Investigation of the structural and electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> with Cr doping

Cr-doped layered oxides Li[Li_0.2Ni_0.2???x Mn_0.6???x Cr_2x ]O₂ (x?=?0, 0.02, 0.04, 0.06) were synthesized by co-precipitation and high-temperature solid-state reaction. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TRTEM), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). XRD patterns and HRTEM results indicate that the pristine and Cr-doped Li_1.2Ni_0.2Mn_0.6O₂ show the layered phase. The Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ shows the best electrochemical properties. The first discharge specific capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 249.6 mA h g^?1 at 0.1 C, while that of Li_1.2Ni_0.2Mn_0.6O₂ is 230.4 mA h g^?1. The capacity retaining ratio of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 97.9% compared with 93.9% for Li_1.2Ni_0.2Mn_0.6O₂ after 80 cycles at 0.2 C. The discharge capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 126.2 mA h g^?1 at 5.0 C, while that of the pristine Li_1.2Ni_0.2Mn_0.6O₂ is about 94.5 mA h g^?1. XPS results show that the content of Mn³⁺ in the Li_1.2Ni_0.2Mn_0.6O₂ can be restrained after Cr doping during the cycling, which results in restraining formation of spinel-like structure and better midpoint voltages. The lithium-ion diffusion coefficient and electronic conductivity of Li_1.2Ni_0.2Mn_0.6O₂ are enhanced after Cr doping, which is responsible for the improved rate performance of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Oxalate precursor preparation of Li1.2Ni0.13Co0.13Mn0.54O2 for lithium ion battery positive electrode

Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ powders have been prepared through co-precipitation of metal oxalate precursor and subsequent solid state reaction with lithium carbonate. X-ray diffraction pattern shows that the massive rock-like structure has a good layered structure and solid solution characteristic. Scanning electron microscope and transition electron microscope images reveal that the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ composed of nanoparticles have the size of 1–2 μm. As a lithium ion battery positive electrode, the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ has an initial discharge capacity of 285.2 mAh g^?1 at 0.1 C within 2.0–4.8 V. When the cutoff voltage is decreased to 4.6 V, the cycling stability of product can be greatly improved, and a discharge capacity of 178.5 mAh g^?1 could be retained at 0.5 C after 100 cycles. At a high charge–discharge rate of 5 C (1,000 mAh g^?1), a stable discharge capacity of 121.4 mAh g^?1 also can be reached. As the experimental results, the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ prepared from oxalate precursor route is suitable as lithium ion battery positive electrode.     

Lithium-rich layered nickel–manganese oxides as high-performance cathode materials: the effects of composition and PEG on performance

Lithium-rich layered nickel–manganese oxide (LRL-NMO) as a cathode material for rechargeable lithium-ion batteries was successfully prepared using an oxalic acid co-precipitation method, with polyethylene glycol (PEG1000) as an additive. The effects of the Ni/Mn ratio and of PEG on the phase purity, morphology, and electrochemical performance of LRL-NMO were investigated with X-ray diffraction, scanning electron microscope, electrochemical impedance spectroscopy, and charge/discharge testing. Li[Li_0.167Ni_0.25Mn_0.580]O₂ delivered the best electrochemical performance among the various Li[Li_1/3?2x/3Ni _x Mn_2/3?x/3]O₂ (0?<?x?<?0.5) materials. Furthermore, the sample to which an appropriate amount of PEG had been added showed much smaller and more uniform particle size, higher discharge capacity and energy density, better cycling stability, and lower resistance. The material prepared by adding 9 wt% PEG exhibited high discharge capacity and stability; after 100 cycles at 2 C, it still delivered a discharge capacity of 125.6 mAh g^?1, which was 50 % higher than that of a sample prepared without PEG.     

The properties research of ferrum additive on Li [Ni<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>] O<Subscript>2</Subscript> cathode material for lithium ion batteries

Li[Ni_1/3Co_(1-x)/3Mn_1/3Fe _x/3] O₂(x?=?0.0, 0.1, 0.3, 0.5, 0.7, and 0.9) cathode materials have been synthesized via hydroxide co-precipitation method followed by a solid state reaction. Thermogravimetry (TG) and differential thermal analysis (DTA) measurements were utilized to determine the calcination temperature of precursor sample. The crystal structure features were characterized by X-ray diffraction (XRD). The electrochemical properties of Li[Ni_1/3Co_(1-x)/3Mn_1/3Fe _x/3]O₂ were compared by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy(EIS), and galvanostatic charge/discharge test. Electrochemical test results indicate that Li[Ni_1/3Co_0.9/3Mn_1/3Fe_0.1/3] O₂ decrease charge transfer resistance and enhance Li⁺ ion diffusion velocity and thus improve cycling and high-rate capability compared with Li[Ni_1/3Co_1/3Mn_1/3]O₂. The initial discharge specific capacity of Li[Ni_1/3Co_0.9/3Mn_1/3Fe_0.1/3] O₂ was 178.5 mAh/g and capacity retention was 87.11 % after 30 cycles at 0.1C, with the battery showing good cycle performance.     

Synthesis of Li(Ni<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>)O<Subscript>2</Subscript> with sodium DL-lactate as an eco-friendly chelating agent and its electrochemical performances for lithium-ion batteries

(Ni_0.6Co_0.2Mn_0.2)(OH)₂ precursor has been successfully prepared using hydroxide co-precipitation method. The thermodynamic model of hydroxide co-precipitation with sodium DL-lactate as an eco-friendly chelating agent is proposed. The microstructures of (Ni_0.6Co_0.2Mn_0.2)(OH)₂ precursors and Li(Ni_0.6Co_0.2Mn_0.2)O₂ cathode materials are investigated using X-ray diffractometer and scanning electronic microscopy, while the electrochemical performances of Li(Ni_0.6Co_0.2Mn_0.2)O₂ cathode materials are measured using a charge–discharge test. The influences of pH value on the structure and morphological and electrochemical performances of Li(Ni_0.6Co_0.2Mn_0.2)O₂ cathode materials have been discussed in detail. The results show that the sample at pH?=?11.5 exhibits the best lamellar structure and lowest cation mixing, while the sample at pH?=?11.0 delivers the most uniform and full particles and possesses the highest initial charge–discharge performance of 183.4 mAh/g and the best coulombic efficiency of 77.9% at the voltage range of 3.0–4.3 V. Even after 100 cycles, its discharge capacity still remains 165.2 mAh/g with the best retention rate of 90.1%. Furthermore, the sample at pH?=?11.0 delivers the highest discharge capacity at each current density. Even if discharged at 5C (1000 mA/g), the capacity of 115.6 mAh/g has been achieved. The sample at pH?=?11.0 exhibits the highest Li-ion diffusion coefficients (2.072?×?10^?12 cm²/s).     

Influence of coated MnO2 content on the electrochemical performance of Li1.2Ni0.2Mn0.6O2 cathodes

Layered cathode material Li_1.2Ni_0.2Mn_0.6O₂ has been synthesized using a coprecipitation method and coated by MnO₂ with varying amounts (1, 3, 5, and 9 wt%). The physical properties and electrochemical performances of the materials are characterized by XRD, SEM, charge/discharge tests, cycle life, and rate capability tests. XRD patterns show that the pristine and coated Li_1.2Ni_0.2Mn_0.6O₂ powders exhibit layered structure. The discharge capacities and coulombic efficiencies of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved and increase with the increasing content of coated MnO₂. The 9 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ delivers 287 mAhg^?1 for the first discharge capacity and 86.7 % for the first coulombic efficiency compared with 228 mAhg^?1 and 65.9 % for pristine Li_1.2Ni_0.2Mn_0.6O₂. However, the 5 wt% MnO₂-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best capacity retention (99.9 % for 50 cycles) and rate capability (88.6 mAhg^?1 at 10 C), while the pristine Li_1.2Ni_0.2Mn_0.6O₂ only shows 91.5 % for 50 cycles and 25.3 mAhg^?1 at 10 C. The charge/discharge curves and differential capacity vs. voltage (dQ/dV) curves show that the coated MnO₂ reacts with Li⁺ during the charge and discharge process, which is responsible for higher discharge capacity after coating. Electrochemical impedance spectroscopy results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after coating, which is responsible for superior rate capability.     

Improved electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> cathode material with fast ionic conductor Li<Subscript>3</Subscript>VO<Subscript>4</Subscript> coating

Layered lithium-enriched nickel manganese oxides Li_1.2Ni_0.2Mn_0.6O₂ have been synthesized and coated by fast ionic conductor Li₃VO₄ with varying amounts (1, 3, and 5 wt%) in this paper. The effect of Li₃VO₄ on the physical and electrochemical properties of Li_1.2Ni_0.2Mn_0.6O₂ has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability, and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulomb efficiency of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved after Li₃VO₄ coating. And, the 3 wt% Li₃VO₄-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best discharge capacity (246.8 mAh g^?1), capacity retention (97.3 % for 50 cycles), and rate capability (90.4 mAh g^?1 at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after Li₃VO₄ coating, which is due to high lithium ion diffusion coefficient of Li₃VO₄, is responsible for superior rate capability.     

Improvement electrochemical performance of Li1.5Ni0.25Mn0.75O2.5 with Li4Ti5O12 coating

Layered cathode Li_1.5Ni_0.25Mn_0.75O_2.5 has been synthesized and coated by Li₄Ti₅O₁₂. The pristine and coated Li_1.5Ni_0.25Mn_0.75O_2.5 powders are characterized by X-ray diffraction (XRD), indicating the materials remained the layered structure before and after coating. The coated Li₄Ti₅O₁₂ has been detected by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (DEX). The electrochemical performance, especially rate performance of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode, is improved effectively after Li₄Ti₅O₁₂ coating. The first discharge capacity, coulombic efficiency, and capacity retention of Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode are 244 mA h g^?1, 81.5 %, and 98.3 % after 50 cycles, respectively. The Li₄Ti₅O₁₂-coated Li_1.5Ni_0.25Mn_0.75O_2.5 electrode exhibits 108 mA h g^?1 at 10 °C rate. Electrochemical impedance spectroscopy (EIS) results show that the charge transfer resistance (R _ct) of Li_1.5Ni_0.25Mn_0.75O_2.5 electrode decreases after coating, which is due to the existence of Li₄Ti₅O₁₂ with high lithium ion diffusion coefficient and suppression of the solid electrolyte interfacial (SEI) layer development and is responsible for the excellent rate capability and cyclic performance.     

Surface-modified Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> nanoparticles with LaF<Subscript>3</Subscript> as cathode for Li-ion battery

The LaF₃-coated Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ nanoparticles were synthesized via co-precipitation method followed by simple chemical deposition process. The crystal structure, particle morphology, and electrochemical properties of the bare and coated materials were studied by XRD, SEM, TEM, charge–discharge tests. The results showed that the surface coating on Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ nanoparticles were amorphous LaF₃ layer with a thickness of about 10–30 nm. After the surface modification with LaF₃ films, the coating layer served as a protective layer to suppress the side reaction between the positive electrode and electrolyte, and the Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ oxide demonstrated the improved electrochemical properties. The LaF₃-coated Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ electrode delivered the capacities of 270.5, 247.9, 197.1, 170.0, 142.7, and 109.5 mAh g^?1 at current rates of 0.1, 0.2, 0.5, 1, 2, and 5 C rate, respectively. Besides, the capacity retention was increased from 85.1 to 94.8 % after 100 cycles at 0.5 C rate. It implied surface modification with LaF₃ played an important role to improve the cyclic stability and rate capacity of the Li-rich nickel manganese oxides.     

Study of electrochemical performances of multi-doped spinel Li1.1Mn1.85Co0.075Ni0.075O4 at 4.3 and 5 V

Li_1.1Mn_2???2x Co _x Ni _x O₄ (x?=?0, 0.075) spinel powders were successfully synthesized using a liquid stirred tank reactor method. The electrochemical performances of the undoped and doped spinels at 4.3 and 5 V were investigated by X-ray diffraction, field-emission scanning electron microscopy, and electrochemical impedance spectroscopy. The capacity of Li_1.1Mn_2???2x Co _x Ni _x O₄ could be divided into two parts, with 4.3 V as the dividing line in the 3–5 V charge–discharge range. Low capacity and good cyclic performance were obtained when cycled in the 3–4.3 V range for the multi-doped Li_1.1Mn_2???2x Co _x Ni _x O₄ spinel. In comparison with multi-doped spinel at 4.3 V, the results of the cyclic performance worsened at 5 V because the structure underwent further shrinkage, the charge transfer resistance rose and the electrolyte decomposed.     

Li4Mn5O12 prepared using l-lysine as additive and its electrochemical performance

l-Lysine was employed as additive to prepare face-centered cubic spinel Li₄Mn₅O₁₂. During the process, l-lysine played important roles such as complexing agent as well as combusting agent and adjusting the pH values of solution. The physical characteristics of Li₄Mn₅O₁₂ were characterized by X-ray diffraction and scanning electron microscopy. The electrochemical capacitance performance of Li₄Mn₅O₁₂ electrode was characterized by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. These analyses indicated that Li₄Mn₅O₁₂ was able to deliver 168 F?g^?1 within the potential range of 0–1.4 V at a scan rate of 5 mV?s^?1 in 1 mol?L^?1 Li₂SO₄. Nine hundred cycles later, the capacitance faded to 165 F?g^?1 with cutting down by 0.003 F?g^?1 per cycling period and also can remain 98.2 % of original value, displaying a good cycling performance.     

Simple co-precipitation synthesis of high-voltage spinel cathodes with different Ni/Mn ratios for lithium-ion batteries

The high-voltage spinel is a promising cathode material in next generation of lithium-ion batteries. Samples LiNi_0.5???xMn_1.5?+?xO₄ (x?=?0, 0.05, 0.1) are synthesized by a simple co-precipitation method, in which pH value and temperature conditions do not need control. In the simple co-precipitation method, NaHCO₃ solution is poured into transition metal solution to produce precursor. Ni and Mn are distributed uniformly in the products. The as-prepared samples are composed of ~?200 nm primary particles. Samples LiNi_0.5???xMn_1.5?+?xO₄ (x?=?0, 0.05, 0.1) are also tested to study the effects of different Ni/Mn ratios. Sample LiNi_0.5Mn_1.5O₄ delivers discharge capacities of 130 mAh g^?1 at 0.2 C. The decreasing of Ni/Mn ratio in samples reduces specific capacity. With the decreasing of Ni/Mn ratios in spinel, amount of Mn³⁺ are increased. Attributed to its high Mn³⁺ contents, sample LiNi_0.4Mn_1.6O₄ delivers the highest discharge capacity of 106 mAh g^?1 at a large current density of 15 C, keeping 84.5% of that at 0.2 C rate. With the increasing of Ni/Mn ratios in spinel, cycling performance is improved. Sample LiNi_0.5Mn_1.5O₄ shows the best cycling stability, keeping 94.4% and 90.4% of the highest discharge capacities after 500 cycles at 1 C and 1000 cycles at 5 C.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Understanding the thermal stability and bonding characteristic of Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> as cathode materials for lithium-ion battery from first principles

The thermodynamic stability is a very important quantity for the electrode materials, because it is not only related to the electrochemical performances of the materials but also the safety issue of the cells. To evaluate the thermodynamic stability of Li _x Ni_0.5Mn_1.5O₄ (x = 0, 1), the formation enthalpies from elemental phases and oxides were obtained. The values for LiNi_0.5Mn_1.5O₄ were calculated to be ?1341.10 and ?141.84 kJ mol^?1, while those for Ni_0.5Mn_1.5O₄ were ?949.11 and ?49.21 kJ mol^?1. These values are much more negative than those of LiCoO₂ and LiNiO₂ compounds, indicating that the thermodynamic stability of Li _x Ni_0.5Mn_1.5O₄ is better than the two classic compounds. To clarify the microscopic origin, the density of states, magnetic moments, and bond orders were systematically investigated. The results showed that the excellent thermodynamic stability of LiNi_0.5Mn_1.5O₄ is attributed to the absence of Jahn-Teller distortions, strong electrostatic interactions of Li–O ionic bond, and strong Ni–O/Mn–O ionic-covalent mixing bonds. After lithium extraction, the disappearance of the pure Li–O bonds leads to an increase of formation enthalpy, indicating a decreasing thermodynamic stability for Ni_0.5Mn_1.5O₄ with respect to LiNi_0.5Mn_1.5O₄.     

Oligo(ethylene oxide)-functionalized trialkoxysilanes as novel electrolytes for high-voltage lithium-ion batteries

Oligo(ethylene oxide)-functionalized trialkoxysilanes were synthesized through hydrosilylation reaction by reacting trialkoxysilane with oligo(ethylene oxide) allyl methyl ether using PtO₂ as a catalyst. The physical properties of these compounds, such as viscosity, dielectric constant, and ionic conductivity, were characterized. Among them, [3-(2-(2-methoxyethoxy)ethoxy)-propyl]triethoxysilane (TESM2) exhibited a commercial viable ionic conductivity of 1.14 mS cm^?1 and a wide electrochemical window of 5.2 V. A preliminary investigation was conducted by using TESM2 as an electrolyte solvent for high-voltage applications in lithium-ion batteries. Using 1 M LiPF₆ in TESM2 with 1 vol% vinyl carbonate as an electrolyte, LiCoO₂/Li half-cell delivered a specific capacity of 153.9 mAh g^?1 and 90 % capacity retention after 80 cycles (3.0–4.35 V, 28 mA g^?1); Li_1.2Ni_0.2Mn_0.6O₂/Li₄Ti₅O₁₂ full cell exhibited the initial capacity of 161.3 mAh g^?1 and 86 % capacity retention after 30 cycles (0.5–3.1 V, 18 mA g^?1).     

Effects of doping Al on the structure and electrochemical performances of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> cathode materials

The Li-rich cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ had been successfully synthesized by a carbonate coprecipitation method. The effects of substituting traces of Al element for different transitional metal elements on the crystal structure and surface morphology had been investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy. The results revealed that all the materials showed similar XRD patterns and surface morphology. It was demonstrated that LNCMAl1 exhibited the superior electrochemical performance. The discharge capacity was 265.2 mAh g^?1 at 0.1 C and still maintained a discharge capacity of 135.6 mAh g^?1 at 5.0 C. The capacity retention could still be 58.2 and 66.8% after 50 cycles at 1.0 and 2.0 C, respectively. Electrochemical impedance spectra results proved that the remarkably improved rate capability and cycling performance could be ascribed to the low charge transfer resistance and enhanced reaction kinetics.     

Preparation and characterization of Li1.2Ni0.13Co0.13Mn0.54O2 cathode materials for lithium-ion battery

Lithium-rich cathode materials Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ with (sample SF) and without (sample SP) formamide was synthesized by a spray-dry method. The crystalline structure and particle morphology of as-prepared materials were characterized by X-ray diffraction and scanning electron microscope. The specific surface area (SSA) of the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ prepared from different routes was determined by a five-point Brunauer–Emmett–Teller (BET) method using N₂ as absorbate gas. Being compared with the material synthesized without spray-drying process (sample CP), sample SP has much higher SSA. The additive formamide is helpful to form regular and solid precursor particles in spray-drying process, which results in a slightly aggregation of grains and reduction of SSA for sample SF. The electrochemical activities of the materials are closely related to their morphology and SSA. In the voltage range of 2–4.8 V at 25 °C, sample SP present a discharge capacity of 257 mAh g^?1 at 0.1 C rate and 170 mAh g^?1 at 1 C rate. The sample CP delivered only 136 mAh g^?1 when discharged at 1 C rate. The elevated specific capacity and rate capability are attributed to smaller primary particle and higher SSA. Both cycle performance and rate capability of Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ were improved when formamide was used in spray-dry process. Discharge capacity of SF is 140.5 mAh g^?1 at 2 C rate, and that of SP is 132.3 mAh g^?1. Overlarge SSA of SP may provoke serious side reaction, so that its electrochemical performance was deteriorated.     

C-rate and temperature dependence of electrochemical performance of Li[Co0.1Ni0.15Li0.2Mn0.55]O2 cathode materials before and after Co3(PO4)2 coating

Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ was synthesized, as a cathode material with high capacity, by a simple combustion method followed by annealing at 800?°C. Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ cathode materials were coated with lithium-active Co₃(PO₄)₂ to improve the electrochemical performance of rechargeable lithium batteries. Morphologies and physical properties of Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ before and after the Co₃(PO₄)₂ coating were analyzed with a scanning electron microscope equipped with an energy dispersive X-ray spectroscope. Transmission electron microscopy, powder X-ray diffraction, and Brunauer?CEmmett?CTeller surface area analyses were also carried out. The electrochemical performances of Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ cathode material before and after Co₃(PO₄)₂ coating were evaluated by galvanostatic charge?Cdischarge testing at different charge and discharge densities. The temperature dependence of the cathode material before and after Co₃(PO₄)₂ coating was investigated at 0, 10, 20, 30, 40, and 50?°C at a rate of 0.1?C. Co₃(PO₄)₂-Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂ exhibited good electrochemical performance under high C-rate and experimental temperature conditions. The enhanced electrochemical performances were attributed to the formation of a lithium-active Co₃(PO₄)₂-coating layer on Li[Co_0.1Ni_0.15Li_0.2Mn_0.55]O₂.     

The ionic conductivity of Li6BaLa2M2O12 with coexisting Nb and Ta on the M sites

In a view to balancing cost and lithium ion conductivity, Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2) was prepared by solid-state reaction, and its corresponding AC impedances were tested at temperatures ranging from 20 to 250 °C in air. Li₆BaLa₂Ta₂O₁₂ exhibits the highest conductivity, 8.77?×?10^?6?S/cm, and the second highest is Li₆BaLa₂Nb₂O₁₂ with 6.69?×?10^?6?S/cm. Partial replacement of Ta with Nb cannot bestow the advantages of cost saving or the enhancement of lithium ion conductivity. X-ray diffraction patterns revealed a gradual change as an increasing amount of Nb replaces Ta in Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2), and it is thought that the trending of Nb and Ta to rest on the crystallographic planes is different.