Abdelbast Guerfi

Effect of Carbon Source as Additives in LiFePO4 as Positive Electrode for Lithium-Ion Batteries

The electrochemical properties of LiFePO4 cathodes with different carbon contents were studied to determine the role of carbon as conductive additive. LiFePO4 cathodes containing from 0 to 12% of conductive additive ~carbon black or mixture of carbon black and graphite! were cycled at different C rates. The capacity of the LiFePO4 cathode increased as conductive additive content increased. Carbon increased the utilization of active material and the electrical conductivity of electrode, but decreased volumetric capacity of electrode. This composition ~LiFePO4 with 3 wt % of carbon and 3 wt % of Graphite! is suitable for HEV application.

LiFePO4/gel/natural graphite cells for the BATT program

LiFePO{sub 4}/gel/natural graphite (NG) cells have been prepared and cycled under a fixed protocol for cycle and calendar life determination. Cell compression of 10 psi was found to represent an optimal balance between cell impedance and the first cycle losses on the individual electrodes with the gel electrolyte. Cells with a Li anode showed capacities of 160 and 78 mAh/g-LiFePO{sub 4} for C/25 and 2C discharge rates, respectively. Rapid capacity and power fade were observed in the LiFePO{sub 4}/gel/NG cells during cycling and calendar life studies. Diagnostic evaluations point to the consumption of cycleable Li though a side reaction as the reason for performance fade with minimal degradation of the individual electrodes.

New Lithium metal polymer solid state battery for an ultra-high energy: Nano C-LiFePO4 versus Nano Li1.2V3O8

Novel lithium metal polymer solid state batteries with nano C-LiFePO4 and nano Li1.2V3O8 counter-electrodes (average particle size 200 nm) were studied for the first time by in situ SEM and impedance during cycling. The kinetics of Li-motion during cycling is analyzed self-consistently together with the electrochemical properties. We show that the cycling life of the nano Li1.2V3O8 is limited by the dissolution of the vanadium in the electrolyte, which explains the choice of nano C-LiFePO4 (1300 cycles at 100% DOD): with this olivine, no dissolution is observed. In combination with lithium metal, at high loading and with a stable SEI an ultrahigh energy density battery was thus newly developed in our laboratory.

A review on hexacyanoferrate-based materials for energy storage and smart windows: challenges and perspectives

Well-known since the 18th century and widely used in painting and later in photography, hexacyanoferrate, or “Prussian blue”, is currently getting its “second life” as a promising material in several of the most advanced fields of the present technological sectors. This is mostly due to the rapid development of the energy storage market, which requires advanced, reliable, but also cost-effective materials for large-scale applications in load-levelling of renewable energy power sources. Non-Li technologies are considered as one of the most fertile R&D directions in this field, and Prussian blue demonstrates extremely promising characteristics for this kind of application. The unique features of this material are due to peculiarities of its atomic structure and ionic and electronic properties. In this article we review and discuss current research efforts in this field employing different hexacyanoferrate-based compounds as potential electrochemical storage and electrochromic devices. After a brief review of its history, we analyze the peculiarities of the atomic structure of these types of systems. We further summarize and analyze the most important and interesting experimental electrochemical data in this field, linking the particular atomic structure of the studied compounds with their observed electrochemical behaviour. This provides us with a snapshot of the current experimental state in this field and allows us to make certain predictions for its future development.

Redox Behaviors of Ni and Cr with Different Counter Cations in Spinel Cathodes for Li-Ion Batteries

The electrochemical performances of the spinels Li[Ni 0.5 M 1.5 ]O 4 , Li[CrM]O 4 , and Li[MnM]O 4 with M = Mn(IV) vs Ti(IV) as cathodes for Li-ion batteries are compared. With M = Mn(IV), reversible access to the valence states Ni(IV) to Ni(II) and Cr(IV) to Cr(III) is possible at a voltage V ≈ 4.7 and 4.85 V (vs Li + /Li), respectively. The solid electrolyte interface (SEI) layer formed with M = Mn(IV) at voltages V > 4.3 V are Li-permeable. The disproportionation reaction 3Cr(IV) = 2Cr(III) + Cr(VI) contributes to the loss of capacity in Li[CrMn]O 4 - With M = Ti(IV), reversible charge/discharge curves were not obtained between 3.5 and 4.9 V (vs Li + /Li). The cathode Fermi energy E FC is lowered by about 0.2 eV on charging from M = Mn(IV) to M = Ti(IV), but this lowering is not sufficient to cause O 2 evolution from the spinel on charge with M = Ti(IV). Whereas Li-permeable SEI layers are formed with M = Mn(IV), we conclude that the SEI layers formed with M = Ti(IV) are Li-blocking. The SEI layer may be a Li-poor, Ti-rich phase formed at the surface of the cathode particle during charge rather than an SEI layer formed by a reaction with the electrolyte.

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca2+

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Rate-dependent phase transitions in Li2FeSiO4 cathode nanocrystals

Nanostructured lithium metal orthosilicate materials hold a lot of promise as next generation cathodes but their full potential realization is hampered by complex crystal and electrochemical behavior. In this work Li2FeSiO4 crystals are synthesized using organic-assisted precipitation method. By varying the annealing temperature different structures are obtained, namely the monoclinic phase at 400°C, the orthorhombic phase at 900°C, and a mixed phase at 700°C. The three Li2FeSiO4 crystal phases exhibit totally different charge/discharge profiles upon delithiation/lithiation. Thus the 400°C monoclinic nanocrystals exhibit initially one Li extraction via typical solid solution reaction, while the 900°C orthorhombic crystals are characterized by unacceptably high cell polarization. In the meantime the mixed phase Li2FeSiO4 crystals reveal a mixed cycling profile. We have found that the monoclinic nanocrystals undergo phase transition to orthorhombic structure resulting in significant progressive deterioration of the materials Li storage capability. By contrast, we discovered when the monoclinic nanocrystals are cycled initially at higher rate (C/20) and subsequently subjected to low rate (C/50) cycling the materials intercalation performance is stabilized. The discovered rate-dependent electrochemically-induced phase transition and stabilization of lithium metal silicate structure provides a novel and potentially rewarding avenue towards the development of high capacity Li-ion cathodes.

Investigation of the reaction mechanism of lithium sulfur batteries in different electrolyte systems by in situ Raman spectroscopy and in situ X-ray diffraction

Lithium–sulfur batteries are of great interest owing to their high theoretical capacity of 1675 mA h g−1 and low cost. Their discharge mechanism is complicated and it is still a controversial issue. In the present work, in situ Raman spectroscopy is employed to investigate the poly-sulfide species in the sulfur cathode and in the electrolyte during the cycling of Li–S batteries. The aim is to understand the discharge mechanism and the influence of the electrolyte on the dissolution of sulfur and poly-sulfides. S8n− is identified as the main species in the high voltage plateau of discharge together with cycloocta S8, in the cell using 0.5 mol L−1 LiTFSI–PY13–FSI as the electrolyte. S42−, S22− and S2− are detected soon after the low voltage plateau is reached. A discharge mechanism in the PY13–FSI is proposed based on the identified species which provides important information for improving and designing cathodes. Electrolytes of 0.5 mol L−1 LiTFSI–PY13–FSI and 1 mol L−1 LiTFSI–DOL–DME are used in studying the dissolution of sulfur and poly-sulfides. The results demonstrate that the same poly-sulfide species are present in the two electrolytes. However, the rates of poly-sulfide formation and diffusion to the anode are slow in the ionic liquid compared to those in the ether-based electrolyte due to different ionic mobilities of various species in the two electrolytes. These differences are evidenced by the observation of poly-sulfide species in the DOL–DME from the very beginning of cell assembly even before starting the discharge whereas their appearances, in the ionic liquid, are delayed and only found at the end of the high voltage plateau. Notably, the soluble elemental sulfur is clearly observed in the ionic liquid electrolyte during the first discharge in the high voltage region, which is very different from the DOL–DME system where the elemental sulfur is quickly reduced to poly-sulfides due to self-discharge reactions. In addition, the elemental sulfur is also detected near the lithium anode in DOL–DME at the end of charge, for the first time to our knowledge, which suggests that the degradation of lithium metal is caused by the multiple reactions of the lithium metal surface with soluble poly-sulfides and/or elemental sulfur.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Electrochemical intercalation of lithium into carbons using a solid polymer electrolyte

Abstract A study of the electrochemical performance of carbon materials from different types was carried out on true solid polymer-based poly(ethylene oxide) (PEO) with LiTFSI for application as the negative electrode in lithium ion solid-state batteries (LISSBs) at 60 °C. The reversible and irreversible capacity depend strongly on the crystallinity, the form of carbon and the impurities. A comparison of particle versus fiber was done when we investigated the charge/discharge characteristics with different current densities. The galvanostatic curves show high reversibility of the lithium—carbon in solid polymer electrolyte. The kinetics of electrochemical intercalation of lithium into carbon was studied by impedance spectroscopy especially for evaluating the diffusion coefficient in different origins of carbon. The degree of ionization of lithium was investigated by using solid-state 7 Li nuclear magnetic resonance spectroscopy when the electrode is fully intercalated or doped down to 0 V. The chemical shift of 7 Li NMR in lithium intercalation or doping in the carbons was classified in two ranges, 42 ppm and 9 ppm. 7 Li NMR suggests the carbon with a 42 ppm range is the best choice for LISSBs.