Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries.
ABSTRACT: The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO₄ positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAh·g-1 for the positive electrode and 305 mAh·g-1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g-1 and the negative electrode with 160 mAh·g-1 at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries.
Project description:Silicon is an attractive anode material for lithium-ion batteries. However, silicon anodes have the issue of volume change, which causes pulverization and subsequently rapid capacity fade. Herein, we report organic binder and conducting diluent-free silicon-carbon 3D electrodes as anodes for lithium-ion batteries, where we replace the conventional copper (Cu) foil current collector with highly conductive carbon fibers (CFs) of 5-10 ?m in diameter. We demonstrate here the petroleum pitch (P-pitch) which adequately coat between the CFs and Si-nanoparticles (NPs) between 700 and 1000 °C under argon atmosphere and forms uniform continuous layer of 6-14 nm thick coating along the exterior surfaces of Si-NPs and 3D CFs. The electrodes fabricate at 1000 °C deliver capacities in excess of 2000 mA h g-1 at C/10 and about 1000 mA h g-1 at 5 C rate for 250 cycles in half-cell configuration. Synergistic effect of carbon coating and 3D CF electrode architecture at 1000 °C improve the efficiency of the Si-C composite during long cycling. Full cells using Si-carbon composite electrode and Li1.2Ni0.15Mn0.55Co0.1O2-based cathode show high open-circuit voltage of >4 V and energy density of >500 W h kg-1. Replacement of organic binder and copper current collector by high-temperature binder P-pitch and CFs further enhances energy density per unit area of the electrode. It is believed that the study will open a new realm of possibility for the development of Li-ion cell having almost double the energy density of currently available Li-ion batteries that is suitable for electric vehicles.
Project description:We report a simple one-step hydrothermal strategy for the fabrication of a C-MoS2/rGO composite with both large surface area and high porosity for the use as advanced electrode material in lithium-sulfur batteries. Double modified defect-rich MoS2 nanosheets are successfully prepared by introducing reduced graphene oxide (rGO) and amorphous carbon. The conductibility of the cathodes can be improved through the combination of amorphous carbon and rGO, which could also limit the dissolution of polysulfides. After annealing at different temperatures, it is found that the C-MoS2/rGO-6-S composite annealed at 600 °C yields a noticeably enhanced performance of lithium-sulfur batteries, with a high specific capacity of 572 mAh·g-1 at 0.2C after 550 cycles, and 551 mAh·g-1 even at 2C, much better than that of MoS2-S nanosheets (249 mAh·g-1 and 149 mAh·g-1) and C-MoS2/rGO-S composites (334 mAh·g-1 and 382 mAh·g-1). Our intended electrode design protocol and annealing process may pave the way for the construction of other high-performance metal disulfide electrodes for electrochemical energy storage.
Project description:This work presents an alternative method for fabricating Li-ion electrodes in which the use of aluminum/copper current collectors and expensive binders is avoided. Low-cost natural cellulose fibers with a 2-mm length are employed as binder and support for the electrode. The objective of this method is to eliminate the use of heavy and inactive current collector foils as substrates and to replace conventional costly binders with cellulose fibers. Moreover, no harmful solvents, such as N-methylpyrrolidone, are employed for film fabrication. Water-soluble carbons are also utilized to reduce the preparation time and to achieve a better repartition of carbon in the electrode, thus improving the electrochemical performance. Flexible and resistant LiFePO4 (LFP), Li4Ti5O12 (LTO), organic 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), and graphite electrodes are obtained with active mass loadings similar to those obtained by the current casting method. The initial discharge capacity of approximately 130 mAh·g-1 at 2?C is obtained for an LFP/LTO paper battery with an approximately 91.6% capacity retention after 1000 cycles. An all-organic prelithiated PTCDA/graphite cell without a transition metal is prepared and electrochemically tested. It is one of the first self-standing batteries that is composed of organic redox active molecules and biodegradable components reported in literature.
Project description:Greater specific energy densities in lithium-ion batteries can be achieved by using three-dimensional (3D) porous current collectors, which allow for greater areal mass loadings of the electroactive material. In this paper, we present the use of embroidered current collectors for the preparation of thick, pouch-type Li-ion batteries. Experiments were performed on LiFePO<sub>4</sub> (LFP) water-based slurries using styrene-butadiene rubber (SBR) as binder and sodium carboxymethyl cellulose (CMC) as thickener, and formulations of different rheological characteristics were investigated. The electrochemical performance (cyclic voltammetry, rate capability) and morphological characteristics of the LFP half-pouch cells (X-ray micro computed tomography and scanning electron microscopy) were compared between the formulations. An optimum electrode formulation was identified, and a mechanism is proposed to explain differences between the formulations. With the optimum electrode formulation, 350?µm casted electrodes with high mechanical stability were achieved. Electrodes exhibited 4-6 times greater areal mass loadings (4-6 mAh cm<sup>-2</sup>) and 50% greater electroactive material weight than with foils. In tests of half- and full-pouch embroidered cells, a 50% capacity utilization at 1C-rate and 11% at 2C-rate were observed, with a full recovery at C/5-rate. The cycling stability was also maintained over 55 cycles.
Project description:The commercial uptake of lithium-sulfur (Li-S) batteries is undermined by their rapid performance decay and short cycle life. These problems originate from the dissolution of lithium polysulfide in liquid electrolytes, causing charge and active material to shuttle between electrodes. The dynamics of intractable polysulfide migration at different length scales often tend to escape the probing ability of many analytical techniques. Spatial and temporal visualization of Li in Li-S electrodes and direct mechanistic understanding of how polysulfides are regulated across Li-S batteries starting from current collector and active layer coating to electrode-electrolyte interface are still lacking. To address this we employ neutron depth profiling across Li-S electrodes using the naturally occurring isotope, 6Li, which yields direct spatial information on Li-S electrochemistry. Using three types of Li-S electrodes, namely, carbon-sulfur, carbon-sulfur with 10% lithium titanium oxide (LTO), and carbon-sulfur with LTO membrane, we provide direct evidence for the migration, adsorption, and confinement of polysulfides in Li-S cells at work. Our findings further provide insights into the dynamics of polysulfide dissolution and re-utilization in relation to Li-S battery capacity and longevity to aid rational electrode designs toward high-energy, safe, and low-cost batteries.
Project description:The conventional polyvinylidene fluoride (PVDF) binder works well with the graphite anode, but when combined with silicon in composites to increase the energy density of Li-ion batteries, it results in severe capacity fade. Herein, by using scanning electron microscopy and energy-dispersive X-ray spectroscopy analyses, we reveal that this failure stems from the loss of connectivity between the silicon (or its agglomerates), graphite, and PVDF binder because of the mechanical stresses experienced during battery cycling. More importantly, we reveal for the first time that the PVDF binder undergoes chemical decomposition during the cycling of not only the composite but also the Si-only or even graphite-only electrodes despite the excellent battery performance of the latter. Through X-ray photoemission electron microscopy and X-ray photoelectron spectroscopy techniques, LiF was identified as the predominant decomposition product. We show that the distribution of LiF in the electrodes due to the differences in the interactions between PVDF and either Si or graphite could correlate with the performance of the battery. This study shows that the most suitable binder for the composite electrode is a polymer with a good chemical interaction with both graphite and silicon.
Project description:Silicon, while suffering from major degradation issues, has been recognized as a next promising material to replace currently used graphite in the anodes of Li-ion batteries. Several pathways to mitigate the capacity fading of silicon has been proposed, including optimization of the electrode composition. Within the present work we evaluated different binder formulations to improve the long-term performance of the Li-ion batteries' anodes based on industrial grade silicon (Si) which is typically characterized by a particle sizes ranging from 100 nm to 5.5 microns. The decrease of pH in a binder formulation was found to detrimental for the cycling performance of Si due to enhanced formation of an ester-type bonding between the carboxylic group of the binder and hydroxyl group on the Si surface as well as cross-linking. Furthermore, the present work was focused on the use of the industrial grade Si with very high loading of Si material (up to 80% by weight) to better highlight the effects of the surface chemistry of Si and its influence on the performance of Si-based anodes in Li-ion batteries. The tested system allowed to establish a pseudo self-healing effect that manifests itself through the restoration of the anode capacity by approximately 25% and initiates after approximately 20 cycles. The stabilization of the capacity is attributed to self-limiting lithiation process. Such effect is closely related to SEI formation and transport properties of an electrode prepared from silicon of industrial grade.
Project description:We report a facile method to prepare a nanoarchitectured lithium manganate/graphene (LMO/G) hybrid as a positive electrode for Li-ion batteries. The Mn(2)O(3)/graphene hybrid is synthesized by exfoliation of graphene sheets and deposition of Mn(2)O(3) in a one-step electrochemical process, which is followed by lithiation in a molten salt reaction. There are several advantages of using the LMO/G as cathodes in Li-ion batteries: (1) the LMO/G electrode shows high specific capacities at high gravimetric current densities with excellent cycling stability, e.g., 84 mAh·g(-1) during the 500th cycle at a discharge current density of 5625 mA·g(-1) (~38.01 C capacity rating) in the voltage window of 3-4.5 V; (2) the LMO/G hybrid can buffer the Jahn-Teller effect, which depicts excellent Li storage properties at high current densities within a wider voltage window of 2-4.5 V, e.g., 93 mAh·g(-1) during the 300th cycle at a discharge current density of 5625 mA·g(-1) (~38.01 C). The wider operation voltage window can lead to increased theoretical capacity, e.g., 148 mAh·g(-1) between 3 and 4.5 V and 296 mAh·g(-1) between 2 and 4.5 V; (3) more importantly, it is found that the attachment of LMO onto graphene can help to reduce the dissolution of Mn(2+) into the electrolyte, as indicated by the inductively coupled plasma (ICP) measurements, and which is mainly attributed to the large specific surface area of the graphene sheets.
Project description:Lithium-ion batteries (LIBs) are generally constructed by lithium-including positive electrode materials, such as LiCoO2, and lithium-free negative electrode materials, such as graphite. Recently, lithium-free positive electrode materials, such as sulfur, are gathering great attention from their very high capacities, thereby significantly increasing the energy density of LIBs. Though the lithium-free materials need to be combined with lithium-containing negative electrode materials, the latter has not been well developed yet. In this work, the feasibility of Li-rich Li-Si alloy is examined as a lithium-containing negative electrode material. Li-rich Li-Si alloy is prepared by the melt-solidification of Li and Si metals with the composition of Li21Si5. By repeating delithiation/lithiation cycles, Li-Si particles turn into porous structure, whereas the original particle size remains unchanged. Since Li-Si is free from severe constriction/expansion upon delithiation/lithiation, it shows much better cyclability than Si. The feasibility of the Li-Si alloy is further examined by constructing a full-cell together with a lithium-free positive electrode. Though Li-Si alloy is too active to be mixed with binder polymers, the coating with carbon-black powder by physical mixing is found to prevent the undesirable reactions of Li-Si alloy with binder polymers, and thus enables the construction of a more practical electrochemical cell.
Project description:The past decades have witnessed the development of many technologies based on nanoionics, especially lithium-ion batteries (LIBs). Now there is an urgent need for developing LIBs with good high-rate capability and high power. LIBs with nanostructured electrodes show great potentials for achieving such goals. However, the nature of Li-ion transport behaviors within the nanostructured electrodes is not well clarified yet. Here, Li-ion transport behaviors in Li(x)CoO(2) nanograins are investigated by employing conductive atomic force microscopy (C-AFM) technique to study the local Li-ion diffusion induced conductance change behaviors with a spatial resolution of ~10 nm. It is found that grain boundary has a low Li-ion diffusion energy barrier and provides a fast Li-ion diffusion pathway, which is also confirmed by our first principles calculation. This information provides important guidelines for designing high performance LIBs from a point view of optimizing the electrode material microstructures and the development of nanoionics.