changes during the Li⁺-insertion/extraction, leading to an improved rate capability; on the other hand, the unique porous structure and small particle size are conductive to increase the exposed electrochemical active surface, shorten Li⁺ diffusion distance and thus enhance the lithium storage capacity.     

The effects of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide–based electrolyte on the electrochemical performance of high capacity cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2

The effects of ionic liquid (IL) N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Py₁₄TFSI) based electrolyte on the electrochemical performance of cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ have been investigated. The results of thermogravimetric analysis (TGA), flammability and differential scanning calorimetry (DSC) tests indicate that Py₁₄TFSI addition enhances thermal stability of the electrolyte and reduces the safety concern of Li-ion battery. Electrochemical measurements demonstrate that the cathode material shows good electrochemical performance in Py₁₄TFSI-added electrolyte. The cathode material is able to deliver high initial discharge capacity of 250 mAh g^?1 in electrolyte with Py₁₄TFSI content up to 80% at 0.1 C. In addition, the cathode material delivers less initial irreversible capacity loss and higher initial coulombic efficiency in electrolyte with higher Py₁₄TFSI content. However, increasing Py₁₄TFSI content in the electrolyte affects rate capability of the cathode material distinctively. With 60% Py₁₄TFSI-added electrolyte, Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ shows better cycling stability with a capacity retention of 84.4% after 150 cycles at 1.0 C than that in IL free electrolyte. The superior cycling performance of the cathode material cycled in Py₁₄TFSI-added electrolyte is mainly ascribed to the formation of stable electrode/electrolyte interfaces, based on the results of scanning electron microscopy (SEM), X-ray photoelectron spectra (XPS) and electrochemical impedance spectroscopy (EIS) investigations.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Hydrothermal synthesis of spherical Li4Ti5O12 material for a novel durable Li4Ti5O12/LiMn2O4 full lithium ion battery

Pure spherical Li₄Ti₅O₁₂ spinel material is quickly synthesized via an efficient hydrothermal procedure. The obtained Li₄Ti₅O₁₂ particle size is about 0.5 µm. The Li₄Ti₅O₁₂ has an initial discharge capacity of 162.2 mA h g⁻¹ and capacity retention of 97.5% after 100 cycles at a rate of 0.2 C. Then, a 2.5 V and long-lasting Li-ion cell with a LiMn₂O₄ cathode and a Li₄Ti₅O₁₂ anode is developed. Electrochemical measurements of the cell indicate that the Li₄Ti₅O₁₂/LiMn₂O₄ full cell, with a weight ratio of 1.5 between cathode and anode, exhibits excellent electrochemical performance, delivering a reversible capacity of 130 mA h g⁻¹ at room temperature. The full cell also exhibits outstanding electrochemical performances at high temperature, as it has an initial discharge capacity of 109.6 mA h g⁻¹, along with a capacity retention rate of 88.9% after 100 cycles at 55 °C.     

Electrochemical properties of nanometer-sized 0.6Li2MnO3·0.4LiNi0.5Mn0.5O2 composite powders prepared by flame spray pyrolysis

Nanometer-sized 0.6Li₂MnO₃·0.4LiNi_0.5Mn_0.5O₂ composite cathode powders are prepared directly by high-temperature flame spray pyrolysis. The precursor powders and the powders post-treated at 800 °C exhibit mixed-layered crystal structures comprising layered Li₂MnO₃ and layered LiNi_0.5Mn_0.5O₂ phases. The discharge capacity of the precursor powders decreased from 193 mAh g^?1 to 96 mAh g^?1 by the 9th cycle, corresponding to a capacity retention of 49.7%. Post-treatment at 800 °C increases the capacity retention of the post-treated composite powders to 94.6% after 50 cycles, corresponding to a decrease in the discharge capacity from 225 to 213 mAh g^?1. The post-treated composite powders that contain a high amount of the Li₂MnO₃ phase have a high initial discharge capacity and good cyclability.     

New insight into the modification of Li-rich cathode material by stannum treatment

In this work, Sn is used to dope the Li-rich cathode material to improve the electrochemical performance of Li ion battery. After Sn treatment, the lattice parameters a, c and lattice volume V become larger. Compared with the pristine sample, the Sn-contained samples show longer plateaux at about 4.5 V in the first charging process, which means that Sn can activate the Li₂MnO₃ component. Meanwhile, with appropriate content of Sn doping, the sample exhibits enhanced rate capability and cycling stability. Especially, the sample S10 shows the best electrochemical performance, with a capacity retention of 88.66% after 100 cycles at 1 C (1 C=250 mA g⁻¹). The mechanisms of Sn doping have also been investigated. The increased activation of Li₂MnO₃ is due to the improved conductivity of Li₂MnO₃ phase by Sn doping, and the enhanced electrochemical performance is mainly ascribed to the increased ability of Li ion diffusing into bulk phase and the improved structure stability during the prolonged charge-discharge cycles. It is suggested that Sn doping is an effective way to improve the electrochemical performance of Li-rich cathode material.     

Reaction sequence and electrochemical properties of lithium vanadium oxide cathode materials synthesized via a hydrothermal reaction

Lithium vanadium oxide (Li_1+xV₃O₈) cathode materials were synthesized via a simple hydrothermal reaction followed by heat treatment at 300 or 400 °C. From both XRD and TG/DTA analyses, a detailed comprehensive reaction sequence for the formation of single-phase LiV₃O₈ is proposed. Li_1+xV₃O₈ (x=0.2) materials with different thermal histories show clear differences in morphologies and sizes, although they maintained an impurity-free single phase regardless of thermal treatment. Samples that were heat treated at 300 °C show an agglomerated particle shape with many nanorod-like Li_1+xV₃O₈ particles over the surface that enhance the surface area of the particles. In contrast, samples treated at 400 °C have a bi-modal particle size distribution with improved crystallinity. Such differences in morphologies clearly influence the electrochemical properties. LiV₃O₈ cathode materials that were treated at 300 and 400 °C showed initial discharge capacacities of 346.52 and 261.23 mA h/g, respectively, and discharge capacities of 78.66 and 157.35 mA h/g, respectively, after 100 cycles. The improved cyclability of LiV₃O₈ cathode materials that were heat treated at 400 °C is due to their increased crystallinity and structural stability.     

Chemical synthesis of Co and Mn co-doped NiO nanocrystalline materials as high-performance electrode materials for potential application in supercapacitors

Co and Mn co-doped with NiO nanostructued materials, such as, Ni_0.95Co_0.01Mn_0.04O_1−δ, Ni_0.95Co_0.04Mn_0.01O_1−δ and Ni_0.95Co_0.025Mn_0.025O_1−δ were synthesized by chemical synthesis route and studied for potential application as electrode materials for supercapacitors. The phase structure of the materials was characterized by X-ray diffraction (XRD) and the crystallographic parameters were found out and reported. FTIR (Fourier Transform Infrared) spectroscopy revealed the presence of M–O bond in the compounds. The particle size of the materials was found to be in the range of 291.5–336.5 nm. The morphological phenomenon of the materials was studied by scanning electron microscopy (SEM) and the particles were found to be in spherical shape with average grain size of 14–28 nm. EDAX analysis confirmed the presence of appropriate levels of elements in the samples. The in-depth morphological characteristics were also studied by HR-TEM (High Resolution Tunneling Electron Microscopy). Cyclic voltammetry, chronopotentiometry and electrochemical impedance measurements were applied in an aqueous electrolyte (6 mol L⁻¹ KOH) to investigate the electrochemical performance of the Co and Mn co-doped NiO nanostructured electrode materials. The results indicate that the doping level of Co and Mn in NiO had a significant role in revealing the capacitive behaviors of the materials. Among the three electrode materials studied, Ni_0.95Co_0.025Mn_0.025O_1−δ electrode material shows a maximum specific capacitance of 673.33 F g⁻¹ at a current density of 0.5 A g⁻¹. The electrochemical characteristics of blank graphite sheet were studied and compared with the performance of Co/Mn co-doped NiO based electrode materials. Also, Ni_0.95Co_0.025Mn_0.025O_1−δ has resulted in a degradation level of 4.76% only after 1000 continuous cycles, which shows its excellent electrochemical performance, indicating a kind of potential candidate for supercapacitors.     

Electrochemical evaluation of LiZnxMn2−xO4 (x≤0.10) cathode material synthesized by solution combustion method

The spinel LiZn_xMn_2−xO₄ (x≤0.10) cathode materials have been synthesized by solution combustion method at 600 °C for 3 h. The structure and the morphology of LiZn_xMn_2−xO₄ were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM), respectively. All the obtained samples were identified as the spinel structure of LiMn₂O₄, the lattice parameters of samples decreased and the particle size increased as the Zn content increased. The effects of Zn-doping on the electrochemical characteristics of LiMn₂O₄ were investigated by galvanostatic charge–discharge experiments, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Among them, LiZn_0.05Mn_1.95O₄ particles presented outstanding cycling stability with a capacity retention of 82.9% at a discharge rate of 1 C (1 C=148 mA h g⁻¹) after 500 cycles. Spinel LiZn_0.05Mn_1.95O₄ had reversible cycling performance, revealing that doping LiMn₂O₄ with Zn improves its electrochemical performance.     

Structural and electrical properties of MgO-doped Mn1.4Ni1.2Co0.4−xMgxO4 (0 ≤ x ≤ 0.25) NTC thermistors

We have prepared polycrystalline Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ (0 ≤ x ≤ 0.25) samples using a solid-state reaction process and investigated the MgO doping effect on the microstructure and the electrical properties. It was found that, as the amount of Mg content in the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples increased, both the grain size and density decreased. The as-sintered Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples contained Mn- and Ni-rich phases with cubic spinel structure. The MgO-doped Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ negative temperature coefficient (NTC) thermistors provided various electrical properties, depending on Mg content. The electrical resistivity, B_25/85 constant, and activation energy of the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ NTC thermistors increased with increasing Mg content. The values of ρ₂₅, B_25/85 constant, and activation energy of the NTC thermistors were 11,185–20,016 Ω cm, 3635–4032 K, and 0.313–0.348 eV, respectively.     

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.