Synthesis and characterizations of Li[CrxLi(1−x)/3Mn2(1−x)/3]O2 (0.15 ≤ x ≤ 0.3) cathode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ (0.15 ≤ x ≤ 0.3) cathode materials was prepared by citric acid-assisted, sol–gel process. Sub-micron sized particles were obtained and the X-ray diffraction (XRD) results showed that the crystal structure was similar to layered lithium transition metal oxides (R-3m space group). The electrochemical performance of the cathodes was evaluated over the voltage range 2.0–4.9 V at a current density of 7.947 mA g⁻¹. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of up to 280 mAh g⁻¹ during cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ yielded a promising cathode material.     

Electrochemical properties of iodine-containing lithium manganese oxide spinel

Iodine-containing, cation-deficient, lithium manganese oxides (ICCD-LMO) are prepared by reaction of MnO₂ with LiI. The MnO₂ is completely transformed into spinel-structured compounds with a nominal composition of Li_1−δMn_2−2δO₄I_x. A sample prepared at 800 °C, viz. Li_0.99Mn_1.98O₄I_0.02, exhibits an initial discharge capacity of 113 mA h g⁻¹ with good cycleability and rate capability in the 4-V region. Iodine-containing, lithium-rich lithium manganese oxides (ICLR-LMO) are also prepared by reaction of LiMn₂O₄ with LiI, which results in a nominal composition of Li_1+xMn_2−xO₄I_x. Li_1.01Mn_1.99O₄I_0.02 shows a discharge capacity of 124 mA h g⁻¹ on the first cycle and 119 mA h g⁻¹ a on the 20th cycle. Both results indicate that a small amount of iodine species helps to maintain cycle performance.     

Effect of (Al,Mg) substitution in LiNiO2 electrode for lithium batteries

Stabilized lithium nickelate is receiving increased attention as a low-cost alternative to the LiCoO₂ cathode now used in rechargeable lithium batteries. Layered LiNi_1−x−yM_xM_yO₂ samples (M_x = Al³⁺ and M_y = Mg²⁺, where x = 0.05, 0.10 and y = 0.02, 0.05) are prepared by the refluxing method using acetic acid at 750 °C under an oxygen stream, and are subsequently subjected to powder X-ray diffraction analysis and coin-cell tests. The co-doped LiNi_1−x−yAl_xMg_yO₂ samples show good structural stability and electrochemical performance. The LiNiAl_0.05Mg_0.05O₂, cathode material exhibits a reversible capacity of 180 mA h g⁻¹ after extended cycling. These results suggest that the threshold concentration for aluminum and magnesium substitution is of the order of 5%. The co-substitution of magnesium and aluminium into lithium nickelate is considered to yield a promising cathode material.     

Electrochemical lithium insertion in TiO2 with the ramsdellite structure

The electrochemical insertion of lithium in the ramsdellite polymorph of titanium dioxide, TiO₂ (R), is studied by electrochemical methods. At room temperature the maximal Li uptake under constant current densities of 0.1, 0.5 and 1.0 mA cm⁻² is 0.85, 0.8 and 0.7 Li/Ti, respectively. Between 2.3 and 1.3 V versus lithium, the specific capacity achieved is as high as 285 A h kg⁻¹ at 0.5 mA cm⁻². This corresponds to 85% of the maximum theoretical capacity (336 A h kg⁻¹), which may be reached by incorporation of one lithium per titanium under equilibrium conditions.     

Metal oxyfluorides TiOF2 and NbO2F as anodes for Li-ion batteries

Lithium insertion and extraction in to/from the oxyfluorides TiOF₂ and NbO₂F is investigated by galvanostatic cycling, cyclic voltammetry and impedance spectroscopy in cells using Li-metal as a counter electrode at ambient temperature. The host compounds are prepared by low-temperature reaction and characterized by powder X-ray diffraction (XRD), Rietveld refinement and Brunauer, Emmett and Teller (BET) surface area. Crystal structure destruction occurs during the first-discharge reaction with Li at voltages below 0.8–0.9 V for Li_xTiOF₂ as shown by ex situ XRD and at ≤1.4 V for Li_xNbO₂F to form amorphous composites, ‘Li_xTi/NbO_y–LiF’. Galvanostatic discharge–charge cycling of ‘Li_xTiO_y’ in the range 0.005–3.0 V at a current density of 65 mA g⁻¹ gives a capacity of 400 (±5) mAh g⁻¹ during 5–100 cycles with no noticeable capacity fading. This value corresponds to 1.52 mol of recycleable Li/Ti. The coulombic efficiency (η) is >98%. Results on ‘Li_xNbO_y’ show good reversibility of the electrode and a η >98% is achieved only after 10 cycles (range 0.005–3.0 V and at 30 mA g⁻¹) and a capacity of 180 (±5) mAh g⁻¹ (0.97 mol of Li/Nb) was stable up to 40 cycles. In both ‘Li_xTiO_y’ and ‘Li_xNbO_y’, the average discharge and charge voltages are 1.2–1.4 and 1.7–1.8 V, respectively. The impedance spectral data measured during the first cycle and after selected numbers of cycles are fitted to an equivalent circuit and the roles played by the relevant parameters as a function of cycle number are discussed.     

Synthesis and electrochemical properties of Mo-doped Li[Ni1/3Mn1/3Co1/3]O2 cathode materials for Li-ion battery

The layered Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Mo_x]O₂ cathode materials (x = 0, 0.005, 0.01, and 0.02) were prepared by a solid-state pyrolysis method (700, 800, 850, and 900 °C). Its structure and electrochemical properties were characterized by XRD, SEM, XPS, cyclic voltammetry, and charge/discharge tests. It can be learned that the doped sample of x = 0.01 calcined at 800 °C shows the highest first discharge capacity of 221.6 mAh g⁻¹ at a current density of 20 mA g⁻¹ in the voltage range of 2.3–4.6 V, and the Mo-doped samples exhibit higher discharge capacity and better cycle-ability than the undoped one at room temperature.     

Effect of titanium substitution in layered LiNiO2 cathode material prepared by molten-salt synthesis

LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) compounds have been synthesized by a direct molten-salt method that uses a eutectic mixture of LiNO₃ and LiOH salts. According to X-ray diffraction analysis, these materials have a well-developed layered structure (R3-m) and are an isostructure of LiNiO₂. The LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) compounds have average particle sizes of 1–5 μm depending on the amount of Ti salt. Charge–discharge tests show that a LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) cathode prepared at 700 °C has an initial discharge capacity as high as 171 mA h g⁻¹ and excellent capacity retention in the range 4.3–2.8 V at a current density of 0.2 mA cm⁻².     

LiMn2O4 cathode materials synthesized by the cellulose–citric acid method for lithium ion batteries

A new technique was employed to synthesize spinel LiMn₂O₄ cathode materials by adding cellulose and citric acid to an aqueous solution of lithium and manganese salts. Various synthesis conditions such as the calcination temperature and the citric acid-to-metal ion molar ratio (R) were investigated to determine the ideal conditions for preparing LiMn₂O₄ with the best electrochemical characteristics. The optimal synthesis conditions were found to be R = 1/3 and a calcination temperature of 800 °C. The initial discharge capacity of the material synthesized using the optimal conditions was 134 mAh g⁻¹, and the discharge capacity after 40 cycles was 125 mAh g⁻¹, at a current density of 0.15 mA cm⁻² between 3.0 and 4.35 V. Details of how the initial synthesis conditions affected the capacity and cycling performance of LiMn₂O₄ are discussed.     

NbSb2 as an anode material for Li-ion batteries

Polycrystalline samples of NbSb₂ have been synthesized and studied as anode material for lithium-ion batteries. The reaction mechanism of lithium with NbSb₂ is investigated by ex situ XRD and cyclic voltammogram studies. Li₃Sb and Nb are formed during first discharge and during charge lithium is extracted from Li₃Sb. The first cycle discharge capacity is 420 mA hg⁻¹ and first cycle charge capacity is 315 mA hg⁻¹.     

Development of high energy density small flat spiral cells and battery pack based on lithium/carbon monofluoride (Li/CFx)

Small spiral-wound lithium–carbon monofluoride (Li/CF_x) cells, which were discharged at the C/40 rate, had a nominal capacity of 300 mAh and a gravimetric energy density of about 464 Wh kg⁻¹. These cells delivered pulse current loads (>22 mA) with good capacity (>200 mAh) if they were subjected to a pre-discharge step. A 17 V, 2.2 kW battery based on Li/CF_x flat cell technology has also been fabricated and tested. The battery had gravimetric and volumetric energy densities of 360 Wh kg⁻¹ and 700 Wh dm⁻³, respectively. This compares with a value of 330 Wh kg⁻¹ and 522 Wh dm⁻³ for an equivalent battery based on Li/SOCl₂.     

A high energy density lithium/sulfur–oxygen hybrid battery

In this paper we introduce a lithium/sulfur–oxygen (Li/S–O₂) hybrid cell that is able to operate either in an air or in an environment without air. In the cell, the cathode is a sulfur–carbon composite electrode containing appropriate amount of sulfur. In the air, the cathode first functions as an air electrode that catalyzes the reduction of oxygen into lithium peroxide (Li₂O₂). Upon the end of oxygen reduction, sulfur starts to discharge like a normal Li/S cell. In the absence of oxygen or air, sulfur alone serves as the active cathode material. That is, sulfur is first reduced to form a soluble polysulfide (Li₂S_x, x ≥ 4) that subsequently discharges into Li₂S through a series of disproportionations and reductions. In general, the Li/S–O₂ hybrid cell presents two distinct discharge voltage plateaus, i.e., one at ～2.7 V attributing to the reduction of oxygen and the other one at ～2.3 V attributing to the reduction of sulfur. Since the final discharge products of oxygen and sulfur are insoluble in the organic electrolyte, it is shown that the overall specific capacity of Li/S–O₂ hybrid cell is determined by the carbon composite electrode, and that the specific capacity varies with the discharge current rate and electrode composition. In this work, we show that a composite electrode composed by weight of 70% M-30 activated carbon, 22% sulfur and 8% polytetrafluoroethylene (PTFE) has a specific capacity of 857 mAh g^?1 vs. M-30 activated carbon at 0.2 mA cm^?2 in comparison with 650 mAh g^?1 of the control electrode consisting of 92% M-30 and 8% PTFE. In addition, the self-discharge of the Li/S–O₂ hybrid cell is expected to be substantially lower when compared with the Li/S cell since oxygen can easily oxidize the soluble polysulfide into insoluble sulfur.     

Chemical and structural instabilities of lithium ion battery cathodes

The chemical and structural stabilities of various layered Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes are compared by characterizing the samples obtained by chemically extracting lithium from the parent Li_1−xNi_1−y−zMn_yCo_zO₂ with NO₂BF₄ in an acetonitrile medium. The nickel- and manganese-rich compositions such as Li_1−xNi_1/3Mn_1/3Co_1/3O₂ and Li_1−xNi_0.5Mn_0.5O₂ exhibit better chemical stability than the LiCoO₂ cathode. While the chemically delithiated Li_1−xCoO₂ tends to form a P3 type phase for (1 − x) < 0.5, Li_1−xNi_0.5Mn_0.5O₂ maintains the original O3 type phase for the entire 0 ≤ (1 − x) ≤ 1 and Li_1−xNi_1/3Mn_1/3Co_1/3O₂ forms an O1 type phase for (1 − x) < 0.23. The variations in the type of phases formed are explained on the basis of the differences in the chemical lithium extraction rate caused by the differences in the degree of cation disorder and electrostatic repulsions. Additionally, the observed rate capability of the Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes bears a clear relationship to cation disorder and lithium extraction rate.     

Synthesis and electrochemical properties of lithium cobalt oxides prepared by molten-salt synthesis using the eutectic mixture of LiCl–Li2CO3

Lithium cobalt oxide powders have been successfully prepared by a molten-salt synthesis (MSS) method using a eutectic mixture of LiCl and Li₂CO₃ salts. The physico-chemical properties of the lithium cobalt oxide powders are investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), particle-size analysis and charge–discharge cycling. A lower temperature and a shorter time (∼700°C and 1 h) in the Li:Co=7 system are sufficient to prepare single-phase HT-LiCoO₂ powders by the MSS method, compared with the solid-state reaction method. Charge–discharge tests show that the lithium cobalt oxide prepared at 800°C has an initial discharge capacity as high as 140 mA h g⁻¹, and 100 mA h g⁻¹ after 40 cycles. The dependence of the synthetic conditions of HT-LiCoO₂ on the reaction temperature, time and amount of flux with respect to starting oxides is extensively investigated.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

Synthesis and electrochemical properties of Li[Li(1−2x)/3NixMn(2−x)/3]O2 as cathode materials for lithium secondary batteries

Layered Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂ materials with x=0.41, 0.35, 0.275 and 0.2 are synthesized by means of a sol–gel method. The layered structure is stabilized by a solid solution between LiNiO₂ and Li₂MnO₃. The discharge capacity increases with increasing lithium content at the 3a sites in the Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂. A Li[Li_0.2Ni_0.2Mn_0.6]O₂ electrode delivers discharge capacities of 200 and 240 mAh g⁻¹ with excellent cycleability at 30 and 55 °C, respectively.     

Synthesis and electrochemical properties of Li[Ni0.8Co0.1Mn0.1]O2 and Li[Ni0.8Co0.2]O2 via co-precipitation

Spherical Li[Ni_0.8Co_0.2−xMn_x]O₂ (x = 0, 0.1) with phase-pure and well-ordered layered structure have been synthesized by heat-treatment of spherical [Ni_0.8Co_0.2−xMn_x](OH)₂ and LiOH·H₂O precursors. The structure, morphology, electrochemical properties, and thermal stability of Li[Ni_0.8Co_0.2−xMn_x]O₂ (x = 0, 0.1) were studied. The average particle size of the powders was about 10–15 μm and the size distribution was narrow due to the homogeneity of the metal hydroxide [Ni_0.8Co_0.2−xMn_x](OH)₂ (x = 0, 0.1). The Li[Ni_0.8Co_0.2−xMn_x]O₂ (x = 0, 0.1) delivered a discharge capacity of 197–202 mAh g⁻¹ and showed excellent cycling performance. Compared to Li[Ni_0.8Co_0.2]O₂, Li[Ni_0.8Co_0.1Mn_0.1]O₂ exhibited greater thermal stability resulting from improved structural stability due to Mn substitution.     

Effects of synthesis conditions on the structural and electrochemical properties of layered Li[Ni1/3Co1/3Mn1/3]O2 cathode material via the hydroxide co-precipitation method LIB SCITECH

The uniform layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material for lithium ion batteries was prepared by using (Ni_1/3Co_1/3Mn_1/3)(OH)₂ synthesized by a liquid phase co-precipitation method as precursor. The effects of calcination temperature and time on the structural and electrochemical properties of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ were systemically studied. XRD results revealed that the optimal prepared conditions of the layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ were 850 °C for 18 h. Electrochemical measurement showed that the sample prepared under the above conditions has the highest initial discharge capacity of 162.1 mAh g⁻¹ and the smallest irreversible capacity loss of 9.2% as well as stable cycling performance at a constant current density of 16 mA g⁻¹ between 3 and 4.3 V versus Li at room temperature.     

Preparation and electrochemical/thermal properties of LiNi0.74Co0.26O2 cathode material

Electrochemical and thermal properties of LiNi_0.74Co_0.26O₂ cathode material with 5, 13 and 25 μm-sized particles have been studied by using a coin-type half-cell Li/LiNi_0.74Co_0.26O₂. The specific capacity of the material ranges from 205 to 210 mA h g⁻¹, depending on the particle size or the Brunauer, Emmett and Teller (BET) surface area. Among the particle sizes, the cathode with a particle size of 13 μm shows the highest specific capacity. Even though the material with a particle size of 5 μm exhibits the smallest capacity value of 205 mA h g⁻¹, no capacity fading was observed after 70 cycles between 4.3 and 2.75 V at the 1 C rate. Differential scanning calorimetry (DSC) studies of the charged electrode at 4.3 V show a close relationship between particle size (BET surface area) and thermal stability of the electrode, namely, a larger particle size (smaller BET surface area) leads to a better thermal stability of the LiNi_0.74Co_0.26O₂ cathode.     

Crystallographic and electrochemical characteristics of La0.7Mg0.3Ni3.5 − x(Al0.5Mo0.5)x (x = 0–0.8) hydrogen storage alloys

The crystal structure, hydrogen storage property and electrochemical characteristics of the La_0.7Mg_0.3Ni_3.5 − x(Al_0.5Mo_0.5)_x (x = 0–0.8) alloys have been investigated systematically. It can be found that with X-ray powder diffraction and Rietveld analysis the alloys are of multiphase alloy and consisted of impurity LaNi phase and two main crystallographic phases, namely the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase, and the lattice parameter and the cell volume of both the La(La, Mg)₂Ni₉ phase and the LaNi₅ phase increases with increasing Al and Mo content in the alloys. The P–C isotherms curves indicate that the hydrogen storage capacity of the alloy first increases and then decreases with increasing x, and the equilibrium pressure decreases with increasing x. The electrochemical measurements show that the maximum discharge capacity first increases from 354.2 (x = 0) to 397.6 mAh g⁻¹ (x = 0.6) and then decreases to 370.4 mAh g⁻¹ (x = 0.8). The high-rate dischargeability of the alloy electrode increases lineally from 55.7% (x = 0) to 73.8% (x = 0.8) at the discharge current density of 1200 mA g⁻¹. Moreover, the exchange current density of the alloy electrodes also increases monotonously with increasing x. The hydrogen diffusion coefficient in the alloy bulk increases with increasing Al and Mo content and thus enhances the low-temperature dischargeability of the alloy electrode.     

Electrochemical lithium insertion into amorphous MoO3·2H2O

Following the route of synthesis of β-MoO₃ through soft chemistry methods a new amorphous material with composition MoO₃·2H₂O has been detected. The hydrated molybdenum oxide showed the capacity for electrochemical lithium insertion. The maximum amount of lithium incorporated in this material (∼3.3 Li/Mo) leads to a specific capacity of 490 Ah kg⁻¹. The charge–discharge curve showed a good reversibility in the potential range from 3.2 to 1.1 V versus Li⁺/Li⁰ where the cell voltage decreased monotonously as a function of the degree of lithium inserted. The electrochemical features of amorphous MoO₃·2H₂O suggest that it can be considered as a possible cathode candidate in rechargeable lithium batteries.