Synthesis of olivine-type LiFePO4 by emulsion-drying method

Olivine-type, orthorhombic, LiFePO₄ powders with small particle size have been successfully synthesized by the emulsion-drying method. The electronic and crystal structure is analyzed by X-ray absorption spectroscopy (XAS) and X-ray diffraction Rietveld refinement. The powder calcined at 750 °C shows the highest discharge capacity of 125 mAh g⁻¹ with excellent cycle stability. The discharge capacity of this powder increases to 154 mAh g⁻¹ on increasing the addition of carbon black as a conductive agent up to 40 wt.%. In a rate capability test, the discharge capacity is completely recovered and retained up to the 700th cycle.     

Porous olivine composites synthesized by sol–gel technique

Porous LiMPO₄/C composites (where M stands for Fe and/or Mn) with micro-sized particles were synthesised by sol–gel technique. Particles porosity is discussed in terms of qualitative results obtained from SEM micrographs and in terms of quantitative results obtained from N₂ adsorption isotherms. Porous particles could be described as an inverse picture of nanoparticulate arrangement, where the pores serve as channels for lithium supply and the distance between the pores determines the materials kinetics. Tests show that the electrochemical behaviour of porous LiMPO₄/C composite is comparable with the results from the literature. The best electrochemical results were obtained with a LiFePO₄/C composite (over 140 mAh g⁻¹ at C/2 rate during continuous cycling). The capacity obtained with LiMnPO₄/C composite is much lower (40 mAh g⁻¹ at C/20 rate), although the textural properties are similar to those observed in the LiFePO₄/C composite.     

Tin–graphite materials prepared by reduction of SnCl4 in organic medium: Synthesis,characterization and electrochemical lithiation

Tin–graphite materials were prepared by chemical reduction of SnCl₄ by t-BuONa-activated NaH. TEM imaging showed that the crude material is composed of an amorphous organic matrix containing tin present either as nanosized particles deposited on the graphite surface or as free aggregates. Subsequent washings with ethanol and water allow removal of side products as well as most part of the organic matrix. Electrochemical insertion of lithium occurred in graphite and in tin. The initial reversible massic capacity of 630 mAh g⁻¹ decayed to a stable value of 415 mAh g⁻¹ after 12 cycles. This capacity value was lower than the expected maximum one of 650 mAh g⁻¹ corresponding to a Sn/12C molar composition and assuming the formation of LiC₆ and Li₂₂Sn₅. Even if this massic capacity is not much improved by comparison with that of graphite, it must be pointed out that the volume capacity of this graphite/Sn material is much larger (2137 mAh cm⁻³) than that corresponding to graphite (837 mAh cm⁻³). It was hypothesized that the part of tin bound to graphite could be responsible for the stable reversible capacity. To the contrary, graphite unsupported tin aggregates would contribute to the observed gradual decline in the storage capacity. Therefore, the improvement in cycleability, compared to that of massive metals, could be attributed both to the nanoscale dimension of the metal particles and to interactions between graphite and metal the nature of which remaining to be precised.     

Nanoparticled Li(Ni1/3Co1/3Mn1/3)O2 as cathode material for high-rate lithium-ion batteries

Nanoparticle of Li(Ni_1/3Co_1/3Mn_1/3)O₂ with size smaller than 40 nm was obtained by non-aqueous system co-precipitation method. The particle morphology and crystal plane orientation were observed by TEM and HRTEM. Electrochemical properties of this nanostructued material were studied with experiment cells. The results show that the material has high capacity of 160 mAh g⁻¹ and excellent rate capability for charge and discharge. For the 50C and 100C rate, its capacity remains above 100 mAh g⁻¹ after tens of cycles.     

Effect of Fe2P on the electron conductivity and electrochemical performance of LiFePO4 synthesized by mechanical alloying using Fe3+ raw material

LiFePO₄ and LiFePO₄/Fe₂P composites have been produced using raw Fe₂O₃ materials by mechanical alloying (MA) and subsequent firing at 900 °C. The LiFePO₄ prepared by firing at 900 °C for 30 min showed a maximum discharge capacity of 160 mAh g⁻¹ at C/20, which is at a higher capacity and improved cell performance compared with the LiFePO₄ prepared using for a longer firing times. LiFePO₄/Fe₂P composites have been synthesized by the reduction reaction of phosphate in excess of carbon. By transmission electron microscopy (TEM) and scanning electron microscopy (SEM) it was determined that the LiFePO₄ phase was agglomerated with a primary particle size of 40–50 nm around the surface of Fe₂P with particle size of 200 nm. The electronic conductivity of the LiFePO₄/Fe₂P composite increased in proportion with the amount that the Fe₂P phase and discharge capacity increased during the cycling. The sample containing 8% of Fe₂P in LiFePO₄/Fe₂P composite showed a high discharge capacity and rate capability at high current.     

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.     

Effect of synthesis conditions on the properties of LiFePO4 for secondary lithium batteries

LiFePO₄ is one of the promising materials for cathode of secondary lithium batteries due to its high energy density, low cost, environmental friendliness and safety. However, LiFePO₄ has very poor electronic conductivity (∼10⁻⁹ S cm⁻¹) and Li-ion diffusion coefficient (∼1.8 × 10⁻¹⁴ cm² s⁻¹) at room temperature. In an attempt to improve electrochemical properties, Li_XFePO₄ with various amounts of Li contents were investigated in this study. Li_XFePO₄ (X = 0.7–1.1) samples were synthesized by solid-state reaction. High resolution X-ray diffraction, Rietveld analysis, BET, scanning electron microscopy, and hall effect measurement system were used to characterize these samples. Electronic conductivities of the samples with Li-deficient and Li-excess in Li_xFePO₄ were 10⁻³ to 10⁻¹ S cm⁻¹. Discharge capacities and rate capabilities of the samples with Li-deficient and Li-excess in Li_XFePO₄ were higher than those of stoichiometric LiFePO₄ sample. Li_0.9FePO₄ samples fired at 700 °C had discharge capacity of 156 and 140 mAh g⁻¹ at 0.1 C- and 2 C-rate, respectively.     

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.     

Electrochemical characteristics of needle coke refined by molten caustic leaching as an anode material for a lithium-ion battery

Needle coke, the remaining material after refining petroleum, is used as an anode of a lithium-ion secondary battery. Sulfur is separated from the needle coke to below 0.1 wt.% using the molten caustic leaching (MCL) method developed at the Korea Institute of Energy Research. The needle coke with high-purity is carbonized at various temperatures, namely 0, 500, 700 and 900 °C. The coke treated at 700 °C gives a first and second discharge capacity of more than 560 and 460 mAh g⁻¹, respectively, between 0 and 2.0 V. By contrast, the first and second discharge capacity of untreated coke is over 420 and 340 mAh g⁻¹, respectively, between 0.05 and 2.0 V.The first discharge capacity of 560 mAh g⁻¹ is beyond the theoretical maximum capacity of 372 mAh g⁻¹ for LiC₆. Though the cycle efficiency is not consistent, the needle coke heat-treated at 700 °C persistently maintains an efficiency of over 90% until the 50th cycle, except on the first cycle. This study demonstrates that the needle coke with high-purity could be a good candidate for an anode material in fabricating high-capacity lithium-ion secondary batteries.     

Preparation,characterization and electrolytic behavior of β-nickel hydroxide

Nickel hydroxide is prepared by neutralizing NiSO₄ solution with 4.8 M NaOH, followed by washing the precipitate and treating the slurry hydrothermally at different temperatures. The parameters varied are: initial nickel concentration; effect of presence of sodium ions during hydrothermal treatment; aging time after hydrothermal treatment. The samples so prepared are chemically analyzed and the physical and electrolytic properties such as tap density, percentage weight loss and discharge capacity are determined. On increasing the temperature from 60 to 160 °C, the discharge capacity increases from 52 to 112 mAh g⁻¹. At 200 °C, the discharge capacity decreases to 94 mAh g⁻¹. Allowing the hydroxide precipitate to age after hydrothermal treatment also causes a decrease in discharge capacity. The presence of excess sodium ions during hydrothermal treatment yields nickel hydroxide with a very low discharge capacity. The maximum discharge capacity of 160 mAh g⁻¹ is obtained for nickel hydroxide prepared under the following conditions: nickel concentration 43 g l⁻¹, neutralizing agent sodium hydroxide, time of hydrothermal treatment 2 h, temperature during hydrothermal treatment 160 °C. XRD patterns and FTIR spectra confirm the precipitate to be β-nickel hydroxide. The sample contains 62.89 wt.% Ni with a tap density of 0.96 g cm⁻³. TG–DTA measurements show a weight loss of 19% with an endothermic peak at 325 °C which corresponds to the decomposition of nickel hydroxide to nickel oxide. The present method of preparing nickel hydroxide through hydrothermal treatment reduces the aging time to 2 h and gives a product with good filtration characteristics.     

Effects of ball-milling on lithium insertion into multi-walled carbon nanotubes synthesized by thermal chemical vapour deposition

The effects of ball-milling on Li insertion into multi-walled carbon nanotubes (MWNTs) are presented. The MWNTs are synthesized on supported catalysts by thermal chemical vapour deposition, purified, and mechanically ball-milled by the high energy ball-milling. The purified MWNTs and the ball-milled MWNTs were electrochemically inserted with Li. Structural and chemical modifications in the ball-milled MWNTs change the insertion–extraction properties of Li ions into/from the ball-milled MWNTs. The reversible capacity (C_rev) increases with increasing ball-milling time, namely, from 351 mAh g⁻¹ (Li_0.9C₆) for the purified MWNTs to 641 mAh g⁻¹ (Li_1.7C₆) for the ball-milled MWNTs. The undesirable irreversible capacity (C_irr) decreases continuously with increase in the ball-milling time, namely, from 1012 mAh g⁻¹ (Li_2.7C₆) for the purified MWNTs to 518 mAh g⁻¹ (Li_1.4C₆) for the ball-milled MWNTs. The decrease in C_irr of the ball-milled samples results in an increase in the coulombic efficiency from 25% for the purified samples to 50% for the ball-milled samples. In addition, the ball-milled samples maintain a more stable capacity than the purified samples during charge–discharge cycling.     

One-step synthesis LiMn2O4 cathode by a hydrothermal method

Spinel LiMn₂O₄ powders have been successfully synthesized by a hydrothermal method directly, which is no any pretreatment and following treatment in the process. The structure and morphology of the powders were studied in detail by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and thermogravimetric analysis (TGA). The data reveal that the products have well-defined stable spinel structure, and the particles show distinctive crystal faces with 50–300 nm in particle sizes. The electrochemical characteristics of the spinel materials are measured in the coin-type cells in a potential range of 3.2–4.35 V versus Li/Li⁺. The as-synthesized LiMn₂O₄ delivers reversible capacity of about 121 mAh g⁻¹ at a current density of 1/10 C. Cycled the cell to 40 cycles, the capacity remains at about 111 mAh g⁻¹ at 1/2 C.     

Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel

LiNi_0.5Mn_1.5O₄ material with a spinel structure is prepared by a sol–gel method. The material is initially fired at 850 °C and then subjected to a post-reaction annealing at 600 °C in order to minimize the nickel deficiency. The elevated firing temperature produces materials with a small surface-area which is beneficial for good capacity retention. Indeed, the spinel LiNi_0.5Mn_1.5O₄ not only shows a good cycle performance, but exhibits an excellent discharge capacity, i.e. 114 mAh g⁻¹ at 4.66 V plateau and 127 mAh g⁻¹ in total. Cyclic voltammetry and ac impedance spectroscopy are employed to characterize the reactions of lithium insertion and extraction in the LiNi_0.5Mn_1.5O₄ electrode. Excellent electrochemical performance and low material cost make this compound an attractive cathode for advanced lithium batteries.     

Effect of chitosan on stabilization of acetates-containing solution: A novel precursor for LiMn2O4 film deposition

Due to the adequate viscosity of the chitosan-added precursor solutions, the films deposited from the chitosan-added precursor solution showed a higher deposition rate than the ones from the PVP-added solution under the same coating parameters. Furthermore, the chitosan-added precursor solution remained stable without any precipitation for at least 10 months. On the other hand, without the addition of chitosan, the precursor solution showed apparent precipitation after being stirred for 12 h. The enhanced stability of the precursor solution by the addition of chitosan is attributed to the complexation between metal ions and the –NH₂ groups of chitosan. And the electrochemical behavior for the deposited films calcined at 700 °C for 1 h was also characterized by charge–discharge test. The result revealed that the film deposited from chitosan-containing precursor solution possesses an initial discharge capacity of 134 mAh g⁻¹ and about 9% capacity loss after 50 charge/discharge cycles, which is better than the one deposited from chitosan-free precursor solution with an initial discharge capacity of 108 mAh g⁻¹ and 24% capacity loss after 50 cycles.     

Preparation of LiMn2O4 at the low temperature of 250 °C using eutectic self-mixing method

Spinel LiMn₂O₄ as a cathode material for lithium rechargeable batteries is prepared at the low temperature of 250 °C without any artificial mixing procedures of reactants. The phase transitions of lithium manganese oxide are found three times on heating at 250 °C. The prepared material exhibits the initial discharge capacity of 85.5 mAh g⁻¹ and the discharge capacity retention of 91.5% after 50 cycles.     

Properties of containing Sn nanoparticles activated carbon fiber for a negative electrode in lithium batteries

Activated carbon fiber (ACF) containing Sn nanoparticles were prepared by impregnation and were investigated as a negative electrode material in lithium batteries. The tin particle size was controlled by selecting an ACF with an adequate surface structure. This Sn/ACF composite cycled versus Li metal showed a first discharge capacity as high as 200 mAh g⁻¹ compared to the pristine ACF which showed only 87 mAh g⁻¹. Excellent cyclability with these composites was obtained with ACF BET SSA as large as 2000 m² g⁻¹ and 30 wt.% Sn.     

Synthesis and characterization of high tap-density layered Li[Ni1/3Co1/3Mn1/3]O2 cathode material via hydroxide co-precipitation

Li[Ni_1/3Co_1/3Mn_1/3]O₂ was prepared by mixing uniform co-precipitated spherical metal hydroxide (Ni_1/3Co_1/3Mn_1/3)(OH)₂ with 7% excess LiOH followed by heat-treatment. The tap-density of the powder obtained was 2.38 g cm⁻³, and it was characterized using X-ray diffraction (XRD), particle size distribution measurement, scanning electron microscope-energy dispersive spectrometry (SEM-EDS) and galvanostatic charge–discharge tests. The XRD studies showed that the material had a well-ordered layered structure with small amount of cation mixing. It can be seen from the EDS results that the transition metals (Ni, Co and Mn) in Li[Ni_1/3Co_1/3Mn_1/3]O₂ are uniformly distributed. Initial charge and discharge capacity of 185.08 and 166.99 mAh g⁻¹ was obtained between 3 and 4.3 V at a current density of 16 mA g⁻¹, and the capacity of 154.14 mAh g⁻¹ was retained at the end of 30 charge–discharge cycles with the capacity retention of 93%.     

A novel sol–gel method to synthesize nanocrystalline LiVPO4F and its electrochemical Li intercalation performances

Lithium vanadium fluorophosphate, LiVPO₄F, a cathode material for lithium ion batteries, was synthesized by a sol–gel method followed by low temperature calcinations. V₂O₅·nH₂O hydro-gel, NH₄H₂PO₄, LiF and carbon were used as starting materials to prepare a precursor, and LiVPO₄F was finally obtained by sintering the precursor at 550 °C for 2 h. X-ray diffraction results show that the LiVPO₄F sample is triclinic structure. TEM image indicates that the LiVPO₄F particles are about 70 nm in diameter embedded in carbon network. The LiVPO₄F system showed the discharge capacity of about 130 mAh g⁻¹ in the range of 3.0–4.6 V at the first cycle, and the discharge capacity remained about 124 mAh g⁻¹ after 30 cycles. The sol–gel method is suitable for the preparation of LiVPO₄F cathode materials with good electrochemical Li intercalation performances.     

Co-doped Mn3O4: a possible anode material for lithium batteries

Undoped Mn₃O₄ shows relatively poor performance as a possible anode material on reversible reaction with lithium. A dramatic increase in cyclability is obtained on partial substitution of Mn by Co. Data are presented for the composition Mn_2.6Co_0.4O₄, which, after the first cycle, shows essentially constant capacity of 400 mAh g⁻¹ at ∼0.6 V.     

Exfoliation-induced nanoribbon formation of poly(3,4-ethylene dioxythiophene) PEDOT between MoS2 layers as cathode material for lithium batteries

A new type of layered nanocomposite synthesized by delaminated MoS₂ nanosheets and poly(3,4-ethylenedioxythiophene) (PEDOT) are restacked to produce alternate polymer nanoribbons between layers of MoS₂ with an interlayer distance of ∼1.38 nm. The unique properties of resulting nanocomposite are investigated by powder XRD, XPS, SEM, TEM, and four-probe conductivity measurements. The obtained nanocomposite can be used as a cathode material for a small power rechargeable lithium battery as demonstrated by the electrochemical insertion of lithium into the PEDOT/MoS₂ nanocomposite. A significant enhancement in the discharge capacity (100 mAh g⁻¹) is observed compared with that (40 mAh g⁻¹) for MoS₂.