12 research outputs found
Chemically Prepared Li0.6FePO4 Solid Solution as a Vehicle for Studying Phase Separation Kinetics in Li-ion Battery Materials
The commercial success of LiFePO4 in high-power Li-ion batteries is strongly related to its unique ultrahigh-rate charge/discharge performance that permits full charge in less than a minute. Since Li1–xFePO4 (0.05 ≤ x ≤ 0.95) separates into two phases with poor electronic and ionic conduction, this raises questions regarding the structural dynamics of phase separation. In this paper, the transformation of metastable solid solution Li0.6FePO4 into a phase-separated material is studied by analysis of the local and bulk structure. 6Li MAS NMR is used to probe the immediate environment where proximity to Fe3+ results in a significant shift in resonance frequency. Conversely, time-resolved X-ray diffraction (XRD) measurements reveal the transformation kinetics at the unit cell scale. The XRD showed no preferential relaxation along the a, b, and c crystal axes, consistent with the absence of a phase boundary perpendicular to the fast diffusion b axis. Key to the analysis is the preparation of the solid solution, which yields phase-pure samples exhibiting no evidence of the thermodynamically stable LiFePO4 or FePO4 phases. Long-term measurement indicated that after 263 days under an argon atmosphere these samples still exhibited a solid solution fraction > 40%. However, in the presence of an electrolyte, phase separation is significantly more rapid. The results presented support Li et al. model [Nat. Mater.2018, 17, 915], where vehicular lithium transport at the surface determines the rate of phase separation and offers a methodology for studying high-energy-density LiMPO4 systems (M = transition metal) that currently are limited by poor high-rate performance
In situ-formed nitrogen-doped carbon/silicon-based materials as negative electrodes for lithium-ion batteries
The development of negative electrode materials with better performance than those currently used in Li-ion technology has been a major focus of recent battery research. Here, we report the synthesis and electrochem-ical evaluation of in situ-formed nitrogen-doped carbon/SiOC. The materials were synthesized by a sol-gel pro-cess using 3-(aminopropyl)triethoxysilane (APTES), sodium citrate and glycerol. The electrochemical performance of pyrolyzed materials was studied using poly(acrylic acid) binder and commercial organic elec-trolyte. Our reported approach enables changes in both the amount of nitrogen and the morphology as a func-tion of the molar ratio of APTES:citrate and reaction time. Spherical-shaped NC/SiOC composite electrodes deliver a delithiation capacity of 622 mAh/g at 0.1 A/g and an initial coulombic efficiency of-63%, while in the large bulk material, respective values of 367 mAh/g and-55% were obtained. After 1000 charge/dis-charge cycles at 1.6 A/g, the latter material exhibits 98% of the initial capacity once it returned to lower cur-rent cycling. Overall, our results indicate that NC/SiOC materials are quite promising for electrochemical applications since both their large capacity and stability demonstrate superior performance compared to tradi-tional graphite. Moreover, our synthesis is simple and, more importantly, environmentally friendly chemicals, such as sodium citrate and glycerol, are used.Peer reviewe
Diazonium-based anchoring of PEDOT on Pt/Ir electrodes via diazonium chemistry
Conducting polymers, specifically poly (3,4-ethylenedioxythiophene) (PEDOT), have recently been coated onto Pt/Ir electrodes intended for neural applications, such as deep brain stimulation (DBS). This modification reduces impedance, increases biocompatibility, and increases electrochemically active surface area. However, direct electropolymerization of PEDOT onto a metallic surface results in physically adsorbed films that suffer from poor adhesion, precluding their use in applications requiring in vivo functionality (i.e. DBS treatment). In this work, we propose a new attachment strategy, whereby PEDOT is covalently attached to an electrode surface through an intermediate phenylthiophene layer, deposited by electrochemical reduction of a diazonium salt. Our electrodes retain their electrochemical performance after more than 1000 redox cycles, whereas physically adsorbed films begin to delaminate after only 40 cycles. Additionally, covalently attached PEDOT maintained strong adhesion even after 10 minutes of ultrasonication
(vs. 10 s for physically adsorbed films), confirming its suitability for long-term implantation in the brain. The simple two-step covalent attachment strategy proposed here is particularly useful for neural applications and could also be adapted to introduce other functionalities on the conducting surface
Interpreting Lithium Batteries Discharge Curves for Easy Identification of the Origin of Performance Limitations
International audienceA simple method is proposed to interpret limited discharge performances of composite positive electrodes in terms of charge transport in the electrolyte vs. charge transport in the active material
Polyphenylene sulfide (PPS) composites reinforced with recycled carbon fiber
Recycled carbon fibers were reclaimed by commercial scale pyrolysis from carbon fiber reinforced thermoset composite waste generated by the aerospace industry. The mechanical and physical properties of the reclaimed carbon fibers were shown to be comparable to those of aerospace grade virgin carbon fibers. The recycled carbon fibers were integrated into a polyphenylene sulfide (PPS) thermoplastic resin by twin screw compounding followed by injection molding. Composites containing 20. wt.% and 40. wt.% recycled carbon fibers were produced. Overall, the fibers were found to be uniformly dispersed in the polymeric matrix. The tensile, flexural and impact properties of the composites were evaluated. The recycled carbon fiber reinforced PPS composites exhibited comparable mechanical properties to equivalent compounds produced using industrial grades of short virgin carbon fiber. In addition, thermogravimetric analysis showed that the introduction of recycled carbon fibers was not detrimental to the inherent thermal stability of PPS.Peer reviewed: YesNRC publication: Ye
Effect of Substrate Permeability on Scanning Ion Conductance Microscopy: Uncertainty in Tip–Substrate Separation and Determination of Ionic Conductivity
Operando Tracking of Solution-Phase Concentration Profiles in Li-Ion Battery Positive Electrodes Using Xray Fluorescence
Structural Transformation of LiFePO<sub>4</sub> during Ultrafast Delithiation
The
prolific lithium battery electrode material lithium iron phosphate
(LiFePO<sub>4</sub>) stores and releases lithium ions by undergoing
a crystallographic phase change. Nevertheless, it performs unexpectedly
well at high rate and exhibits good cycling stability. We investigate
here the ultrafast charging reaction to resolve the underlying mechanism
while avoiding the limitations of prevailing electrochemical methods
by using a gaseous oxidant to deintercalate lithium from the LiFePO<sub>4</sub> structure. Oxidizing LiFePO<sub>4</sub> with nitrogen dioxide
gas reveals structural changes through in situ synchrotron X-ray diffraction
and electronic changes through in situ UV/vis reflectance spectroscopy.
This study clearly shows that ultrahigh rates reaching 100% state
of charge in 10 s does not lead to a particle-wide union of the <i>olivine</i> and <i>heterosite</i> structures. An extensive
solid solution phase is therefore <i>not</i> a prerequisite
for ultrafast charge/discharge
Exploring the Synergistic Effects of Dual‐Layer Electrodes for High Power Li‐Ion Batteries
Abstract The electrification of the transport sector has created an increasing demand for lithium‐ion batteries that can provide high power intermittently while maintaining a high energy density. Given the difficulty in designing a single redox material with both high power and energy density, electrodes based on composites of several electroactive materials optimized for power or capacity are being studied extensively. Among others, fast‐charging LiFePO4 and high energy Li(NixMnyCoz)O2 are commonly employed in industrial cell manufacturing. This study focuses on comparing different approaches to combining these two active materials into a single electrode. These arrangements were compared using standard electrochemical (dis)charge procedures and using synchrotron X‐ray fluorescence to identify variations in solution concentration gradient formation. The electrochemical performance of the layered electrodes with the high‐power material on top is found to be enhanced relative to its blended electrode counterpart when (dis)charged at the same specific currents. These findings highlight dual‐layer lithium‐ion batteries as an inexpensive way of increasing energy and power density of lithium‐ion batteries as well as a model system to study and exploit the synergistic effects of blended electrodes