Morphology of carbon nanostructures and their electrochemical performance for lithium ion battery

A comparative study has been carried out on anodes made from carbon nanostructures of five different morphologies—single walled, double walled and multiwalled carbon nanotubes (with two different diameters), and carbon nanofibers. The specific area of the samples of these carbon nanostructures has been determined and their structure and morphology have been characterized by microscopy, X-ray diffraction and Raman spectroscopy. Depending on the morphology and the size of the nanostructures in the anode, the reversible capacity obtained ranges from 450 to 600 mAh g⁻¹ and the coulombic efficiency is in the range of 85–98% after 12 cycles. Increasing the surface area, both inside and outside for the tubes of a nano-size, gives rise to increased number of surface sites, which may be intercalated reversibly leading to increased specific charge capacity. Formation of the solid electrolyte interface layer covers a part of these surface sites as well as results in capacity fading, which also increases with increasing surface area. Increased defect sites responsible for elastic scattering in Raman spectra do not appear to have deciding influence on either enhanced capacity or capacity fading. Nano-sized constituent in the electrode appears to improve mechanical characteristics ensuring good mechanical integrity on cycling and high coulombic efficiency.     

Performance enforcement of gel polymer electrolyte for lithium ion battery with co-doping silicon dioxide and zirconium dioxide nanoparticles

In this work, we report a new method to enforce the comprehensive performances of gel polymer electrolyte (GPE) for lithium ion battery. Poly(methyl methacrylate-acrylonitrile-vinyl acetate) [P(MMA-AN-VAc)] is synthesized as polymer matrix. The physical and electrochemical performances of the matrix and the corresponding GPEs, doped with nano-SiO₂ and nano-ZrO₂ particles individually or simultaneously, are investigated by scanning electron microscopy, thermogravimetry, electrochemical impedance spectroscopy, and charge/discharge test. It is found that the membrane co-doped with 5 wt.% nano-SiO₂?+?5 wt.% nano-ZrO₂ and the corresponding GPE combine the advantages of those doped individually with 10 wt.% nano-SiO₂ or 10 wt.% nano-ZrO₂. Accordingly, the comprehensive performances of the membrane and the corresponding GPE, in terms of thermal stability, ionic conductivity, and electrochemical stability on the anode and cathode of lithium ion battery, is enforced by co-doping 5 wt.% nano-SiO₂ and 5 wt.% nano-ZrO₂.     

Performance studies on composite gel polymer electrolytes for rechargeable magnesium battery application

Effect of micron-sized MgO particles dispersion on poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF–HFP) based magnesium-ion (Mg²⁺) conducting gel polymer electrolyte has been studied using various electrical and electrochemical techniques. The composite gel films are free-standing and flexible with enough mechanical strength. The optimized composition with 10 wt% MgO particles offers a maximum electrical conductivity of ∼6×10⁻³ S cm⁻¹ at room temperature (∼25°C). The Mg²⁺ ion conduction in gel film is confirmed from cyclic voltammetry, impedance spectroscopy and transport number measurements. The applicability of the composite gel electrolyte to a rechargeable battery system has been examined by fabricating a prototype cell consisting of Mg (or Mg–MWCNT composite) and V₂O₅ as negative and positive electrodes, respectively. The rechargeability of the cell has been improved, when Mg metal was substituted by Mg–MWCNT composite as negative electrode.     

Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

Effect of monocationic ionic liquids as electrolyte additives on the electrochemical and thermal properties of Li-ion batteries

The conventional electrolyte system has been compared with the ionic liquid (IL) additive containing electrolyte system at room temperature as well as elevated temperature. In this work, two types of monocationic ILs such as 1-butyl-3-methylpyrrolidinium hexafluorophosphate (Pyr IL) and 1-ethyl-3-methylimidazolium hexafluorophosphate (IMI IL) are added as an additive at two different weight ratios in 1.15 M LiPF₆ (EC/EMC = 3/7 v/v) electrolyte solution, the structural, electrochemical and thermal characteristics of LiNi_0.80Co_0.15Al_0.05O₂ (NCA)/carbon full-cell in different electrolyte formulations have been reconnoitered. X-ray diffraction (XRD) studies have proved that IL as an electrolyte additive does not alter the structural stability of cathode materials after cycling. Under room temperature, Pyr IL additives at 1 wt% and 3 wt% deliver better cycleability than others, with the retention ratios of 93.62% and 92.8%, respectively. At elevated temperature, only 1 wt% Pyr IL additive is giving stable capacity retention ratio of 80.74%. Ionic conductivity and self-extinguishing time (SET) values are increasing with respect to the amount of additive added to the electrolyte. Thermal studies reveal that 3 wt% Pyr IL is favorable regarding the safety of the battery as it shows shifting of peak to higher temperature of 272.10 °C. Among the IL additives evaluated in this study, addition of 1 wt% Pyr IL is the most desirable additive for achieving the best cycling performance as well as thermal behavior of Li-ion batteries.     

A novel approach to synthesize lithium ion battery spinel cathode materials

Spinel LiMn₂O₄ and LiMg_0.2Mn_1.8O₄ have been synthesized by a soft chemistry method using citric acid as the chelating agent and acryl amide as the gelling agent. This technique offers better homogeneity, preferred surface morphology, reduced heat treatment conditions, sub-micron-sized particles, and better crystallinity. The synthesized spinel materials are characterized by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and charge–discharge studies.     

Study of the temperature dependent transport properties in nanocrystalline lithium lanthanum titanate for lithium ion batteries

The nano-crystalline Li_0.5La_0.5TiO₃ (LLTO) was prepared as an electrolyte material for lithium-ion batteries by the sol–gel method. The prepared LLTO material is characterized by structural, morphological and electrical characterizations. The LLTO shows the cubic perovskite structure with superlattice formation. The uniform distribution of LLTO particles has been analyzed by the SEM and TEM analysis of the sample. Impedance measurements at various temperatures were carried out and the temperature dependent conductivity of as prepared LLTO nanopowders at different temperatures from room temperature to 448 K has been analyzed. The transport mechanism has been analyzed using the dielectric and modulus analysis of the sample. Maximum grain conductivity of the order of 10⁻³ S cm⁻¹ has been obtained for the sample at higher temperatures.     

Numerical modeling of lithium ion battery for predicting thermal behavior in a cylindrical cell

The thermal behavior of lithium ion battery during charge and discharge is investigated by a numerical simulation. The commercially available cylindrical 18650 battery is modeled in this study. Two different models are used. The porous electrode model is simulated to obtain the Li content inside the particles. The transient thermo-electric model is used to predict the temperature distribution inside the cell. The results suggest that the increase in temperature during discharge is higher than that during charge. The temperature difference between charge and discharge is decreased with increasing C-rates. At a rate of 1C, the discharge temperature increases with a waving region at the beginning, whereas the charge temperature increases until certain point and then decreases. The thermal behavior is closely related to the change in entropy and applied current.     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

Synthesis and electrochemical properties of different sizes of the CuO particles

Well-dispersed cupric oxide (CuO) nanoparticles with the size from 10 to 100 nm were successfully synthesized by thermal decomposition of CuC₂O₄ precursor at 400 °C. The prepared CuO nanoparticles of different sizes used as anode materials for Li ion battery all exhibit high electrochemical capacity at the first discharge. However, with the particles size changing, an interesting phenomenon appears. That is, the larger size of the particles is, the discharge capacity of the first time smaller is, while that of the second time is larger. At the same time, the mechanism of the above phenomenon is discussed in this paper. Surprisingly, we have synthesized the copper nanoparticles with different sizes by the CuO of different sizes as the electrodes.     

Effects of lithium phosphorous oxynitride film coating on electrochemical performance and thermal stability of graphite anodes

In this study, we investigated the effects of lithium phosphorus oxynitride (LiPON) solid electrolyte thin-film deposition on the electrochemical performance and thermal stability of pristine graphite and carbon-coated graphite composite anodes. The LiPON film was deposited by radio frequency (rf) magnetron sputtering. We studied the thermal stability of the lithiated electrodes when immersed in the presence of a liquid electrolyte by differential scanning calorimetry (DSC).The LiPON thin-film coating suppressed the impedance growth during the cycling process and inhibited the reaction between the lithiated electrode and the electrolyte, thus improving the cycle performance and thermal stability of the graphite electrode. However, for the carbon-coated graphite electrode, the heat evolution below 250 °C decreased, whereas that below 300 °C increased. We attributed this phenomenon to the low thermal stability of the LiPON thin-film coating owing to an exothermic reaction between the LiPON film and the electrolyte that occurs at approximately 290 °C.     

Electrochemical cell performance studies on all-solid-state battery using nano-composite polymer electrolyte membrane

All-solid-state proton-conducting polymeric batteries have been fabricated in the cell configurations: Zn + ZnSO₄·7H₂O (anode) || polyethylene oxide (PEO):NH₄HSO₄ + SiO₂ || MnO₂ + C (cathode) and Zn + ZnSO₄·7H₂O (anode) || PEO:NH₄HSO₄ + SiO₂ || PbO₂ + V₂O₅ + C (cathode). Nano-composite proton-conducting polymeric membrane in wt.% composition, 92PEO: 8 NH₄HSO₄ + 3 SiO₂, synthesized by solution cast technique, has been used as electrolyte. Dispersal of nanosized (8 nm) fumed-SiO₂ particles resulted into an enhancement in the room temperature conductivity of polymer electrolyte host, 92PEO: 8 NH₄HSO₄ (wt.%), approximately by an order of magnitude with the substantial increase in the mechanical strength of the films. Details on the electrolyte film casting and ion transport characterization studies have been discussed elsewhere in the literature. However, a brief mention has been made for reference. An open circuit voltage in the range 1.5–1.8 V, obtained for both the batteries, is in very good agreement with the value reported. The cell performance has been studied under varying load conditions. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Preparation of alkaline solid polymer electrolyte based on PVA-TiO2-KOH-H2O and its performance in Zn-Ni battery

A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO₂) ceramic fillers, KOH, and H₂O was prepared by a solution casting method. The properties of PVA-TiO₂-KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO₂ filler was added. The SEM result showed that TiO₂ particles dispersed into the PVA matrix although some TiO₂ aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm⁻¹. The Zn-Ni secondary battery with the alkaline polymer electrolyte PVA-TiO₂-KOH had excellent electrochemical property at the low charge-discharge rate.     

Role of the polymer matrix in determining the chemical–physical and electrochemical properties of gel polymer electrolytes for lithium batteries

Gel polymer polymer membranes, prepared by immobilizing lithium-conducting solutions in a polymer matrix, are promising electrolyte materials for promoting the advancement of the lithium battery technology. However, so far, not much attention has been devoted to the definition of the role of the constituents in determining the properties of these electrolytes. In this work we have examined the characteristics of three common examples of polymer electrolytes based on a poly(vinylidene fluoride)-fluoropropylene, poly(vinyilidene fluoride)–hexa-fluoropropylene copolymer matrix. The three selected electrolytes differed from the nature of their polymer matrix. The results, based on X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and conductivity tests, show that, indeed, the type of the polymer matrix may influence the properties of the electrolytes, especially in terms of conductivity.     

A novel and shortcut method to prepare ionic liquid gel polymer electrolyte membranes for lithium-ion battery

The ionic liquid polymer electrolyte (IL-PE) membrane is prepared by ultraviolet (UV) cross-linking technology with polyurethane acrylate (PUA), methyl methacrylate (MMA), ionic liquid (Py₁₃TFSI), lithium salt (LiTFSI), ethylene glycol dimethacrylate (EGDMA), and benzoyl peroxide (BPO). N-methyl-N-propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py₁₃TFSI) ionic liquid is synthesized by mixing N-methyl-N-propyl pyrrolidinium bromide (Py₁₃Br) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The addition of Py₁₃TFSI to polymer electrolyte membranes leads to network structures by the chain cross-linking. The resultant electrolyte membranes display the room temperature ionic conductivity of 1.37 × 10^?3 S cm^?1 and the lithium ions transference number of 0.22. The electrochemical stability window of IL-PE is about 4.8 V (vs. Li⁺/Li), indicating sufficient electrochemical stability. The interfacial resistances between the IL-PE and the electrodes have the less change after 10 cycles than before 10 cycles. IL-PE has better compatibility with the LiFePO₄ electrode and the Li electrode after 10 cycles. The first discharge performance of Li/IL-PE/LiFePO₄ half-cell shows a capacity of 151.9 mAh g^?1 and coulombic efficiency of 87.9%. The discharge capacity is 131.9 mAh g^?1 with 95.5% coulombic efficiency after 80 cycles. Therefore, the battery using the IL-PE exhibits a good cycle and rate performance.     

A study on the blending effect of polyvinyledene fluoride in the ionic transport mechanism of plasticized polyvinyl chloride + lithium perchlorate gel polymer electrolytes

The gel polymer electrolytes composed of the blend of polyvinylchloride (PVC) and polyvinylidene fluoride (PVdF) as host polymers, the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizer, and LiClO₄ as a salt was studied. An attempt was made to investigate the effect of PVdF in the plasticized PVC + LiClO₄ system in three blend ratios. The differential scanning calorimetry study confirms the formation of polymer–salt complex and miscibility of the PVC and PVdF. The X-ray diffraction results of plasticized PVC (S1, S2, S3) and PVdF-blended films (S4, S5, S6) were compared, in that an increase in PVC concentration decreases the degree of crystallinity for S1 and S3, respectively, but drastically increases for PVC (S2). The increase in PVC content has not accounted in the conductivity studies also noted. However, the blending effect of PVdF showed decreases in crystallinity homogeneously for (S6 > S5 > S4), which were reflected in ionic conductivity measurements. The surface morphology of the films were also studied by scanning electron microscope, and it corroborates the same. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Effect of branching in base polymer on ionic conductivity in hyperbranched polymer electrolytes

Novel hyperbranched polymer, poly[bis(diethylene glycol)benzoate] capped with a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group (poly-Bz1a), was prepared, and its polymer electrolyte with LiN(CF₃SO₂)₂, poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte, was all evaluated in thermal properties, ionic conductivity, and electrochemical stability window. The poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte exhibited higher ionic conductivity compared with a polymer electrolyte based on poly[bis(diethylene glycol)benzoate] capped with an acetyl group (poly-Ac1a), and the ionic conductivity of poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte was to be 7×10⁻⁴ S cm⁻¹ at 80 °C and 1×10⁻⁶ S cm⁻¹ at 30 °C, respectively. The existence of a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group as a branching unit present at ends in the base polymer improved significantly ionic conductivity of the hyperbranched polymer electrolytes. The polymer electrolyte exhibited the electrochemical stability window of 4.2 V at 70 °C and was stable until 300 °C.     

圆柱形锂电池液冷热管理实验研究

对92根加热棒组成的等效电池组的液冷热管理进行了实验研究,波浪形扁管穿插入电池组构成冷却通道。结果表明：电池组的最高温度和最大温差均随着冷却液流量的增大而降低,但降幅逐渐减小,冷却液泵功随着流量的增大而快速增长,综合考虑10 L/h为冷却液最佳流量;电池组的最高温度随着冷却液进口温度的降低而降低,但电池组温度的均匀性随着冷却液温度的降低而恶化;四种不同冷却液相比,体积分数为50%乙二醇溶液的电池组温度最高,均匀性最差,去离子水居中,由于石蜡的相变潜热和颗粒的微对流效应,体积分数为2%和5%相变微胶囊悬浮液对电池组的冷却效果最佳,且悬浮液浓度越高,电池组温度越低,均匀性越好。