Low-temperature behavior of graphite-tin composite anodes for Li-ion batteries

The challenge of increasing low-temperature performances of anodes for Li-ion batteries is faced by preparing graphite-tin composite electrodes. The anodes are prepared by mixing partially oxidized graphite with nanometric Sn powder or by coating the oxidized graphite electrode with a thin Sn layer. Long-term cycling stability and intercalation/deintercalation performances of the composite anodes in the temperature range 20 °C to −30 °C are evaluated. Kinetics is investigated by cyclic voltammetry and electrochemical impedance spectroscopy, in the attempt to explain the role of Sn in reducing the overall electrode polarization at low temperature. Two possible mechanisms of action for bulk metal powder and surface metal layer are proposed.     

Structures and electrochemical performances of pyrolized carbons from graphite oxides for electric double-layer capacitor

The structural features and the electrochemical performances of pyrolized needle cokes from oxidized cokes are examined and compared with those of KOH-activated needle coke. The structure of needle coke is changed to a single phase of graphite oxide after oxidation treatment with an acidic solution having an NaClO₃/needle coke composition ratio of above 7.5, and the inter-layer distance of the oxidized needle coke is expanded to 6.9 Å with increasing oxygen content. After heating at 200 °C, the oxidized needle coke is reduced to a graphite structure with an inter-layer distance of 3.6 Å. By contrast, a change in the inter-layer distance in KOH-activated needle coke is not observed.     

Influence of the nature of conductive support on the electrocatalytic activity of electrodeposited Ni films towards methanol oxidation in 1 M KOH

The study of electrochemical behaviour of dispersed Ni on graphite, glassy carbon, and Ti electrodes, obtained by an electro-deposition method, is carried out in 1 M KOH + 1 M CH₃OH at 25 °C. Results show that the nature of substrate influences the apparent electrocatalytic activities of the Ni over layer greatly. It is observed that at E = 0.50 V vs. Hg/HgO (25 °C), the dispersed Ni on graphite is approx. 300 times more active than that dispersed on Ti and is approx. 260 times more active than that dispersed on glassy carbon. Further, these electrodes show quite good resistance against electrode poisoning by the methanol oxidation intermediates/products.     

Lithium oxalyldifluoroborate/carbonate electrolytes for LiFePO4/artificial graphite lithium-ion cells

The electrolytes based on lithium oxalyldifluoroborate (LiODFB) and carbonates have been systematically investigated for LiFePO₄/artificial graphite (AG) cells, by ionic conductivity test and various electrochemical tests, such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. The conductivity of nine electrolytes as a function of solvent composition and LiODFB salt concentration has been studied. The coulombic efficiency of LiFePO₄/Li and AG/Li half cells with these electrolytes have also been compared. The results show that 1 M LiODFB EC/PC/DMC (1:1:3, v/v) electrolyte has a relatively higher conductivity (8.25 mS cm⁻¹) at 25 °C, with high coulombic efficiency, good kinetics characteristics and low interface resistance. With 1 M LiODFB EC/PC/DMC (1:1:3, v/v) electrolyte, LiFePO₄/AG cells exhibit excellent capacity retention ∼92% and ∼88% after 100 cycles at 25 °C and at elevated temperatures up to 65 °C, respectively; The LiFePO₄/AG cells also have good rate capability, the discharge capacity is 324.8 mAh at 4 C, which is about 89% of the discharge capacity at 0.5 C. However, at −10 °C, the capacity is relatively lower. Compared with 1 M LiPF₆ EC/PC/DMC (1:1:3, v/v), LiFePO₄/AG cells with 1 M LiODFB EC/PC/DMC (1:1:3, v/v) exhibited better capacity utilization at both room temperature and 65 °C. The capacity retention of the cells with LiODFB-based electrolyte was much higher than that of LiPF₆-based electrolyte at 65 °C, while the capacity retention and the rate capacity of the cells is closed to that of LiPF₆-based electrolyte at 25 °C. In summary, 1 M LiODFB EC/PC/DMC (1:1:3, v/v) is a promising electrolyte for LiFePO₄/AG cells.     

Lithium bis(fluorosulfonyl)imide-PYR14TFSI ionic liquid electrolyte compatible with graphite

Lithium bis(fluorosulfonyl)imide (LiFSI) in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₄TFSI) was successfully tested as an electrolyte for graphite composite anodes at elevated temperature of 55 °C. The graphite anode showed a good cyclability during the galvanostatic testing at C/10 rate and 55 °C with the capacity close to theoretical. The formation of SEI in different electrolytes was the subject of study using impedance spectroscopy on symmetrical cells containing two lithium electrodes. The 0.7 m LiFSI in PYR₁₄TFSI exhibits a good ionic conductivity (5.9 mS cm⁻¹ at 55 °C) along with high electrochemical stability and high thermal stability. These properties allow their potential application in large-scale lithium ion batteries with improved safety.     

Spherical silicon/graphite/carbon composites as anode material for lithium-ion batteries

A spherical nanostructured Si/graphite/carbon composite is synthesized by pelletizing a mixture of nano-Si/graphite/petroleum pitch powders, followed by heat treatment at 1000 °C under an argon atmosphere. The structure of the composite sphere is examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDAX). The resultant composite sphere consists of nanosized silicon and flaked graphite embedded in a carbon matrix pyrolyzed from petroleum pitch, in which the flaked graphite sheets are concentrically distributed in a parallel orientation. The composite material exhibits good electrochemical properties, a high reversible specific capacity of ∼700 mAh g⁻¹, a high coulombic efficiency of 86% on the first cycle, and a stable capacity retention. The enhanced electrochemical performance is attributed to the structural stability of the composite sphere during the charging–discharging process.     

Low temperature behaviour of TiO2 rutile as negative electrode material for lithium-ion batteries

High surface nanosized rutile TiO₂ is prepared via a sol-gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant, at pH 0. Its electrochemical behaviour has been investigated at low temperature using two different potential windows. Typically, the potential window of the rutile system is 1-3 V but the use of an enlarged potential window (0.1-3 V), leads to an excellent reversible capacity of 341 mAh g⁻¹ which is comparable to graphite anodes. The electrochemical performance was investigated by cyclic voltammetry and galvanostatic techniques at temperatures ranging from −40 to 20 °C. Nanosized TiO₂ exhibits excellent rate capability (341 mAh g⁻¹ at 20 °C, 197 mAh g⁻¹ at −10 °C, 138 mAh g⁻¹ at −20 °C, and 77 mAh g⁻¹ at −40 °C at a C/5 rate) and good cycling stability. The superior low-temperature electrochemical performance of nanosized rutile TiO₂ may make it a promising candidate as lithium-ion battery material.     

Performance and life-time behaviour of NiCu–CGO anodes for the direct electro-oxidation of methane in IT-SOFCs

An anodic cermet of NiCu alloy and gadolinia doped ceria has been investigated for CH₄ electro-oxidation in IT-SOFCs. Polarization curves have been recorded in the temperature range from 650 to 800 °C. A maximum power density of 320 mW cm⁻² at 800 °C has been obtained in the presence of dry methane in an electrolyte-supported cell. The electrochemical behaviour during 1300 h operation in dry methane and in the presence of redox-cycles has been investigated at 750 °C; variation of the electrochemical properties during these experiments have been interpreted in terms of anode morphology modifications. The methane cracking process at the anode catalyst has been investigated by analysing the oxidative stripping of deposited carbon species.     

Microstructure and electrochemical performance of Si-SiO2-C composites as the negative material for Li-ion batteries

Si-SiO₂-C composites are synthesized by ball milling the mixture of SiO, graphite and coal pitch, and subsequent heat treatment at 900 °C in inert atmosphere. The electrochemical performance and microstructure of the composites are investigated. XRD and TEM tests indicate that the carbon-coating structure of Si-SiO₂-C composites form in pyrolysis process, which can remarkably improve the electrochemical cycling performance. The coal pitch as carbon precursor and graphite demonstrate the same important effect on the Li-alloying/de-alloying property of the Si-SiO₂-C composites. The Si-SiO₂-C composites exhibit the electrochemical reversible Li-alloying/de-alloying capacity of 700 mAh g⁻¹ and excellent cyclic stability even at about the 90th cycle.     

Thermal and electrochemical durability of carbonaceous composites used as a bipolar plate of proton exchange membrane fuel cell

Thermal and electrochemical durability of carbonaceous composite plates, which are made from graphite powders and a resin for use as bipolar plates of PEMFC (proton exchange membrane fuel cell), were investigated. The thermal durability was investigated by TG (thermal gravimetry) coupled with DTA (differential thermal analysis) technique under air up to 600 °C. A weight loss was significant over 300 °C, but the hydrophobicity was decreased after heated at 80 °C for 192 h.The electrochemical durability was investigated in 10 μmol dm⁻³ of hydrochloric acid solution under nitrogen or oxygen atmosphere by means of potential holding test from 0.8 to 1.5 V against RHE (reversible hydrogen electrode) at 80 °C. During the potential holding tests, CO₂ production due to the corrosion was quantified by a GC (gas-chromatography) and the production was detectable above 1.3 V irrespective with atmosphere; on the other hand, it was clarified from the contact angle measurements that the hydrophobicity was changed below 1.3 V. The results of this study showed that the carbonaceous composite plates were electrochemically degraded under PEMFC condition and were seriously degraded in URFC (unitized regenerative fuel cell) condition.     

Suppression of Li deposition on surface of graphite using carbon coating by thermal vapor deposition process

10 wt.% carbon-coated natural graphite (NC-10) is prepared by thermal vapor deposition. The carbon coating is electrochemically investigated at −5 °C; it improves lithium intercalation in the graphite's interlayer spacing. NC-10 graphite clearly shows 3 voltage plateaus and a higher capacity during the first charge/discharge cycle at −5 °C than uncoated natural graphite. XRD study of the electrode after the first charging shows increased lithium intercalation into the graphite layers and also suppression of lithium deposition on the graphite's surface. Due to the homogeneous potential profile on the graphite surface, carbon coating enhance lithium intercalation at −5 °C. In addition, NC-10 shows less lithium deposition on the surface than bare natural graphite.     

Electrochemical investigation of polarization phenomena and intercalation kinetics of oxidized graphite electrodes coated with evaporated metal layers

The electrochemical behavior of partially oxidized graphite electrodes coated with 50 Å thick Au, Cu, In, Pb or Sn layers has been studied by slow scan rate cyclic voltammetry and galvanostatic charge–discharge. Electrochemical impedance spectroscopy (EIS) has also been applied to Cu- and Sn-coated electrodes in order to study the effect of the metal coating on the interfacial intercalation/deintercalation kinetics.

The results demonstrate that certain metallic layers produce remarkable improvements of intercalation kinetics of graphite electrodes by reducing the charge-transfer and the solid–electrolyte interface (SEI) resistance making this type of surface modification attractive for the development of high rate anodes for lithium-ion batteries.     

Polymer-derived-SiCN ceramic/graphite composite as anode material with enhanced rate capability for lithium ion batteries

We report on a new composite material in view of its application as a negative electrode in lithium-ion batteries. A commercial preceramic polysilazane mixed with graphite in 1:1 weight ratio was transformed into a SiCN/graphite composite material through a pyrolytic polymer-to-ceramic conversion at three different temperatures, namely 950 °C, 1100 °C and 1300 °C. By means of Raman spectroscopy we found successive ordering of carbon clusters into nano-crystalline graphitic regions with increasing pyrolysis temperature. The reversible capacity of about 350 mAh g⁻¹ was measured with constant current charging/discharging for the composite prepared at 1300 °C. For comparison pure graphite and pure polysilazane-derived SiCN ceramic were examined as reference materials. During fast charging and discharging the composite material demonstrates enhanced capacity and stability. Charging and discharging in half an hour lead to about 200 and 10 mAh g⁻¹, for the composite annealed at 1300 °C and pure graphite, respectively. A clear dependence between the final material capacity and pyrolysis temperature is found and discussed with respect to possible application in batteries, i.e. practical discharging potential limit. The best results in terms of capacity recovered under 1 V and high rate capability were also obtained for samples synthesized at 1300 °C.     

Low-temperature preparation by polymeric complex solution synthesis of Cu-Gd-doped ceria cermets for solid oxide fuel cells anodes: Sinterability, microstructures and electrical properties

A homogeneous dispersion of fine CuO in a gadolinia-doped ceria (CGO) ceramic matrix by the polymeric organic complex solution method has been achieved. Highly sinterable powders were prepared by this method after calcining the precursor at 600 °C and attrition milled. The powders consist of individual particles of few tens of nanometer in size with a low agglomeration state. The isopressed compacts were sintered in air at 1000 °C and reducing in N₂ 90%-H₂ 10% atmosphere to form Cu-CGO cermets. The microstructures showed a uniform distribution of porous metallic Cu particles surrounded by microporous spaces. The influence of Cu content in Cu-CGO cermets on the electrode performance has been investigated in order to create the most suitable microstructure. The electrical properties of Cu-CGO cermets have been also studied using impedance spectroscopy, in the temperature range form 150 to about 700 °C in argon atmosphere. These measurements determined a high value of electrical conductivity at 700 °C, similar to that corresponded to pure metallic cupper.     

Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium-ion batteries: Physicochemical and electrochemical properties

Lithium bis(fluorosulfonyl)imide (LiFSI) has been studied as conducting salt for lithium-ion batteries, in terms of the physicochemical and electrochemical properties of the neat LiFSI salt and its nonaqueous liquid electrolytes. Our pure LiFSI salt shows a melting point at 145 °C, and is thermally stable up to 200 °C. It exhibits far superior stability towards hydrolysis than LiPF₆. Among the various lithium salts studied at the concentration of 1.0 M (= mol dm⁻³) in a mixture of ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3:7, v/v), LiFSI shows the highest conductivity in the order of LiFSI > LiPF₆ > Li[N(SO₂CF₃)₂] (LiTFSI) > LiClO₄ > LiBF₄. The stability of Al in the high potential region (3.0-5.0 V vs. Li⁺/Li) has been confirmed for high purity LiFSI-based electrolytes using cyclic voltammetry, SEM morphology, and chronoamperometry, whereas Al corrosion indeed occurs in the LiFSI-based electrolytes tainted with trace amounts of LiCl (50 ppm). With high purity, LiFSI outperforms LiPF₆ in both Li/LiCoO₂ and graphite/LiCoO₂ cells.     

Understanding the sucrose-assisted combustion method: Effects of the atmosphere and fuel amount on the synthesis and electrochemical performances of LiNi0.5Mn1.5O4 spinel

The present paper comprises results of our studies about the influence of the atmosphere and fuel amount on the synthesis and electrochemical performance of LiNi_0.5Mn_1.5O₄ spinel (LNMS). Reaction of mixtures of metal nitrates with and without sucrose (fuel) in Ar and in air flow has been studied by thermal analysis and coupled mass spectrometry (TG/DTA/MS). Products obtained after the thermal study have been identified and characterized by powder X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Gases evolved along the thermal treatment have been identified by coupled mass spectrometry (MS). From all these results the synthesis reactions have been put forward. When the reaction is conducted in air sub-micrometric LiNi_0.5Mn_1.5O₄ spinel is obtained independently of the amount of sucrose. When the reaction is done in Ar the spinel is only obtained in absence of fuel. The electrochemical performances at 25 °C and 55 °C of the synthesized LNMSs have been evaluated by galvanostatic cycling. The samples prepared in air furnish high capacity (≈120 mAh g⁻¹) and they work at high voltage (≈4.7 V). Besides, they exhibit remarkable cycling properties, even at elevated temperature (55 °C), with capacity retentions higher than 90% after 50 cycles.     

Development of preform moulding technique using expanded graphite for proton exchange membrane fuel cell bipolar plates

A preform moulding technique using expanded graphite is developed to manufacture composite bipolar plates for proton exchange membrane fuel cells (PEMFCs). The preform is composed of expanded graphite, graphite flake and phenol resin. Preforms utilizing the tangled structure of expanded graphite are easily fabricated at a low pressure of 0.07–0.28 MPa. A pre-curing temperature (100 °C) slightly above the melting point of phenol powders (90 °C) induces moderate curing, but also prevents excessive curing. After the preform is placed in a steel mould, compression moulding is carried out at high pressure (10 MPa) and temperature (150 °C). The fabrication conditions are optimized by checking the electrical conductivity, flexural strength and microstructure of the composite. The optimized electrical conductivity and flexural strength, 250 S cm⁻¹ and 50 MPa, respectively, met the requirements for PEMFC bipolar plates.     

A mixture of triethylphosphate and ethylene carbonate as a safe additive for ionic liquid-based electrolytes of lithium ion batteries

A binary mixture of triethylphosphate (TEP) and ethylene carbonate (EC) has been examined as a new non-flammable additive for ionic liquid-based electrolytes for lithium-ion batteries. The optimized electrolyte composition consists of 0.6 mol dm⁻³ (=M) LiTFSI in PP13TFSI mixed with TEP and EC in volume ratio of 80:10:10, where TFSI and PP13 denote bis(trifluoromethanesulfonyl)imide and N-methyl-N-propylpiperidinium, respectively. The ionic conductivity of PP13TFSI dissolving 0.4 M LiTFSI was improved from 8.2 × 10⁻⁴ S cm⁻¹ to 3.5 × 10⁻³ S cm⁻¹ (at 20 °C) with the addition of TEP and EC. The electrochemical behavior of 0.4 M LiTFSI/PP13TFSI with and without TEP and EC was studied by cyclic voltammetry, which showed no deteriorating effect by the addition of TEP and EC on the electrochemical window of PP13TFSI. The flammability of the electrolyte was tested by a direct flame test. The proposed ionic liquid-based electrolyte revealed significant improvements in the electrochemical charge-discharge characteristics for both graphite negative and LiMn₂O₄ positive electrodes.     

Effect of nickel hydroxide composition on the electrochemical performance of spherical Ni(OH)2 positive materials for Ni–MH batteries

A special method “conduit synthesis technology” has been utilized to produce spherical nickel hydroxide powders with different chemical compositions. Three kinds of powers A, B, C were prepared by chemically coprecipitating Ni, Co, Zn, Ca, Mg and Cu. It was found that powder B produced better performance than the others. The discharge capacities of powder B could achieve 280 mAh g⁻¹ for both 1C and 2C rates at 65 °C, respectively. The cyclic voltammetry analysis showed that the difference between the oxidation potential and the oxygen evolution potential of powder B is 122 mV. It indicated that Co could improve conductivity of electrons, restrict the oxygen evolution reaction and thus promote the high rate charge/discharge and high-temperature performance. Ca and Mg might effectively enhance the oxygen evolution potential in the charge process. Furthermore, the proper addition of Zn, Ca and Cu could lower the ionization energy and elevated the transition energy, and thus the transfer of electrons in electrode materials was accelerated and the electrochemical performance of nickel hydroxide electrode was improved. It was a promising way to improve the electrochemical performance of spherical nickel hydroxide for Ni–MH batteries.     

LiCr0.2Ni0.4Mn1.4O4 spinels exhibiting huge rate capability at 25 and 55 °C: Analysis of the effect of the particle size

The comparison of the rate capability of LiCr_0.2Ni_0.4Mn_1.4O₄ spinels synthesized by the sucrose aided combustion method at 900, 950 and 1000 °C is presented. XRD and TEM studies show that the spinel cubic structure remains unchanged on heating but the particle size is notably modified. Indeed, it increases from 695 nm at 900 °C to 1465 nm at 1000 °C. The electrochemical properties have been evaluated by galvanostatic cycling at 25 and 55 °C between 1 C and 60 C discharge rates. At both temperatures, all samples exhibit high working voltage (∼4.7 V), elevated capacity (∼140 mAh g⁻¹) and high cyclability (capacity retention ∼99% after 50 cycles even at 55 °C). The samples also have huge rate capability. They retain more than 70% of their maximum capacity at the very fast rate of 60 C. The effect of the particle size on the rate capability at 25 and at 55 °C has been investigated. It was demonstrated that LiCr_0.2Ni_0.4Mn_1.4O₄ annealed at 900 °C, with the lowest particle size, has the best electrochemical performances. In fact, among the LiNi_0.5Mn_1.5O₄-based cathodes, SAC900 exhibits the highest rate capability ever published. This spinel, able to deliver 31,000 W kg⁻¹ at 25 °C and 27,500 W kg⁻¹ at 55 °C is a really promising cathode for high-power Li-ion battery.