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 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.     

LiFePO4/carbon cathode materials prepared by ultrasonic spray pyrolysis

Small crystallites LiFePO₄ powder with conducting carbon coating can be synthesized by ultrasonic spray pyrolysis. Cheaper trivalent iron ion is used as the precursor. The pure olivine phase can be prepared with the duplex process of spray pyrolysis (synthesized at 450, 550 or 650 °C) and subsequent heat-treatment (at 650 °C for 4 h). The results indicate that the pyrolysis temperature of 450 °C is appropriate for best results. The carbon coating on the LiFePO₄ surface is critical to the electrochemical performance of LiFePO₄ cathode materials of the lithium secondary battery, since the carbon coating does not only increase the electronic conductivity via carbon on the surface of particles, but also enhance the ion mobility of lithium ion due to prohibiting the grain growth during post-heat-treatment. The carbon of 15 wt.% evenly distributed on the final LiFePO₄ powders can get the highest initial discharge capacity of 150 mA h g⁻¹ at C/10 and 50 °C.     

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.     

Electrochemical cycling behavior of LiCoO2 cathode prepared by mechanical alloying of hydroxides

Well-ordered high-temperature LiCoO₂ (HT-LiCoO₂) is synthesized by mechanical alloying (MA) of LiOH·H₂O and Co(OH)₂ powders and subsequent firing. Its electrochemical properties are investigated. The maximum discharge capacity of a sample mechanically alloyed and fired at 600 °C for 2 h is 152 mAh g⁻¹ at the C/40 rate, which is comparable to that obtained from a sample made by conventional solid state reactions. The cycleability is inferior, however, due to a relatively low crystallinity. When the firing temperature is increased to 850 °C, the first discharge capacity of 142 mAh g⁻¹ at the C/5 rate is increased by more than 10%, and retains 93% of its maximum value after 30 cycles. These cycling properties are about the same, or slightly higher, than those synthesized by firing a sample mixture of the same starting materials at 600 °C for 8 h and then at 850 °C for 24 h. Consequently, given the lower firing temperature and/or reduced reaction time, MA could prove a promising synthetic process for cathode materials used in rechargeable lithium batteries.     

Nanostructured electrodes for next generation rechargeable electrochemical devices

Nanostructured intercalating electrodes offer immense potential for significantly enhancing the performance of rechargeable rocking chair (e.g. Li⁺ and Mg²⁺) and asymmetric hybrid batteries. The objective of this work has been to develop a variety of cathode (e.g. V₂O₅, LiMnO₂ and LiFePO₄) and anode (e.g. Li₄Ti₅O₁₂) materials with unique particle characteristics and controlled composition to reap the maximum benefits of nanophase electrodes for rechargeable Li-based batteries. Different processing routes, which were chosen on the basis of the final composition and the desired particle characteristics of electrode materials, were developed to synthesize a variety of electrode materials. Vapor phase processes were used to synthesize nanopowders of V₂O₅ and TiO₂. TiO₂ was the precursor used for producing ultrafine particles of Li₄Ti₅O₁₂. Liquid phase processes were used to synthesize nanostructured LiMn_xM_1−xO₂ and LiFePO₄ powders. It was found that (i) nanostructured V₂O₅ powders with a metastable structure have 30% higher retention capacity than their coarse-grained counterparts, for the same number of cycles; (ii) the specific capacity of nanostructured LiFePO₄ cathodes can be significantly improved by intimately mixing nanoparticles with carbon particles and that cathodes made of LiFePO₄/C composite powder exhibited a specific capacity of ∼145 mAh/g (85% of the theoretical capacity); (iii) nanostructured, layered LiMn_xM_1−xO₂ cathodes demonstrated a discharge capacity of ∼245 mAh/g (86% of the theoretical capacity) at a slow discharge rate; however, the composition and structure of nanoparticles need to be optimized to improve their rate capabilities and (iv) unlike micron-sized (1–10 μm) powders, ultrafine Li₄Ti₅O₁₂ showed exceptional retention capacity at a discharge rate as high as 10 C in Li-test cells.     

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.     

Graphite–FeSi alloy composites as anode materials for rechargeable lithium batteries

Iron–silicon are prepared by annealing elemental mixtures at 1000 °C followed by mechanical milling. Graphite–Fe₂₀Si₈₀ alloy composites have been prepared by ball-milling a mixture of Fe₂₀Si₈₀ alloy and graphite powder. The microstructure and electrochemical performance of the composites are characterized by X-ray diffraction and an electrochemical method. The FeSi₂ matrix is stable for extended cycles and acts as a buffer for the active centre, Si. The Fe₂₀Si₈₀ alloy electrode delivers large initial capacity, but the capacity degrades rapidly with cycling. Fe₂₀Si₈₀ alloy–graphite composite electrodes, however, show good cycleability and a high reversible capacity of about 600 mAh g⁻¹. These composites appear to be promising candidates for negative electrodes in lithium rechargeable batteries.     

SnO2-carbon composites for lithium-ion battery anodes

A SnO₂-carbon composite prepared by heat treating a mixture of colloidal SnO₂ and sucrose demonstrated a reversible lithium storage capacity of 680 mA h/g on the 1st cycle. The discharge curve of the composite did not exhibit the 1.0 V plateau characteristic of SnO₂. The high reversible capacity of the composite suggests that lithium is stored in both tin and carbon. The composite demonstrated reduced capacity fade over SnO₂ as well as SnO:graphite and Sn:graphite composites.     

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.     

Cracking causing cyclic instability of LiFePO4 cathode material

The capacity of pure LiFePO₄ faded gradually from initial 149 mAh g⁻¹–117 mAh g⁻¹ under current density of 30 mA g⁻¹ at room temperature after 60 cycles. Some obvious cracks are observed in LiFePO₄ particles after cycling. The formation of cracks would lead to poor electric contact and capacity fading. A possible mechanism is proposed for the appearance of the cracks.     

Amphoteric effects of Fe2P on electrochemical performance of lithium iron phosphate–carbon composite synthesized by ball-milling and microwave heating

Lithium iron phosphate–carbon (LiFePO₄–C) composites with various amounts of Fe₂P are synthesized by ball-milling coupled with microwave heating to serve as cathodes for lithium-ion batteries. LiFePO₄–C in which Fe₂P is restrained below a critical concentration gives as very high discharge capacity of 165 mAh g⁻¹, excellent rate capability (85.4% C/50-rate discharge capacity at 2C) and stable cyclic retention for 250 cycles. Above the critical concentration however, electrochemical performance deterioated. Analysis and debate, based on a comparison of the physical and electrochemical properties among LiFePO₄–C composites with the variation of Fe₂P, proceeded to the conclusion that below the critical concentration, Fe₂P enhanced the conductivity of LiFePO₄–C, whereas above the critical concentration, it blocked the one-dimensional Li⁺ pathways in LiFePO₄ and might hinder Li⁺ movement in LiFePO₄. Therefore, in order to obtain a LiFePO₄–C composite that enhances electrochemical performance, it is concluded that the amount of Fe₂P should be carefully controlled below its critical concentration.     

High power BaFe(VI)O4/MnO2 composite cathode alkaline super-iron batteries

This short communication demonstrates that not only pure Fe(VI) cathodes, but also MnO₂/Fe(VI) composite cathodes can substantially enhance the high power discharge of alkaline batteries. The 2.8 Ω and 0.7 W high power discharge of alkaline cells are investigated for 3:1 and 1:1 composite MnO₂/BaFeO₄ cathode cells, provide discharge energies intermediate to that found in the (non-composite) BaFeO₄ cathode cell. At a constant 2.8 Ω load, the 1:1 composite MnO₂/BaFeO₄ cell delivers up to 40% higher energy capacity than the MnO₂ pure cathode alkaline cell, and up to three-fold the capacity of the constant 0.7 W power MnO₂ discharge.     

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.     

Ionic liquid and plastic crystalline phases of pyrazolium imide salts as electrolytes for rechargeable lithium-ion batteries

A new member of the plastic crystal, pyrazolium imide family, N,N′-diethyl-3-methylpyrazolium bis-(trifluoromethanesulfonyl)imide (DEMPyr123) was prepared. It showed a single, plastic crystalline phase that extends from 4.2 °C to its melting at 11.3 °C. When 10 mol% LiTFSI salt was added, the mixture showed ionic conductivities reaching 1.7 × 10⁻³ S cm⁻¹ at 20 °C, in the liquid state and 6.9 × 10⁻⁴ S cm⁻¹ at 5 °C, in the solid, plastic phase. A wide electrochemical stability window's of 5.5 V was observed by cyclic voltammetry of the molten salt mixture. Batteries were assembled with LiFePO₄/Li₄Ti₅O₁₂ electrodes and the salt mixture as an electrolyte. They showed a charge/discharge efficiency of 93% and 87% in the liquid and the plastic phase, respectively. The capacity retention was very good in both states with 90% of the initial capacity still available after 40 cycles. In general, the batteries showed good rate capability and cycle life performance in the ionic liquid phase that were sustained when the electrolyte transformed to the plastic phase. Comparison of the battery results with those of a classic (non-plastic crystal) ionic liquid has proven the advantage of the dual state of matter character in this electrolyte.     

In situ polyol-assisted synthesis of nano-SnO2/carbon composite materials as anodes for lithium-ion batteries

Nano-SnO₂/carbon composite materials were synthesized in situ using the polyol method by oxidizing SnCl₂·2H₂O in the presence of a carbon matrix. All the as-synthesized composites consisted of SnO₂ nanoparticles (5–10 nm) uniformly embedded into the carbon matrix as evidenced by TEM. XRD confirmed the presence of nano-sized SnO₂ particles that are crystallized in a rutile structure and XPS revealed a tin oxidation state of +4. Cyclic voltammetry of the composites showed an irreversible peak at 1.4 V in the first cycle and a typical alloying/de-alloying process at 0.1–0.5 V. The best composite (“composite I”, 15 wt% SnO₂) showed an improved lithium storage capacity of 370 mAh g^?1 at 200 mA g^?1 (～C/2) which correspond to 32% improvement and lower capacity fade compared to commercial SnO₂ (50 nm). We have also investigated the effect of the heating method and we found that the use of a microwave was beneficial in not only shortening reaction time but also in producing smaller SnO₂ particles that are also better dispersed within the carbon matrix which also resulted in higher lithium storage capacity.     

Thermal conductivity of ethylene glycol and water mixture based Fe3O4 nanofluid

Thermal conductivity of ethylene glycol and water mixture based Fe₃O₄ nanofluid has been investigated experimentally. Magnetic Fe₃O₄ nanoparticles were synthesized by chemical co-precipitation method and the nanofluids were prepared by dispersing nanoparticles into different base fluids like 20:80%, 40:60% and 60:40% by weight of the ethylene glycol and water mixture. Experiments were conducted in the temperature range from 20 °C to 60 °C and in the volume concentration range from 0.2% to 2.0%. Results indicate that the thermal conductivity increases with the increase of particle concentration and temperature. The thermal conductivity is enhanced by 46% at 2.0 vol.% of nanoparticles dispersed in 20:80% ethylene glycol and water mixture compared to other base fluids. The theoretical Hamilton–Crosser model failed to predict the thermal conductivity of the nanofluid with the effect of temperature. A new correlation is developed for the estimation of thermal conductivity of nanofluids based on the experimental data.     

Uneven temperature and voltage distributions due to rapid discharge rates and different boundary conditions for series-connected LiFePO4 batteries

This paper presents the surface temperature and voltage distributions on a prismatic lithium-ion battery pack at 1C, 2C, 3C, and 4C discharge rates and 5 °C, 15 °C, 25 °C, and 35 °C boundary conditions (BCs) for water cooling and ~ 22 °C for air cooling methods. It provides quantitative data regarding thermal behaviour of lithium-ion batteries for designing thermal management systems and developing reliable thermal models. In this regard, three large LiFePO₄ 20 Ah capacity, prismatic batteries are connected in series with four cold plates used between cells and eighteen thermocouples are placed at distributed locations on the principle surface of all three cells: the first six for the first cell, the second six for the second cell, and the third six for the third cell, and the average and peak surface temperatures as well as voltage distributions are measured and presented in this study. In addition, the simulated heat generation rate, temperature and voltage distributions are validated with an experimental data for the above mentioned C-rates and BCs. The present study shows that increasing discharge rates and BCs results in increase in the maximum and average surface temperatures at the three locations (near the anode, cathode, and mid surface of the body). The highest value of the average surface temperature is obtained for 4C and 35 °C BC (36.36 °C) and the lowest value is obtained for 1C and 5 °C BC (7.22 °C) for water cooling method.     

Electrochemical properties of LiFe0.9Mn0.1PO4/Fe2P cathode material by mechanical alloying

LiFePO₄, olivine-type LiFe_0.9Mn_0.1PO₄/Fe₂P composite was synthesized by mechanical alloying of carbon (acetylene back), M₂O₃ (M = Fe, Mn) and LiOH·H₂O for 2 h followed by a short-time firing at 900 °C for only 30 min. By varying the carbon excess different amounts of Fe₂P second phase was achieved. The short firing time prevented grain growth, improving the high-rate charge/discharge capacity. The electrochemical performance was tested at various C/x-rate. The discharge capacity at 1C rate was increased up to 120 mAh g⁻¹ for the LiFe_0.9Mn_0.1PO₄/Fe₂P composite, while that of the unsubstituted LiFePO₄/Fe₂P and LiFePO₄ showed only 110 and 60 mAh g⁻¹, respectively. Electronic conductivity and ionic diffusion constant were measured. The LiFe_0.9Mn_0.1PO₄/Fe₂P composite showed higher conductivity and the highest diffusion coefficient (3.90 × 10⁻¹⁴ cm² s⁻¹). Thus the improvement of the electrochemical performance can be attributed to (1) higher electronic conductivity by the formation of conductive Fe₂P together with (2) an increase of Li⁺ ion mobility obtained by the substitution of Mn²⁺ for Fe²⁺.     

Synthesis of lithium insertion material Li4Ti5O12 from rutile TiO2 via surface activation

The synthesis of spinel-type lithium titanate, Li₄Ti₅O₁₂, a promising anode material of secondary lithium-ion battery, from “inert” rutile TiO₂, is investigated. On the purpose of increasing the reactivity of rutile TiO₂, it is treated by concentrated HNO₃. By applying such activated rutile TiO₂ as the titanium source in combination with the cellulose-assisted combustion synthesis, phase-pure Li₄Ti₅O₁₂ is successfully synthesized at 800 °C, at least 150 °C lower than that based on solid-state reaction. The resulted oxide shows a reversible discharge capacity of ～175 mAh g^?1 at 1 C rate, near the theoretical value. The resulted oxide also shows promising high rate performance with a discharge capacity of ～100 mAh g^?1 at 10 C rate and high cycling stability.